CA1338334C - Propylene isoblock polymer and process for its manufacture - Google Patents
Propylene isoblock polymer and process for its manufactureInfo
- Publication number
- CA1338334C CA1338334C CA000606883A CA606883A CA1338334C CA 1338334 C CA1338334 C CA 1338334C CA 000606883 A CA000606883 A CA 000606883A CA 606883 A CA606883 A CA 606883A CA 1338334 C CA1338334 C CA 1338334C
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- propylene
- isoblock
- metallocene
- bis
- 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.)
- Expired - Fee Related
Links
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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 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
- C08F4/65927—Component covered by group C08F4/64 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
Abstract
Propylene isoblock polymers with 0.5 to 10 mol%, based on the total polymer, of randomly distributed ethylene units and with a narrow molecular weight distribution are ob-tained when propylene is polymerized using a catalyst consisting of a chiral metallocene, containing bridges, of formula I:
Description
Description 05 Propylene i~oblock polymer ~nd process for its manu-facture The invention relates to a propylene isoblock polymer with long isotactic seguences and randomly di~tributed ethylene units and to a process for its manufacture.
It is known that polypropylene exists in various struc-tural isomers:
(a) highly isotactic polypropylene in whose molecular chains almost all tertiary C atoms have the same configuration, (b) isotactic stereoblock PP in whose molecular chains isotactic blocks of opposite configuration alternate regularly with one another, (c) syndiotactic polypropylene in whose molecular chains every other tertiary C atom ha~ the same configura-tion, (d) atactic polypropylene in whose molecular chains the tertiary C atoms have a random configuration, and (e) atactic-isotactic stereoblock PP in whose molecular chains isotactic and atactic blocks alternate with one another.
A process for the manufacture of isotactic stereoblock polymers is known in which propylene is polymerized with the aid of a metallocene of a metal of group IVb, Vb or VIb of the periodic table (q.v. US patent 4,522,982).
This metallocene is a mono-, di- or tri-cyclopentadienyl or substituted cyclopentadienyl compound of a metal, es-pecially titanium. An aluminoxane is used a~ cocatalyst.
However, the titA~ocenes which are preferably u~ed do not have sufficient heat stability in dilute solution to be usable in an industrial process. Moreo~er, in this process, products with longer isotactic seguences (n greater than 6) are only obtained at very low temperature 05 (-60C). Finally, the cocatalysts must be used in com-paratively high concentration in order to achieve an adequate catalytic yield, 80 the catalyst residue~ con-tained in the polymer product have to be removed in a separate purification step.
It is further known that stereoblock polymers of 1-ole-fins with long isotactic sequences can be obtained at indu~trially favorable polymerization temperatures by means of a catalyst con~isting of a metallocene compound lS with cyclopentadienyl radicals substituted by chiral groups, and of an aluminoxane (q.v. European patent ap-plication A 269987).
It is further known that stereoblock polymers of 1-ole-fin~ with a broad monomodal or multimodal molecular weight distribution can be obtained when 1-olefins are polymerized using a catalyst consisting of a chiral metallocene containing bridges and of an aluminoxane (g.v. European patent application A 269986). The polymers are particularly suitable for the production of transparent sheets.
It is also known that when a catalyst based on bis-cyclo-pentadienyl compounds of zirconium and on an aluminoxane is used in the polymerization of propylene, only stactic polymer is obtained (g.v. European patent application A
69951).
~inally, highly isotactic poly~,o~lene can be manufac-tured by mean~ of ~oluble stereorigid chir~l zirconium compounds (g.v. European patent application A 185 918).
A polymerization process has been found in which a poly-mer of regular molecular structure and high molecular - _ 3 ~ 338334 weight is obtained in high yield at industrially favo-rable process temperatures.
The invention thus relates to an isoblock polymer of 05 propylene with molecular chain~ containing isotactic sequences which are separated from one another in each ca~e by one monomer unit of opposite configuration, and 0.5 to 10 mol%, based on the total poly~er, of randomly distributed ethylene units, and with a seguence length of 3 to 50 monomer units.
The invention further relates to a proces~ for the ~anu-facture of the above-mentioned i~oblock polymer by the polymerization of propylene at a temperature of -60 to 100C and a pres~ure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst consisting of a metallocene and an aluminoxane, wherein the metallocene is a compound of formula I:
R3--~--R4 R 1 R ~\R 7 26 R~ 5 (I), in which M1 is ~ metal of group IVb, Vb or VIb of the periodic table, R1 and R2 are identical or different and are a hydrogen atom, a C1-Clo-alkyl group, a C1-C~o-alkoxy group, a C~-C1o-aryl group, a Cs-Clo-aryloxy group, a C2-C1o-alkenyl group, a C7-C~o-arylalkyl group, a C7-C40-alkylaryl group, a C~-C~o-srylAl~enyl group or a halo-gen atom, i 338334 .
R3, R~, R~ and R~ are identicsl or different and are 8hydrogen atom, 8 halogen atom, a C1-Clo-alkyl group, 05 -NR82, -SRB, ~OSirR83rl1, ~SirR83rl1 or -PR8z, in which R~ i8 a halogen atom or a C1-C1o-alkyl group, or pairs of ad~acent radicals R3, R~, R~ and R~ form a ring with the C atoms to which they are bonded, and R7 i8 _9 ~9 ~9 -9 R9 _~2 (CR9RlO)m-~ _~2 o ,~2 , _~2_(CR9RlO)m-M2-, ~,10 R10 ,~10 ?~10 ~10 _9 o-M2- (CR9R10)m--~10 -Sn-, -S-S-, -S0-S0-, -S0-0-S0-, BR9-BR9-BR9--9 qg -PR9-0-PR9-, -~-0-P-, -N=~-NR9- or -N=P-NR~-, O O O
in which R~ and R10 are identical or different and are a hydrogen stom, a halogen atom, a C1-C1o-alkyl group, a C -C1O-fluoroslkyl group, a C~-Clo-aryl group, a C~-C1o-fluoroaryl group, a C1-C~o-alkoxy group, a Cz-C~o-alkenyl group, a C7-C~o-arylalkyl group, a C8-c~o-arylalkenyl group or a C7-C~o-alkylaryl group, or R~
and R10 form a ring with the atoms to which they are bonded, M2 i8 sil~con, germanium or tin and 1~1 i8 zero or 1.
The invention further relates to the use of the isoblock polymer according to the present invention for the manufacture of polymer mixtures, and for the manufacture of polypropylene blends.
The isobloc~ polymer according to the invention i5 a propylene polymoer.
The molecular chains of this polymer contain isotactic sequences which are separated from one another in each ca~e by one monomer unit of opposite configuration. The molecular chains preferably consist of isotactic se-05 quences which are separated from one another in each caseby one monomer unit of opposite configuration. The iso-tactic sequences have a length of 3 to 50 monomer units.
The molecular chains simultaneously contain randomly dis-tributed ethylene units which are preferably located in the isotactic sequences and have been formed by the re-arrangement of propylene during polymerization. The ethylene units can be detected by 13C NMR spectroscopy (q.v. Soga et al., Makrom. Chem. Rap. Comm. R, 305-310 (1987)). They are in an amount of 0.5 to 10, preferably 3 to 5 mol%, based on the total polymer.
A~ a consequence of this steric structure, the isoblock polymers according to the invention are amorphous or partly crystalline according to the molecular weight and the length of the isotactic ~equences. Depending on the crystallinity, the polymers are obtained as granular powders or as compact masses. The partly crystalline isoblock polymers have a low melting point by comparison with isotactic polymers. Isoblock polymers possess rubber-like properties.
The catalyst to be used for the process according to the invention consists of a metallocene compound of formula I
and an alllm;noxane. In formula I:
R ~
35 ~7 (I).
6 l 338334 M1 is a metal of group IVb, Vb or VIb of the periodic table, for example titanium, zirconium, hafnium, vana-dium, niobium, tantalum, chromium, molybdenum or tungs-ten, preferably zirconium or hafnium.
Rl and R2 are identical or different and are a hydrogen atom, a C1-Clo-, preferably C1-C3-alkyl group, a Cl-Clo-, preferably Cl-C3-alkoxy group, a C6-Clo-, preferably C~-Cs-aryl group, a C~-Clo-, preferably C6-Cs-aryloxy group, a C2-Clo-, preferably C2-C~-alkenyl group, a C7-C~o-, preferably C7-Clo-arylalkyl group, a C7-C40-, preferably C7-Cl2-alkylaryl group, a C8-C40-, preferably C8-C12-arylalkenyl group or a halogen atom, preferably chlorine.
R3, R4, R6 and R8 are identical or different, preferably different, and are a hydrogen atom, a halogen atom, pre-ferably a fluorine, chlorine or bromine atom, a Cl-Clo-, preferably Cl-C3-alkyl group, -NR82, -SRB, ~OSirRB3rll~
~SirR83~ll or -PRB2, in which R8 i8 a halogen atom, pre-ferably a chlorine atom, or a Cl-Clo-, preferably Cl-C3-alkyl group, or pairs of adjacent radicals R3, R~, R6 and Rfi form a ring with the C atoms to which they are bonded.
R7 is -M2-(CR9R1O)m-~ -M2-0-~2-~ _~2_(CR9R1O)m-M2-, -o-M2-(CR9R1O)m--Sn-, -5-S-, -S0-S0-, -50-0-S-,-BR9-BR9-BR9--PR9-0-PR9-, -P-0-P-, -N=P-NR9- or -N=P-NR~-, in which R~ and Rl are identical or different and are a hydrogen atom, a halogen atom, a C1-C1o-alkyl group, preferably a Cl-C~-alkyl group and especially a methyl group, a C1-C1o-fluoroalkyl group, preferably a CF3 group, a C6-C1o-, preferably C~-C~-aryl group, a C6-C1o-fluoroaryl group, preferably a hexafluorophenyl 05 group, a Cl-C1o-, preferably C1-C4-alkoxy group, es-pecially a methoxy group, a C2-C1o-, preferably C2-C~-alkenyl group, a C7-C~o-, preferably C7-C1o-arylalkyl group, a C8-C~o-, preferably Cs-C12-arylalkenyl group or a C7-C40-, preferably C7-Cl2-alkylaryl group, or R~
and R10 form a ring together with the atom~ to which they are bonded.
M2 is Si, Ge or Sn.
lS R7 is preferably =SiR~Rl0-SiR~R10-.
m is zero or 1.
The metallocenes described above can be prepared accor-ding to the following reaction scheme:
H2Ra ~ ButylLi ~ HRaLi \ X - R7 - X~ HRa _ R7 - RbH
25 H2Rb ~ ButylLi ~ HRbLi '~
~X = Cl, ~r,~, 0-1osyl, HR~ = ~ ,HR
HRa R7 - RbH ~ 2 8utylLi ~ LiRa _ R7 - RbLi / ~ " , Cl LiRa _ R7 - RbLi MlCl~ R7 ~ ~
\ 'b Cl ~ 8 l 338334 ~a ~a ,Ra 05 R7 l~\ R1Li~ R7 Y~ R2~i> R7 \ ' It i~ especially preferred to use bis(indenyl)bis(di-methylsilyl)hafnium dichloride (= 1) and bis(indenyl)bis-(dimethylsilyl)zirconium dichloride (= 2) as the metal-locene compounds.
The activator is an aluminoxane of formula (II):
Rll Rll Rll I
Al - 0 - Al - 0 - Al ~ \ R
Rll _n ll (II) for the linear type and/or of formula (III):
Rll I
- Al - 0 -(III) _n+2 for the cyclic type. In these formulae, Rll is a C1-C~-alkyl group, preferably methyl, ethyl or isobutyl, in particular methyl, and n is an integer from 2 to 50, pre-ferably 10 to 40. The exact structure of the al~ noxAne i8 not certain, however, 80 formulae II and III are only approximate formulae.
The aluminoxane can be prepared in a variety of ways.
One possibility i~ carefully to add water to a dilute solution of an aluminum trialkyl, the aluminum trialkyl 05 solution and the water each being introduced in small portion~ into a larger amount of an inert solvent and the evolution of ga~ being allowed to finish between succes-sive addition~.
In another proce~, finely powdered copper sulfate penta-hydrate is su~pended in toluene and, in a glass flask, aluminum trialkyl is added, under inert gas at about -20C, in an amount such that about 1 mol of CuS04 5H20 i~ available for every 4 A1 atoms. After slow hydrolysis with the elimination of alkane, the reaction mixture is left for 24 to 48 hours at room temperature, during which time it must be cooled, if necessary, to prevent the tem-perature from rising above 30C. The al~lm~noYAne dis-solved in the toluene is then isolated from the copper sulfate by filtration and the solution i8 concentrated under vacuum. It is assumed that, in this preparative process, the low-molecular aluminoxanes condense to form higher-molecular oligomers with the elimination of alu-minum trialkyl.
Furthermore, al~l~inoxanes are obtained when aluminum tri-alkyl, preferably aluminum trimethyl, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted, at a temperature of -20 to 100C, with aluminum salts containing water of crystallization, preferably aluminum sulfate. The volume ratio of solvent to aluminum alkyl used i8 1: 1 to 50:1 - preferably S:1 -and the reaction time, which can be monitored by ~eans of the alkane eliminated, is 1 to 200 hours - preferably 10 to 40 hours.
Aluminum salts containing water of crystallization which are used in particular are those with a hiBh content of water of crystallization. Aluminum sulfate hydrates are - lo i 338334 -especially preferred, in particular the compounds Al2(S0~) 3 16H20 and Al2(S0~) 3 ~ 18H20 with the especially high contents of water of crystallization of 16 and 18 mol of H20/mol of Al2(S04)3 respectively.
Another variant for the preparation of aluminoxanes con-sists in dissolving aluminum trial~yl, preferably alu-minum trimethyl, in the suspending agent, preferably in the liguid monomer or in heptane or toluene, previously placed in the polymerization kettle, and then reacting the aluminum compound with water.
There are other processes for the preparation of alumin-oxanes which can be used in addition to those described above.
Before it is u~ed in the polymerization reaction, the metallocene can be preactivated with an alum~noxane of formula (II) and/or (III), which markedly increases the polymerization activity.
The preactivation of the transition metal compound i8 carried out in solution, the metallocene preferably being dis~olved in a solution of the al~inoYA~e in an inert hydrocarbon. An aliphatic or aromatic hydrocarbon is suitable for this purpose. Toluene is preferably used.
The concentration of the al~ nox~ne in the solution is in the range from approx. 1% by weight to the saturation limit, preferably from 6 to 30% by weight, based in each case on the total solution. The metallocene can be used in the same concentration, although it is preferably uset in an amount of 10-~ - 1 mol per mol of alum~nox~ne~ The preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. The reaction temperature is -78C to 100C, preferably 0 to 70C.
The catalyst to be used according to the invention iB
employed for the polymerization of 1-olefins of the formula R-CH=CH2, in which R iB an alkyl radical having 1 to 28 C atoms, preferably 1 to 10 C atom~, in particular one C atom, for example propylene, but-1-ene, hex-1-ene, 4-methylpent-1-ene or oct-1-ene. Propylene i8 especially 05 preferred.
The polymerization is carried out in known manner in solution, in suspen~ion or in the gas phase, continuously or batchwise, in one or more steps, at a temperature of -60 to 100C, preferably 0 to 80C. The pre~sure is 0.5 to 100 bar. Polymerization preferably takes place in the pressure range from 5 to 60 bar, which is of particular intere~t to industry.
The metallocene compound is used in a concentration of 10-3 to 10-7, preferably 10-~ to 10-~ mol of transition metal per dm3 of solvent or per dm3 of reactor volume.
The aluminoxane is used in a concentration of 10-4 to 10-1 mol, preferably 10-3 to 10-2 mol per dm3 of solvent or per dm3 of reactor volume. In principle, however, higher concentrations are also possible.
If the polymerization is carried out in suspension or solution, the reaction is performed in an inert solvent conventionally used for the Ziegler low-pressure process, for example in an aliphatic or cycloaliphatic hydro-carbon; examples of such hydrocarbons which may be men-tioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane. It is also possible to use a naphtha or hydrogenated diesel oil fraction from which oxygen, sulfur compounds snd moisture have been carefully removed. Toluene can also be used. Prefer-ably, the monomer to be polymerized is used a8 the 801-vent or suspending sgent. The molecular weight of the polymer can be regulated in known manner, hydrogen pre-ferably being used for this purpose. The polymerization time is arbitrary ~ince the time-dependent 10~8 of poly-merization activity shown by the catalyst system to be used sccording to the invention i8 only ~light.
~~ - 12 l 338334 The process sccording to the invention i8 distinguished by the fact that the zirconium and hafnium compounds which are preferably used are very temperature-resistant, 80 they can al~o be used at temperatures up to 90C.
05 Moreover, the aluminoxaneA used a~ cocatalysts can be added in a smaller concentration than hitherto. Finally, it is now pos~ible to manufacture isoblock polymers at temperatures which are of interest to indu~try.
The following Example~ will serve to illustrate the in-vention. The abbreviations used have the meanings given below:
VN = viscosity number in cm3/g, Mw = weight-average molecular weight in g/mol, Mw/Mn = molecular weight distribution determined by gel permeation chromatography (GPC), II = isotacticity index determined by 13C NMR spec-troscopy, and n1.0 = average length of the isotactic sequences.
Isoblock polymers can be detected and distinguished from other 1-olefin polymers by NMR spectroscopy with the aid of triple resonance analysis (q.v. A. Zambelli et al., Macromolecules ~, 687-689 (1975)). Markoff statistics are valid for isoblock polymers if the following equation is satisfied:
2(rr)/(mr) = 1 The ethylene content was determined by NMR and IR spec-troscopy.
E~a~ple 1 A dry 16 dm3 kettle was flushed with nitrogen and filled with 10 dm3 of liquid propylene. 40 cm3 of a toluene solution of methylaluminoxane (= MA0, corresponding to 26.8 mmol of Al, average degree of oligomerization n =
~ - 13 l 338334 30) were then added and the reaction mixture was stirred at 30C for 15 minutes.
In a parallel procedure, 47.9 mg (0.088 mmol) of bis-05 (indenyl)bis(dimethyl~ilyl)zirconium dichloride were dis-solved in 20 cm3 of MA0 (= 13.4 mmol of Al) and pre-activated by standing for 16 minutes. The solution waR
then introduced into the kettle. The polymerization system was brought to a temperature of 70C and then kept for 5 hours at this temperature.
1.62 kg of isoblock polymer were obtained. The activity of the metallocene was therefore 6.8 kg of polymer/g of metallocene/h.
The following analytical data were determined on the polymer:
VN = 14 cm3/g, Mw = 9000, Mn = 4760, Mw/Mn = 1.9, II =
73.6%, n1.0 = 5.8, C (-(CH2)~-) = 4.71 mol%.
~ample 2 The procedure was analogous to that in Example 1 except that 60C was selected as the polymerization temperature.
The polymerization time was 5 hours. 100.0 mg of metal-locene compound were used. 0.87 kg of isoblock polymer wa~ obtained. The activity of the metallocene was there-fore 1.7 kg of polymer/g of metallocene/h. The following analytical data were determined on the polymer:
VN = 17 cm3/g, Mw = 10, 200, Mn = 5700, Mw/M~ ~ 1.8, II =
74.3%, n~.0 = 6.0, C (-(CH2)4-) = 3.65 mol%.
E~ample 3 The procedure was analogous to that in Example 1 except that 50C was selected as the polymerization temperature.
The polymerization time was 26 hours. 64.8 mg of metal-locene compound were used in the appropriate amount of MAO. O. 46 kg of isoblock polymer was obtained. The ~ 14 l 338334 activity of the metallocene was therefore l.B7 kg of polymer/g of metallocene/h. The following analytical data were determined on the polymer:
VN = 21 cm3/g, Mw = 11,900~ Mn = 6300, Mw/Mn = 1.9, II =
05 75.1%, n1,O = 6.4, C (-(CH2)~-) = 2.71 mol%.
~ample 4 The procedure wa~ analogous to that in Example 1 except that 40C was selected as the polymerization temperature.
The polymerization time was 5 hours. 44.7 mg of metal-locene compound were used. 0.14 kg of isoblock polymer was obtained. The activity of the metallocene was there-fore 0.63 kg of polymer/g of metallocene/h. The fol-lowing analytical data were determined on the polymer:VN = 9 cm3/g, Mw = 12,400, Mn = 6200, Mw/Mn = 2.0, II =
76.4%, n1,O = 6.5, C (-(CH2)~-) = 1.4 mol%.
~smple 5 The procedure was analogous to that in Example 1 except that 10C was selected as the polymerization temperature.
The polymerization time was 12 hours. 180.0 mg of metal-locene compound were used. 0.17 kg of isoblock polymer wa~ obtained. The activity of the metallocene was 0.08 kg of polymer/g of metallocene/h. The following snaly-tical data were determined on the polymer:
VN = 58 cm3/g, Mw = 48,600, Mn = 23,800, Mw/Mn = 2.0~ II
= 81.0%, n~.O = 8.4, C (-(CHz)~-) = 0.5 mol%.
~xample 6 The procedure was analogous to that in Example 1 except that bis(indenyl)bis(dimethylsilyl)hafnium dichloride, in sn amount of 5.0 mg (= 0.013 mmol), wa~ selectod as the metallocene compound (the metallocene was dissolved in 20 cm3 of MA0 (= 13.4 mmol of Al)~ snd 40 cm3 of MA0 (= 26.8 mmol of Al) were added to the liguid propylene).
l 33,~334 The polymerization system was brought to a temperature of 60C and then kept for 5 hours at this temperature. 0.73 kg of isoblock polymer wa~ obtained. The acti~ity of the metallocene was therefore 6.75 kg of polymer/g of metal-05 locene/h. The following analytical data were determinedon the polymer:
VN = 59 cm3/g, II = 77,5~,n~,0 =7,1 , C (-(CH2)~-) = 2.38 mo1%.
Comparative Example In an experiment analogous to Example 1, a polymer with a VN of 43.5 cm3/g, an Mw of 35,200 and an Mw/Mn of 2.5 was obtained with rac-bis(indenyl)(dimethylsilyl)zirconium dichloride. The isotacticity index was 96.6% and the length of the isotactic sequences was found to be 51.
It is known that polypropylene exists in various struc-tural isomers:
(a) highly isotactic polypropylene in whose molecular chains almost all tertiary C atoms have the same configuration, (b) isotactic stereoblock PP in whose molecular chains isotactic blocks of opposite configuration alternate regularly with one another, (c) syndiotactic polypropylene in whose molecular chains every other tertiary C atom ha~ the same configura-tion, (d) atactic polypropylene in whose molecular chains the tertiary C atoms have a random configuration, and (e) atactic-isotactic stereoblock PP in whose molecular chains isotactic and atactic blocks alternate with one another.
A process for the manufacture of isotactic stereoblock polymers is known in which propylene is polymerized with the aid of a metallocene of a metal of group IVb, Vb or VIb of the periodic table (q.v. US patent 4,522,982).
This metallocene is a mono-, di- or tri-cyclopentadienyl or substituted cyclopentadienyl compound of a metal, es-pecially titanium. An aluminoxane is used a~ cocatalyst.
However, the titA~ocenes which are preferably u~ed do not have sufficient heat stability in dilute solution to be usable in an industrial process. Moreo~er, in this process, products with longer isotactic seguences (n greater than 6) are only obtained at very low temperature 05 (-60C). Finally, the cocatalysts must be used in com-paratively high concentration in order to achieve an adequate catalytic yield, 80 the catalyst residue~ con-tained in the polymer product have to be removed in a separate purification step.
It is further known that stereoblock polymers of 1-ole-fins with long isotactic sequences can be obtained at indu~trially favorable polymerization temperatures by means of a catalyst con~isting of a metallocene compound lS with cyclopentadienyl radicals substituted by chiral groups, and of an aluminoxane (q.v. European patent ap-plication A 269987).
It is further known that stereoblock polymers of 1-ole-fin~ with a broad monomodal or multimodal molecular weight distribution can be obtained when 1-olefins are polymerized using a catalyst consisting of a chiral metallocene containing bridges and of an aluminoxane (g.v. European patent application A 269986). The polymers are particularly suitable for the production of transparent sheets.
It is also known that when a catalyst based on bis-cyclo-pentadienyl compounds of zirconium and on an aluminoxane is used in the polymerization of propylene, only stactic polymer is obtained (g.v. European patent application A
69951).
~inally, highly isotactic poly~,o~lene can be manufac-tured by mean~ of ~oluble stereorigid chir~l zirconium compounds (g.v. European patent application A 185 918).
A polymerization process has been found in which a poly-mer of regular molecular structure and high molecular - _ 3 ~ 338334 weight is obtained in high yield at industrially favo-rable process temperatures.
The invention thus relates to an isoblock polymer of 05 propylene with molecular chain~ containing isotactic sequences which are separated from one another in each ca~e by one monomer unit of opposite configuration, and 0.5 to 10 mol%, based on the total poly~er, of randomly distributed ethylene units, and with a seguence length of 3 to 50 monomer units.
The invention further relates to a proces~ for the ~anu-facture of the above-mentioned i~oblock polymer by the polymerization of propylene at a temperature of -60 to 100C and a pres~ure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst consisting of a metallocene and an aluminoxane, wherein the metallocene is a compound of formula I:
R3--~--R4 R 1 R ~\R 7 26 R~ 5 (I), in which M1 is ~ metal of group IVb, Vb or VIb of the periodic table, R1 and R2 are identical or different and are a hydrogen atom, a C1-Clo-alkyl group, a C1-C~o-alkoxy group, a C~-C1o-aryl group, a Cs-Clo-aryloxy group, a C2-C1o-alkenyl group, a C7-C~o-arylalkyl group, a C7-C40-alkylaryl group, a C~-C~o-srylAl~enyl group or a halo-gen atom, i 338334 .
R3, R~, R~ and R~ are identicsl or different and are 8hydrogen atom, 8 halogen atom, a C1-Clo-alkyl group, 05 -NR82, -SRB, ~OSirR83rl1, ~SirR83rl1 or -PR8z, in which R~ i8 a halogen atom or a C1-C1o-alkyl group, or pairs of ad~acent radicals R3, R~, R~ and R~ form a ring with the C atoms to which they are bonded, and R7 i8 _9 ~9 ~9 -9 R9 _~2 (CR9RlO)m-~ _~2 o ,~2 , _~2_(CR9RlO)m-M2-, ~,10 R10 ,~10 ?~10 ~10 _9 o-M2- (CR9R10)m--~10 -Sn-, -S-S-, -S0-S0-, -S0-0-S0-, BR9-BR9-BR9--9 qg -PR9-0-PR9-, -~-0-P-, -N=~-NR9- or -N=P-NR~-, O O O
in which R~ and R10 are identical or different and are a hydrogen stom, a halogen atom, a C1-C1o-alkyl group, a C -C1O-fluoroslkyl group, a C~-Clo-aryl group, a C~-C1o-fluoroaryl group, a C1-C~o-alkoxy group, a Cz-C~o-alkenyl group, a C7-C~o-arylalkyl group, a C8-c~o-arylalkenyl group or a C7-C~o-alkylaryl group, or R~
and R10 form a ring with the atoms to which they are bonded, M2 i8 sil~con, germanium or tin and 1~1 i8 zero or 1.
The invention further relates to the use of the isoblock polymer according to the present invention for the manufacture of polymer mixtures, and for the manufacture of polypropylene blends.
The isobloc~ polymer according to the invention i5 a propylene polymoer.
The molecular chains of this polymer contain isotactic sequences which are separated from one another in each ca~e by one monomer unit of opposite configuration. The molecular chains preferably consist of isotactic se-05 quences which are separated from one another in each caseby one monomer unit of opposite configuration. The iso-tactic sequences have a length of 3 to 50 monomer units.
The molecular chains simultaneously contain randomly dis-tributed ethylene units which are preferably located in the isotactic sequences and have been formed by the re-arrangement of propylene during polymerization. The ethylene units can be detected by 13C NMR spectroscopy (q.v. Soga et al., Makrom. Chem. Rap. Comm. R, 305-310 (1987)). They are in an amount of 0.5 to 10, preferably 3 to 5 mol%, based on the total polymer.
A~ a consequence of this steric structure, the isoblock polymers according to the invention are amorphous or partly crystalline according to the molecular weight and the length of the isotactic ~equences. Depending on the crystallinity, the polymers are obtained as granular powders or as compact masses. The partly crystalline isoblock polymers have a low melting point by comparison with isotactic polymers. Isoblock polymers possess rubber-like properties.
The catalyst to be used for the process according to the invention consists of a metallocene compound of formula I
and an alllm;noxane. In formula I:
R ~
35 ~7 (I).
6 l 338334 M1 is a metal of group IVb, Vb or VIb of the periodic table, for example titanium, zirconium, hafnium, vana-dium, niobium, tantalum, chromium, molybdenum or tungs-ten, preferably zirconium or hafnium.
Rl and R2 are identical or different and are a hydrogen atom, a C1-Clo-, preferably C1-C3-alkyl group, a Cl-Clo-, preferably Cl-C3-alkoxy group, a C6-Clo-, preferably C~-Cs-aryl group, a C~-Clo-, preferably C6-Cs-aryloxy group, a C2-Clo-, preferably C2-C~-alkenyl group, a C7-C~o-, preferably C7-Clo-arylalkyl group, a C7-C40-, preferably C7-Cl2-alkylaryl group, a C8-C40-, preferably C8-C12-arylalkenyl group or a halogen atom, preferably chlorine.
R3, R4, R6 and R8 are identical or different, preferably different, and are a hydrogen atom, a halogen atom, pre-ferably a fluorine, chlorine or bromine atom, a Cl-Clo-, preferably Cl-C3-alkyl group, -NR82, -SRB, ~OSirRB3rll~
~SirR83~ll or -PRB2, in which R8 i8 a halogen atom, pre-ferably a chlorine atom, or a Cl-Clo-, preferably Cl-C3-alkyl group, or pairs of adjacent radicals R3, R~, R6 and Rfi form a ring with the C atoms to which they are bonded.
R7 is -M2-(CR9R1O)m-~ -M2-0-~2-~ _~2_(CR9R1O)m-M2-, -o-M2-(CR9R1O)m--Sn-, -5-S-, -S0-S0-, -50-0-S-,-BR9-BR9-BR9--PR9-0-PR9-, -P-0-P-, -N=P-NR9- or -N=P-NR~-, in which R~ and Rl are identical or different and are a hydrogen atom, a halogen atom, a C1-C1o-alkyl group, preferably a Cl-C~-alkyl group and especially a methyl group, a C1-C1o-fluoroalkyl group, preferably a CF3 group, a C6-C1o-, preferably C~-C~-aryl group, a C6-C1o-fluoroaryl group, preferably a hexafluorophenyl 05 group, a Cl-C1o-, preferably C1-C4-alkoxy group, es-pecially a methoxy group, a C2-C1o-, preferably C2-C~-alkenyl group, a C7-C~o-, preferably C7-C1o-arylalkyl group, a C8-C~o-, preferably Cs-C12-arylalkenyl group or a C7-C40-, preferably C7-Cl2-alkylaryl group, or R~
and R10 form a ring together with the atom~ to which they are bonded.
M2 is Si, Ge or Sn.
lS R7 is preferably =SiR~Rl0-SiR~R10-.
m is zero or 1.
The metallocenes described above can be prepared accor-ding to the following reaction scheme:
H2Ra ~ ButylLi ~ HRaLi \ X - R7 - X~ HRa _ R7 - RbH
25 H2Rb ~ ButylLi ~ HRbLi '~
~X = Cl, ~r,~, 0-1osyl, HR~ = ~ ,HR
HRa R7 - RbH ~ 2 8utylLi ~ LiRa _ R7 - RbLi / ~ " , Cl LiRa _ R7 - RbLi MlCl~ R7 ~ ~
\ 'b Cl ~ 8 l 338334 ~a ~a ,Ra 05 R7 l~\ R1Li~ R7 Y~ R2~i> R7 \ ' It i~ especially preferred to use bis(indenyl)bis(di-methylsilyl)hafnium dichloride (= 1) and bis(indenyl)bis-(dimethylsilyl)zirconium dichloride (= 2) as the metal-locene compounds.
The activator is an aluminoxane of formula (II):
Rll Rll Rll I
Al - 0 - Al - 0 - Al ~ \ R
Rll _n ll (II) for the linear type and/or of formula (III):
Rll I
- Al - 0 -(III) _n+2 for the cyclic type. In these formulae, Rll is a C1-C~-alkyl group, preferably methyl, ethyl or isobutyl, in particular methyl, and n is an integer from 2 to 50, pre-ferably 10 to 40. The exact structure of the al~ noxAne i8 not certain, however, 80 formulae II and III are only approximate formulae.
The aluminoxane can be prepared in a variety of ways.
One possibility i~ carefully to add water to a dilute solution of an aluminum trialkyl, the aluminum trialkyl 05 solution and the water each being introduced in small portion~ into a larger amount of an inert solvent and the evolution of ga~ being allowed to finish between succes-sive addition~.
In another proce~, finely powdered copper sulfate penta-hydrate is su~pended in toluene and, in a glass flask, aluminum trialkyl is added, under inert gas at about -20C, in an amount such that about 1 mol of CuS04 5H20 i~ available for every 4 A1 atoms. After slow hydrolysis with the elimination of alkane, the reaction mixture is left for 24 to 48 hours at room temperature, during which time it must be cooled, if necessary, to prevent the tem-perature from rising above 30C. The al~lm~noYAne dis-solved in the toluene is then isolated from the copper sulfate by filtration and the solution i8 concentrated under vacuum. It is assumed that, in this preparative process, the low-molecular aluminoxanes condense to form higher-molecular oligomers with the elimination of alu-minum trialkyl.
Furthermore, al~l~inoxanes are obtained when aluminum tri-alkyl, preferably aluminum trimethyl, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted, at a temperature of -20 to 100C, with aluminum salts containing water of crystallization, preferably aluminum sulfate. The volume ratio of solvent to aluminum alkyl used i8 1: 1 to 50:1 - preferably S:1 -and the reaction time, which can be monitored by ~eans of the alkane eliminated, is 1 to 200 hours - preferably 10 to 40 hours.
Aluminum salts containing water of crystallization which are used in particular are those with a hiBh content of water of crystallization. Aluminum sulfate hydrates are - lo i 338334 -especially preferred, in particular the compounds Al2(S0~) 3 16H20 and Al2(S0~) 3 ~ 18H20 with the especially high contents of water of crystallization of 16 and 18 mol of H20/mol of Al2(S04)3 respectively.
Another variant for the preparation of aluminoxanes con-sists in dissolving aluminum trial~yl, preferably alu-minum trimethyl, in the suspending agent, preferably in the liguid monomer or in heptane or toluene, previously placed in the polymerization kettle, and then reacting the aluminum compound with water.
There are other processes for the preparation of alumin-oxanes which can be used in addition to those described above.
Before it is u~ed in the polymerization reaction, the metallocene can be preactivated with an alum~noxane of formula (II) and/or (III), which markedly increases the polymerization activity.
The preactivation of the transition metal compound i8 carried out in solution, the metallocene preferably being dis~olved in a solution of the al~inoYA~e in an inert hydrocarbon. An aliphatic or aromatic hydrocarbon is suitable for this purpose. Toluene is preferably used.
The concentration of the al~ nox~ne in the solution is in the range from approx. 1% by weight to the saturation limit, preferably from 6 to 30% by weight, based in each case on the total solution. The metallocene can be used in the same concentration, although it is preferably uset in an amount of 10-~ - 1 mol per mol of alum~nox~ne~ The preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. The reaction temperature is -78C to 100C, preferably 0 to 70C.
The catalyst to be used according to the invention iB
employed for the polymerization of 1-olefins of the formula R-CH=CH2, in which R iB an alkyl radical having 1 to 28 C atoms, preferably 1 to 10 C atom~, in particular one C atom, for example propylene, but-1-ene, hex-1-ene, 4-methylpent-1-ene or oct-1-ene. Propylene i8 especially 05 preferred.
The polymerization is carried out in known manner in solution, in suspen~ion or in the gas phase, continuously or batchwise, in one or more steps, at a temperature of -60 to 100C, preferably 0 to 80C. The pre~sure is 0.5 to 100 bar. Polymerization preferably takes place in the pressure range from 5 to 60 bar, which is of particular intere~t to industry.
The metallocene compound is used in a concentration of 10-3 to 10-7, preferably 10-~ to 10-~ mol of transition metal per dm3 of solvent or per dm3 of reactor volume.
The aluminoxane is used in a concentration of 10-4 to 10-1 mol, preferably 10-3 to 10-2 mol per dm3 of solvent or per dm3 of reactor volume. In principle, however, higher concentrations are also possible.
If the polymerization is carried out in suspension or solution, the reaction is performed in an inert solvent conventionally used for the Ziegler low-pressure process, for example in an aliphatic or cycloaliphatic hydro-carbon; examples of such hydrocarbons which may be men-tioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane. It is also possible to use a naphtha or hydrogenated diesel oil fraction from which oxygen, sulfur compounds snd moisture have been carefully removed. Toluene can also be used. Prefer-ably, the monomer to be polymerized is used a8 the 801-vent or suspending sgent. The molecular weight of the polymer can be regulated in known manner, hydrogen pre-ferably being used for this purpose. The polymerization time is arbitrary ~ince the time-dependent 10~8 of poly-merization activity shown by the catalyst system to be used sccording to the invention i8 only ~light.
~~ - 12 l 338334 The process sccording to the invention i8 distinguished by the fact that the zirconium and hafnium compounds which are preferably used are very temperature-resistant, 80 they can al~o be used at temperatures up to 90C.
05 Moreover, the aluminoxaneA used a~ cocatalysts can be added in a smaller concentration than hitherto. Finally, it is now pos~ible to manufacture isoblock polymers at temperatures which are of interest to indu~try.
The following Example~ will serve to illustrate the in-vention. The abbreviations used have the meanings given below:
VN = viscosity number in cm3/g, Mw = weight-average molecular weight in g/mol, Mw/Mn = molecular weight distribution determined by gel permeation chromatography (GPC), II = isotacticity index determined by 13C NMR spec-troscopy, and n1.0 = average length of the isotactic sequences.
Isoblock polymers can be detected and distinguished from other 1-olefin polymers by NMR spectroscopy with the aid of triple resonance analysis (q.v. A. Zambelli et al., Macromolecules ~, 687-689 (1975)). Markoff statistics are valid for isoblock polymers if the following equation is satisfied:
2(rr)/(mr) = 1 The ethylene content was determined by NMR and IR spec-troscopy.
E~a~ple 1 A dry 16 dm3 kettle was flushed with nitrogen and filled with 10 dm3 of liquid propylene. 40 cm3 of a toluene solution of methylaluminoxane (= MA0, corresponding to 26.8 mmol of Al, average degree of oligomerization n =
~ - 13 l 338334 30) were then added and the reaction mixture was stirred at 30C for 15 minutes.
In a parallel procedure, 47.9 mg (0.088 mmol) of bis-05 (indenyl)bis(dimethyl~ilyl)zirconium dichloride were dis-solved in 20 cm3 of MA0 (= 13.4 mmol of Al) and pre-activated by standing for 16 minutes. The solution waR
then introduced into the kettle. The polymerization system was brought to a temperature of 70C and then kept for 5 hours at this temperature.
1.62 kg of isoblock polymer were obtained. The activity of the metallocene was therefore 6.8 kg of polymer/g of metallocene/h.
The following analytical data were determined on the polymer:
VN = 14 cm3/g, Mw = 9000, Mn = 4760, Mw/Mn = 1.9, II =
73.6%, n1.0 = 5.8, C (-(CH2)~-) = 4.71 mol%.
~ample 2 The procedure was analogous to that in Example 1 except that 60C was selected as the polymerization temperature.
The polymerization time was 5 hours. 100.0 mg of metal-locene compound were used. 0.87 kg of isoblock polymer wa~ obtained. The activity of the metallocene was there-fore 1.7 kg of polymer/g of metallocene/h. The following analytical data were determined on the polymer:
VN = 17 cm3/g, Mw = 10, 200, Mn = 5700, Mw/M~ ~ 1.8, II =
74.3%, n~.0 = 6.0, C (-(CH2)4-) = 3.65 mol%.
E~ample 3 The procedure was analogous to that in Example 1 except that 50C was selected as the polymerization temperature.
The polymerization time was 26 hours. 64.8 mg of metal-locene compound were used in the appropriate amount of MAO. O. 46 kg of isoblock polymer was obtained. The ~ 14 l 338334 activity of the metallocene was therefore l.B7 kg of polymer/g of metallocene/h. The following analytical data were determined on the polymer:
VN = 21 cm3/g, Mw = 11,900~ Mn = 6300, Mw/Mn = 1.9, II =
05 75.1%, n1,O = 6.4, C (-(CH2)~-) = 2.71 mol%.
~ample 4 The procedure wa~ analogous to that in Example 1 except that 40C was selected as the polymerization temperature.
The polymerization time was 5 hours. 44.7 mg of metal-locene compound were used. 0.14 kg of isoblock polymer was obtained. The activity of the metallocene was there-fore 0.63 kg of polymer/g of metallocene/h. The fol-lowing analytical data were determined on the polymer:VN = 9 cm3/g, Mw = 12,400, Mn = 6200, Mw/Mn = 2.0, II =
76.4%, n1,O = 6.5, C (-(CH2)~-) = 1.4 mol%.
~smple 5 The procedure was analogous to that in Example 1 except that 10C was selected as the polymerization temperature.
The polymerization time was 12 hours. 180.0 mg of metal-locene compound were used. 0.17 kg of isoblock polymer wa~ obtained. The activity of the metallocene was 0.08 kg of polymer/g of metallocene/h. The following snaly-tical data were determined on the polymer:
VN = 58 cm3/g, Mw = 48,600, Mn = 23,800, Mw/Mn = 2.0~ II
= 81.0%, n~.O = 8.4, C (-(CHz)~-) = 0.5 mol%.
~xample 6 The procedure was analogous to that in Example 1 except that bis(indenyl)bis(dimethylsilyl)hafnium dichloride, in sn amount of 5.0 mg (= 0.013 mmol), wa~ selectod as the metallocene compound (the metallocene was dissolved in 20 cm3 of MA0 (= 13.4 mmol of Al)~ snd 40 cm3 of MA0 (= 26.8 mmol of Al) were added to the liguid propylene).
l 33,~334 The polymerization system was brought to a temperature of 60C and then kept for 5 hours at this temperature. 0.73 kg of isoblock polymer wa~ obtained. The acti~ity of the metallocene was therefore 6.75 kg of polymer/g of metal-05 locene/h. The following analytical data were determinedon the polymer:
VN = 59 cm3/g, II = 77,5~,n~,0 =7,1 , C (-(CH2)~-) = 2.38 mo1%.
Comparative Example In an experiment analogous to Example 1, a polymer with a VN of 43.5 cm3/g, an Mw of 35,200 and an Mw/Mn of 2.5 was obtained with rac-bis(indenyl)(dimethylsilyl)zirconium dichloride. The isotacticity index was 96.6% and the length of the isotactic sequences was found to be 51.
Claims (5)
1. An isoblock polymer of propylene with molecular chains containing isotactic sequences which are separated from one another in each case by one monomer unit of opposite configuration, and 0.5 to 10 mol%, based on the total polymer, of randomly distributed ethylene units, and with a sequence length of 3 to 50 monomer units.
2. The isoblock polymer sccording to claim 1 with mole-cular chains consisting of isotactic sequences which are separated from one another in each case by one monomer unit of opposite configuration, and containing 0.5 to 10 mol%, based on the total polymer, of randomly distributed ethylene units.
3. A process for the manufacture of the isoblock polymer according to claim 1 by the polymerization of propylene at a temperature of -60 to 100°C snd a pressure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst consistine of a metallocene and an aluminoxane, wherein the metallocene is bis(indenyl)-bis(dimethylsilyl)hafnium dichloride or bis(indenyl)-bis(dimethylsilyl)zirconium dichloride
4. Use of the isoblock polymer according to claim 1 for the manufacture of polymer mixtures.
5. Use according to claim 4 for the manufacture of poly-propylene blends.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3826074.3 | 1988-07-30 | ||
| DE3826074A DE3826074A1 (en) | 1988-07-30 | 1988-07-30 | PROPYLENE ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1338334C true CA1338334C (en) | 1996-05-14 |
Family
ID=6359997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000606883A Expired - Fee Related CA1338334C (en) | 1988-07-30 | 1989-07-28 | Propylene isoblock polymer and process for its manufacture |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0355447B1 (en) |
| JP (1) | JP3095754B2 (en) |
| AU (1) | AU612507B2 (en) |
| CA (1) | CA1338334C (en) |
| DE (2) | DE3826074A1 (en) |
| ES (1) | ES2058413T3 (en) |
| ZA (1) | ZA895768B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3826075A1 (en) * | 1988-07-30 | 1990-02-01 | Hoechst Ag | 1-OLEFIN ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
| DE3916553A1 (en) * | 1989-05-20 | 1990-11-22 | Hoechst Ag | SYNDIO ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
| US5420217A (en) * | 1989-09-13 | 1995-05-30 | Exxon Chemical Patents Inc. | Process for producing amorphous poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
| DE4120009A1 (en) * | 1991-06-18 | 1992-12-24 | Basf Ag | SOLUBLE CATALYST SYSTEMS FOR THE PRODUCTION OF POLYALK-1-ENEN WITH HIGH MOLES |
| DE4130352A1 (en) * | 1991-09-12 | 1993-03-18 | Basf Ag | DISABLED AND REACTIVATED METALLOCENE CATALYST SYSTEMS |
| EP0544308B1 (en) * | 1991-11-28 | 1998-02-18 | Showa Denko Kabushikikaisha | Novel metallocene and process for producing polyolefin using the same |
| GB9205996D0 (en) * | 1992-03-19 | 1992-04-29 | Exxon Chemical Patents Inc | Polymers and additive compositions |
| DE4317654A1 (en) * | 1993-05-27 | 1994-12-01 | Basf Ag | Statistical copolymers of propylene |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3640924A1 (en) * | 1986-11-29 | 1988-06-01 | Hoechst Ag | 1-OLEFIN STEREOBLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
| DE3726067A1 (en) * | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
| IL89525A0 (en) * | 1988-03-21 | 1989-09-10 | Exxon Chemical Patents Inc | Silicon-bridged transition metal compounds |
| DE3825814A1 (en) * | 1988-07-29 | 1990-02-01 | Hoechst Ag | METHOD FOR PRODUCING L-OLEFIN POLYMERS |
| DE3832082A1 (en) * | 1988-09-21 | 1990-03-29 | Basf Ag | METHOD FOR PRODUCING HOMOPOLYMERISATEN OR COPOLYMERISATEN DER PROPYLENS |
| DE3907965A1 (en) * | 1989-03-11 | 1990-09-13 | Hoechst Ag | METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN |
-
1988
- 1988-07-30 DE DE3826074A patent/DE3826074A1/en not_active Withdrawn
-
1989
- 1989-07-25 DE DE8989113743T patent/DE58904700D1/en not_active Expired - Fee Related
- 1989-07-25 ES ES89113743T patent/ES2058413T3/en not_active Expired - Lifetime
- 1989-07-25 EP EP89113743A patent/EP0355447B1/en not_active Expired - Lifetime
- 1989-07-27 JP JP01192771A patent/JP3095754B2/en not_active Expired - Fee Related
- 1989-07-28 CA CA000606883A patent/CA1338334C/en not_active Expired - Fee Related
- 1989-07-28 AU AU39054/89A patent/AU612507B2/en not_active Ceased
- 1989-07-28 ZA ZA895768A patent/ZA895768B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0355447A2 (en) | 1990-02-28 |
| ES2058413T3 (en) | 1994-11-01 |
| ZA895768B (en) | 1990-04-25 |
| AU612507B2 (en) | 1991-07-11 |
| JP3095754B2 (en) | 2000-10-10 |
| JPH0275610A (en) | 1990-03-15 |
| DE3826074A1 (en) | 1990-02-01 |
| DE58904700D1 (en) | 1993-07-22 |
| EP0355447B1 (en) | 1993-06-16 |
| EP0355447A3 (en) | 1991-03-20 |
| AU3905489A (en) | 1990-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5700896A (en) | Polymer having long isotactic sequences and randomly-distributed ethylene content obtained by polymerizing propylene in presence of specific catalysts | |
| US6413899B1 (en) | 1-olefin isoblock polymer and process for its manufacture | |
| US6197902B1 (en) | Syndio-isoblock polymer and process for its preparation | |
| AU641638B2 (en) | Process for the preparation of a syndiotactic polyolefin | |
| CA1319784C (en) | Process for the preparation of a 1-olefin polymer | |
| KR950008154B1 (en) | Hafnium metallocene catalyst for the polymerization of olefins | |
| KR100196262B1 (en) | Process and catalyst for producing syndiotactic polyemrs | |
| US6713426B1 (en) | Metallocene capable of being used for the process for the preparation of a syndiotactic polyolefin | |
| US5962719A (en) | Process for the preparation of a polyolefin wax | |
| KR100197327B1 (en) | Syndiotactic polypropylene | |
| KR950008152B1 (en) | Catalyst systems for producing polyolefins having a broad molecular weight distribution | |
| US5539066A (en) | Process for the preparation of syndiotactic polyolefins having a broad molecular weight distribution | |
| CA1326676C (en) | Transition-metal compound having a bis-substituted- cyclopentadienyl ligand of bridged structure | |
| KR100414759B1 (en) | Metallocene compounds, process for their preparation, and their use in catalysts for the polymerization of olefins | |
| EP0984989B1 (en) | Use of metallocene catalysts for producing regiospecific, isotactic polyolefins | |
| AU595661B2 (en) | Process for the preparation of a 1-olefin stereoblock polymer | |
| EP0581754A1 (en) | Process and catalyst for producing isotactic polyolefins | |
| EP0628574A1 (en) | Olefin polymerization catalyst and olefin polymerization process | |
| CA2042324A1 (en) | Process for the preparation of a polyolefin | |
| CA1319785C (en) | Process for the preparation of 1-olefin polymers | |
| EP0328580B1 (en) | Catalyst and process for preparation of syndiotactic polystyrene | |
| CA1338334C (en) | Propylene isoblock polymer and process for its manufacture | |
| EP1095081B1 (en) | Polyolefin production | |
| US6326444B2 (en) | Preparation of polymers of alkenes by suspension polymerization | |
| US5677255A (en) | Polysiloxane supported metallocene catalyst for olefin polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |