US RE39156 E1
A process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula Ra—CH═CH—Rb, in which Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms or Ra and Rb, together with the atoms connecting them, can form a ring, at a temperature of from −60° to 200° C., at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst formed from a metallocene in the meso-form or a meso:rac mixture, with meso:rac>1:99, as transition-metal compound and a cocatalyst, wherein the metallocene is a compound of the formula I,
in which M1 is Zr or Hf, R1 and R2 are identical or different and are methyl or chlorine, R3 and R6 are identical or different and are methyl, isopropyl, phenyl, ethyl or trifluoromethyl, R4 and R5 are hydrogen or as defined for R3 and R6, or R4 forms an aliphatic or aromatic ring with R6, or adjacent radicals R4 form a ring of this type, and R7 is a
radical, and m plus n is zero or 1.
M1 is a metal from group IVb, Vb or VIb of the Periodic Table,
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,
the radicals R4 and R5 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, which may be halogenated, a C6-C10-aryl group, which may be halogenated, or an —NR10 2, —SR10, —OSiR10 3, —SiR10 3 or —PR10 2 radical in which R10 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group,
R3 and R6 are identical or different and are as defined as for R4, with the proviso that R3 and R6 are not hydrogen,
or two or more of the radicals R3 to R6, together with the atoms connecting them, form a ring system,
>BR11, >AlR11, —Ge—, —Sn—, —O—, —S—, >SO, >SO2, >NR11, >CO, >PR11 or >P(O)R11,
R11 , R12 and R13 are identical orand R12 are different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoroaryl 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,
R13 is a hydrogen atom, a halogen atom, a C 1 -C 10-alkyl group, a C 1 -C 10-fluoroalkyl group, a C 6 -C 10-aryl group, a C 6 -C 10-fluoroaryl group, a C 1 -C 10-alkoxy group, a C 2 -C 10-alkenyl group, a C 7 -C 40-arylalkyl group, a C 8 -C 40-arylalkenyl group or a C 7 -C 40-alkylaryl group,
or R11 and R12 or R11 and R13, in each case together with the atoms connecting them, form a ring,
M2 is silicon, germanium or tin,
R8 and R9 are identical or different and are as defined for R11, and
m and n are identical or different and are zero, 1 or 2, where m plus n is zero, 1 or 2.
2. A compound as claimed in
radical, and m plus n are zero or 1.
3. A compound as claimed in
This is a divisional of copending application Ser. No. 08/107,187 filed on Aug. 16, 1993.
For the preparation of highly isotactic polyolefins by means of stereospecific racemic metallocene/cocatalyst systems, the highest possible isotacticity is desired. This means that very stereoselective racemic metallocene types are employed which are able to build up polymer chains having very few construction faults. The consequence of this is that products having high crystallinity, high melting point and thus also high hardness and excellent modulus of elasticity in flexing are obtained as desired.
However, it is disadvantageous that these polymers are difficult to process, and in particular problems occur during extrusion, injection molding and thermoforming. Admixing of flow improvers and other modifying components could help here, but results in the good product properties, such as, for example, the high hardness, being drastically reduced. In addition, tackiness and fogging also occur. The object was thus to improve the processing properties of highly isotactic polyolefins of this type without in this way impairing the good properties of the moldings produced therefrom.
Surprisingly, we have found that if rac/meso mixtures of certain metallocenes are used, the processing problems can be eliminated without the abovementioned good product properties being lost.
In addition, the use of these specific metallocenes in their pure meso-form makes it possible to prepare high-molecular-weight atactic polyolefins which can be homogeneously admixed, as additives, with other polyolefins.
This was not possible with the low-molecular weight polyolefins accessible hitherto due to the large differences in viscosity between the polyolefin matrix and the atactic component.
Such admixtures improve polyolefin moldings with respect to their surface gloss, their impact strength and their transparency. In addition, the processing properties of such polyolefins are likewise improved by admixing the high-molecular-weight atactic polyolefin. Likewise, tackiness and fogging do not occur.
Homogeneous miscibility of the atactic component is so important because only with a homogeneous material can a usable molding with a good surface and long service life be produced and only in the case of homogeneous distribution do the qualities of the atactic component come out in full.
The invention thus relates to the preparation of polyolefins which
Polyolefins which conform to the description under 2) can either be prepared directly in the polymerization or are prepared by melt-mixing in an extruder or compounder.
The invention thus relates to a process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula Ra—CH═CH—Rb, in which Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, together with the atoms connecting them, can form a ring, at a temperature of from −60° to 200° C., at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst formed from a metallocene as transition-metal compound and a cocatalyst, wherein the metallocene is a compound of the formula I which is used in the pure meso-form for the preparation of polyolefins of type 1 and used in a meso:rac ratio of greater than 1:99, preferably greater than 2:98, for the preparation of type 2 polyolefins,
Alkyl is straight-chain or branched alkyl. Halogen (halogenated) means fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
The substitutents R3, R4, R5 and R6 may be different in spite of the same indexing.
The catalyst to be used for the process according to the invention comprises a cocatalyst and a metallocene of the formula I.
In the formula I, M1 is a metal from group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium.
R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-, preferably C1-C3-alkyl group, a C1-C10-, preferably C1-C3-alkoxy group, a C6-C10-, preferably C6-C8-aryl group, a C6-C10-, preferably C6-C8-aryloxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-arylalkyl group, a C7-C40-, preferably a C7-C12-alkylaryl group, a C8-C40-, preferably a C8-C12-arylalkenyl group, or a halogen atom, preferably chlorine.
The radicals R4 and R5 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C1-C10-, preferably C1-C4-alkyl group, which may be halogenated, a C6-C10-, preferably a C6-C9-aryl group, which may be halogenated, an —NR10 2, —SR10, —OSiR10 3, —SiR10 3 or —PR10 2 radical, in which R10 is a halogen atom, preferably a chlorine atom, or a C1-C10-, preferably a C1-C3-alkyl group, or a C6-C10-, preferably C6-C8-aryl group. R4 and R5 are particularly preferably hydrogen, C1-C4-alkyl or C6-C9-aryl.
R3 and R6 are identical or different and are defined for R4, with the proviso that R3 and R6 must not be hydrogen. R3 and R6 are preferably (C1-C4)-alkyl or C6-C9-aryl, both of which may be halogenated, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl, phenyl, tolyl or mesityl, in particular methyl, isopropyl or phenyl.
Two or more of the radicals R3 to R6 may alternatively, together with the atoms connecting them, form an aromatic or aliphatic ring system. Adjacent radicals, in particular R4 and R6, together preferably form a ring.
═BR11, ═AlR11, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO2, ═NR11, ═CO, ═PR11 or ═P(O)R11, where R11, R12 and R13 are identical and are a hydrogen atom, a halogen atom, a C1-C10-, preferably C1-C4-alkyl group, in particular a methyl group, a C1-C10-fluoroalkyl group, preferably a CF3 group, a C6-C10-, preferably C6-C8-aryl group, a C6-C10-fluoroaryl group, preferably a pentafluorophenyl group, a C1-C10-, preferably a C1-C4-alkoxy group, in particular a methoxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-arylalkyl group, a C8-C40-, preferably C8-C12-arylalkenyl group or a C7-C40-, preferably C7-C12-alkylaryl group, or R11 and R12 or R11 and R13, in each case together with the atoms connecting them, form a ring.
M2 is silicon, germanium or tin, preferably silicon or germanium.
R7 is preferably ═CR11R12, ═SiR11R12, ═GeR11R12, —O—, —S—, ═SO, ═PR11 or ═P(O)R11.
R8 and R9 are identical or different and are as defined for R11.
m and n are identical or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.
Particularly preferred metallocenes are thus the compounds of the formulae A and B
M1 is Zr or Hf; R1 and R2 are methyl or chlorine; R3 and R6 are methyl, isopropyl, phenyl, ethyl or trifluoromethyl; R4 and R5 are hydrogen or as defined for R3 and R6, or R4 can form an aliphatic or aromatic ring with R6; the same also applies to adjacent radicals R4; and R8, R9, R11 and R12 are as defined above, in particular the compounds I listed in the working examples.
This means that the indenyl radicals of the compounds I are substituted, in particular, in the 2,4-position, in the 2,4,6-position, in the 2,4,5-position or in the 2,4,5,6-position, and the radicals in the 3- and 7-positions are preferably hydrogen.
The metallocenes described above can be prepared by the following reaction scheme, which is known from the literature:
The compounds are formed from the synthesis as rac/meso mixtures. The meso or rac form can be increased in concentration by fractional crystallization, for example in a hydrocarbon. This procedure is known and is part of the prior art.
The cocatalyst used according to the invention is preferably an aluminoxane of the formula (II)
The radicals R14 are preferably identical and are preferably methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicals R14 are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, where hydrogen and isobutyl are preferably present to the extent of 0.01-40% (number of radicals R14).
The aluminoxane can be prepared in various ways by known processes. One of the methods is, for example, to react an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (in gas, solid, liquid or bonded form—for example as water of crystallization) in an inert solvent (such as, for example, toluene). In order to prepare an aluminoxane containing different alkyl groups R14 two different trialkylaluminum compounds (AlR3+AlR′3) corresponding to the desired composition are reacted with water (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
The precise structure of the aluminoxanes II and III is unknown.
Regardless of the preparation method, all the aluminoxane solutions have in common a varying content of unreacted aluminum starting compound, in free form or as an adduct.
It is possible to preactivate the metallocene by means of an aluminoxane of the formula (II) and/or (III) before use in the polymerization reaction. This significantly increases the polymerization activity and improves the grain morphology.
The preactivation of the transition-metal compound is carried out in solution. The metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic and aromatic hydrocarbons. Toluene is preferably used.
The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in each case based on the solution as a whole. The metallocene can be employed in the same concentration, but is preferably employed in an amount of from 10−4 to 1 mol per mol of aluminoxane. The preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The reaction is carried out at a temperature of from −78° C. to 100° C., preferably from 0° to 70° C.
The metallocene can also be prepolymerized or applied to a support. Prepolymerization is preferably carried out using the (or one of the) olefin(s) employed in the polymerization.
Examples of suitable supports are silica gels, aluminum oxides, solid aluminoxane or other inorganic support materials. Another suitable support material is a polyolefin powder in finely divided form.
According to the invention, compounds of the formulae RxNH4-xBR′4, RxPH4-xBR′4, R3CBR′4 or BR′3 can be used as suitable cocatalysts instead of or in addition to an aluminoxane. In these formulae, x is a number from 1 to 4, preferably 3, the radicals R are identical or different, preferably identical, and are C1-C10-alkyl, or C6-C18-aryl or 2 radicals R, together with the atom connecting them, form a ring, and the radicals R′ are identical or different, preferably identical, and are C6-C18-aryl, which may be substituted by alkyl, haloalkyl or fluorine.
In particular, R is ethyl, propyl, butyl or phenyl, and R′ is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (cf. EP-A 277 003, EP-A 277 004 and EP-A 426 638).
When the abovementioned cocatalysts are used, the actual (active polymerization catalyst comprises the product of the reaction of the metallocene and one of said compounds. For this reason, this reaction product is preferably prepared first outside the polymerization reactor in a separate step using a suitable solvent.
In principle, suitable cocatalysts are according to the invention any compounds which, due to their Lewis acidity, are able to convert the neutral metallocene into a cation and stabilize the latter (“labile coordination”). In addition, the cocatalyst or the anion formed therefrom should not undergo any further reactions with the metallocene cation formed (cf. EP-A 427 697).
In order to remove catalyst poisons present in the olefin, purification by means of an alkylaluminum compound, for example AlMe3 or AlEt3, is advantageous. This purification can be carried out either in the polymerization system itself, or the olefin is brought into contact with the Al compound before addition to the polymerization system and is subsequently separated off again.
The polymerization or copolymerization is carried out in known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more steps, at a temperature of from −60° to 200° C., preferably from 30° to 80° C., particularly preferably at from 50° to 80° C. The polymerization or copolymerization is carried out using olefins of the formula Ra—CH═CH—Rb. In this formula, Ra and Rb are identical or different and are a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms. However, Ra and Rb, together with the carbon atoms connecting them, may alternatively form a ring. Examples of such olefins are ethylene, propylene, 1-butane, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene and norbonadiene. In particular, propylene and ethylene are polymerized.
If necessary, hydrogen is added as molecular weight regulator and/or to increase the activity. The overall pressure in the polymerization system is 0.5 to 100 bar. The polymerization is preferably carried out in the industrially particularly relevant pressure range of from 5 to 64 bar.
The metallocene is used in a concentration, based on the transition metal, of from 10−3 to 10−8 mol, preferably from 10−4 to 10−7 mol, of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminoxane is used in a concentration of from 10−5 to 10−1 mol, preferably from 10−4 to 10−2 mol, per dm3 of solvent or per dm3 of reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts with respect to the metallocene. In principle, however, higher concentrations are also possible.
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent which is customary for the Ziegler low-pressure process is used. For example, the process is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of such hydrocarbons which may be mentioned are propane, butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
It is also possible to use a benzine or hydrogenated diesel oil fraction. Toluene can also be used. The polymerization is preferably carried out in the liquid monomer.
If inert solvents are used, the monomers are metered in as gases or liquids.
The polymerization can have any desired duration, since the catalyst system to be used according to the invention only exhibits a slight drop in polymerization activity as a function of time.
The process according to the invention is distinguished by the fact that the meso-metallocenes described give atactic polymers of high molecular weight in the industrially particularly relevant temperature range between 50° and 80° C. rac/meso mixtures of the metallocenes according to the invention give homogeneous polymers with particular good processing properties. Moldings produced therefrom are distinguished by good surfaces and high transparency. In addition, high surface hardnesses and good moduli of elasticity in flexing are characteristics of these moldings.
The high-molecular-weight atactic component is not tacky, and the moldings are furthermore distinguished by very good fogging behavior.
The examples below serve to illustrate the invention in greater detail.
The following abbreviations are used:
A dry 24 dm3 reactor was flushed with propylene and filled with 12 dm3 of liquid propylene. 35 cm3 of a toluene solution of methylaluminoxane (corresponding to 52 mmol of Al, mean degree of oligomerization p=18) were then added, and the batch was stirred at 30° C. for 15 minutes. In parallel, 7.5 mg of the meso-metallocene shown in Table 1 were dissolved in 13.5 cm3 of a toluene solution of methylaluminoxane (30 mmol of Al) and preactivated by standing for 15 minutes. The solution was then introduced into the reactor and heated to 70° C. or 50° C. (Table 1, 10° C./min). The polymerization duration was 1 hour. The polymerization was terminated by addition of 20 dm3 (s.t.p.) of CO2 gas. The metallocene activities and the viscosity indices of the atactic polymers obtained are collated in Table 1. The 13C-NMR analyses gave in all cases isotactic block lengths niso of <4, typically niso=2, and the syndiotactic block length was typically likewise in the region of 2. The triad distributions mm/mrar were typically about 25:50:25, and the isotactic index (mm+ 1/2 mr) was less than 60%. The products were therefore undoubtedly typical atactic polypropylenes. This is also confirmed by the solubility in boiling heptane or in diethyl ether.
The DSC spectrum showed no defined melting point. Tg transitions were observed in the range from 0° C. to −20° C.
Examples 1, 4, 7, 9, 12, 15 and 16 were repeated but the pure meso-metallocene was replaced by a rac:meso=1:1 mixture.
The polymers obtained were extracted with boiling ether or dissolved in a hydrocarbon having a boiling range of 140°-170° C. and subjected to fractional crystallization; the high-molecular-weight atactic component was separated off and could thus be analyzed separately from the isotactic residue. The results are collated in Table 2. Products are non-tacky, and moldings produced therefrom do not exhibit fogging and have an excellent surface and transparency.
Example 5 was repeated, but the pure meso-form of the metallocene was replaced by rac:meso ratios of 98:2, 95:5, 90:10, 85:15 and 75:25. The results are collated in Table 3. A non-tacky powder is obtained, and moldings produced therefrom have a good surface, are non-tacky and do not exhibit fogging. The molding hardness is good, as is the transparency.
Example 24 was repeated using 12 dm3 (s.t.p.) of hydrogen in the polymerization system. The polymerization duration was 30 minutes. The metallocene activity was 586 kg of PP/g of metallocene×h. The ether-soluble proportion was 1.1% by weight, with a VI of 107 cm3/g, and the ether-insoluble proportion was 98.9% by weight, with a VI of 151 cm3/g.
Example 25 was repeated, but 70 g of ethylene were metered in continuously during the polymerization. The polymerization duration was 45 minutes. The metallocene activity was 468 kg of PP/g of metallocene×h, the ethylene content of the copolymer was 3.3% by weight, and, according to 13C-NMR spectroscopy, the ethylene was incorporated substantially in an isolated manner (random compolymer).
A dry 150 dm3 reactor was flushed with nitrogen and filled at 20° C. with 80 dm3 of a benzine cut having the boiling range from 100° to 120° C. from which the aromatic components had been removed. The gas space was then flushed with propylene until free of nitrogen, and 50 l of liquid propylene and 64 cm3 of a toluene solution of methylaluminoxane (100 mmol of Al, p=18) were added. The reactor contents were heated to 60° C., and the hydrogen content in the reactor gas space was adjusted to 0.1% by metering in hydrogen and was kept constant during the entire polymerization time by further metering (checking on-line by gas chromatography). 10.7 mg of rac:meso (95:5) of the metallocene dimethylsilane-diylbis(2-methyl-4,5-benzoindenyl)zirconium dichloride were dissolved in 32 cm3 of a toluene solution of methyl-aluminoxane (50 mmol) and introduced into the reactor. The polymerization was carried out in first step for 8 hours at 60° C. In a second step, 2.8 kg of ethylene were added rapidly at 47° C. and, after polymerization for a further 5 hours at this temperature, the polymerization was completed by discharging the reactor contents into a 280 l reactor containing 100 l of acetone. The polymer powder was separated off and dried for 48 hours at 80° C./200 mbar. 21.4 kg of block copolymer powder were obtained. VI=359 cm3/g; Mw=402,000 g/mol, M2/Mn=4.0; MFI (230/5)=9.3 dg/min. The block copolymer contained 12.2% by weight of ethylene. Fractionation gave a content of 31.5% by weight of ethylene/propylene rubber and 3.7% by weight of atactic polypropylene, with a VI of 117 cm3/g in the polymer as a whole.
The procedure was as in Examples 1-16, but the metallocene was the compound meso-Me2Si(2-methyl-4-(1-naphthyl)-1-indenyl)2ZrCl2. The results are collated in Table 4.
The procedure was as in Example 32, but the metallocene was Ph(Me)Si(2-methyl-4-phenyl-1-indenyl)2ZrCl2 and was employed as a 1:1 meso:rac mixture. The results are collated in Table 5.
Fractionation of the polymer samples by ether extraction gave contents of atactic polypropylene of 3.6% by weight (polymerization temperature of 50° C.) and 7.0% by weight (polymerization temperature of 70° C.). The VI values were 158 and 106 cm3/g respectively.
The isolated atactic component had an elastomeric consistency and was completely transparent.
The polymer powder obtained from the polymerization is non-tacky, and moldings produced therefrom have a good surface, are very transparent and do not exhibit fogging.
The process was as in Example 32, but the metallocene used was rac/meso-Me2Si(2-methyl-4-phenyl-1-indenyl)2ZrCl2 in supported form, with a rac:meso ratio of 1:1. The supported metallocene was prepared in the following way:
a) Preparation of the supported cocatalyst
Polymerization were carried out in a manner comparable to the above examples using 1:1 rac:meso mixtures of metallocenes not according to the invention at polymerization temperatures of 70° C. and 30° C. The resultant polymers were likewise subjected to ether separation in order to characterize the polymer components. The results are collated in Table 6 and show that in no case could a polymer according to the invention having a high-molecular-weight atactic polymer component (ether-soluble component) be prepared. Products are generally tacky, and the moldings produced therefrom are soft, have a speckled surface and exhibit considerable fogging.
Comparative Examples 1 to 10 were repeated using the pure meso-forms of the metallocenes used therein. Atactic polypropylene was obtained, but in no case was a viscosity index VI of >70 cm3/g obtained. These metallocenes which are not according to the invention can thus not be used to prepare high-molecular-weight atactic polypropylene. The products are liquid or at least soft and highly tacky.