CA2055397C - Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers - Google Patents
Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers Download PDFInfo
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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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
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Abstract
Abstract of the disclosure Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers Polymers of polycyclic olefins, such as, for example, norbornene or tetracyclododecene, or copolymers of polycyclic olefins with cycloolefins and/or 1-olefins are obtained without ring opening, in high space-time yield, with a high cycloolefin incorporation rate and at in-dustrially favorable polymerization temperatures, by bulk polymerization in which a catalyst is used which comprises an aluminoxane and a stereorigid chiral metal-locene compound of an element from groups IVb to VIb, where the hydrocarbon radicals forming the sandwich structure are different.
Description
HOECHST AKTIENGESELLSCHAFT HOE 90/F 339 Dr.LO/pe Description Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers The invention relates to a process for the preparation of homopolymers and copolymers of polycyclic olefins in Which ring opening does not take place.
It is known that polycyclic olefins can be polymerized by means of various Ziegler catalysts. Depending on the catalyst, the polymerization proceeds via ring opening (cf. US 4,178,424) or opening of the double bond (cf.
EP-A 156 464 and EP-A 283 164).
The disadvantage of ring-opening polymerization is that the polymer obtained contains double bonds which can result in chain crosslinking and thus considerably limit the processability of the material by extrusion or injection molding.
Polymerization of cyclic olefins with opening of the double bond results in a relatively low polymerization rate (conversion rate).
A certain increase in the reaction rate has been achieved by using soluble metallocene compounds such as bis ( cyclo-pentadienyl)zirconium dichloride (cf. JP 61/221,206).
Catalysts which can be employed for cyclic olefins are stereorigid, chiral metallocene compounds, such as, for example, ethylenebis(indenyl)zirconium dichloride (cf.
EP-A 283 164) or dimethylsilylbis(indenyl)zirconium dichloride (cf. ZA 90/5308), with the polymerization taking place With retention of the ring.
It is known that polycyclic olefins can be polymerized by means of various Ziegler catalysts. Depending on the catalyst, the polymerization proceeds via ring opening (cf. US 4,178,424) or opening of the double bond (cf.
EP-A 156 464 and EP-A 283 164).
The disadvantage of ring-opening polymerization is that the polymer obtained contains double bonds which can result in chain crosslinking and thus considerably limit the processability of the material by extrusion or injection molding.
Polymerization of cyclic olefins with opening of the double bond results in a relatively low polymerization rate (conversion rate).
A certain increase in the reaction rate has been achieved by using soluble metallocene compounds such as bis ( cyclo-pentadienyl)zirconium dichloride (cf. JP 61/221,206).
Catalysts which can be employed for cyclic olefins are stereorigid, chiral metallocene compounds, such as, for example, ethylenebis(indenyl)zirconium dichloride (cf.
EP-A 283 164) or dimethylsilylbis(indenyl)zirconium dichloride (cf. ZA 90/5308), with the polymerization taking place With retention of the ring.
The current state of the art is to carry out the homopolymerization and copolymerization of cycloolefins in solution in the presence of soluble metallocene catalysts, with the solvents employed principally being hydrocarbons.
Experiments have shown that, under the polymerization conditions corresponding to the state of the art, in solution and at relatively low pressures, which are generally below 10 bar, the space-time yield (reaction rate) decreases With increasing concentration of the cycloolefin in the reaction medium, ie. also with in-creasing incorporation rate of the cycloolefin. Examples of corresponding cycloolefins are norbornene and tetra-cyclododecene. The low space-time yield at the same time as a high cycloolefin incorporation rate makes the preparation of cycloolefin copolymers having a high cycloolefin content very complex arid economically un-favorable.
Due to their high glass transition temperature, cyclo-olefin copolymers having a high incorporation rate of cycloolefin have a very high heat distortion temperature.
They are therefore interesting materials which should advantageously be usable as thermoplastic molding compo-sitions or in the form of solutions for surface coatings.
However, experiments have shown that such solutions can only be processed at high temperatures, in particular due to their tendency to gel.
The object was therefore to find a process for the preparation of cycloolefin homopolymers and copolymers which, based on the polymerization via the double bond, gives, at a high space-time yield, copolymers which have a high cycloolefin incorporation rate and do not gel in solution at room temperature.
It has been found that this ob ject can be achieved by selecting certain reaction conditions and using certain 2Q5539'~
Experiments have shown that, under the polymerization conditions corresponding to the state of the art, in solution and at relatively low pressures, which are generally below 10 bar, the space-time yield (reaction rate) decreases With increasing concentration of the cycloolefin in the reaction medium, ie. also with in-creasing incorporation rate of the cycloolefin. Examples of corresponding cycloolefins are norbornene and tetra-cyclododecene. The low space-time yield at the same time as a high cycloolefin incorporation rate makes the preparation of cycloolefin copolymers having a high cycloolefin content very complex arid economically un-favorable.
Due to their high glass transition temperature, cyclo-olefin copolymers having a high incorporation rate of cycloolefin have a very high heat distortion temperature.
They are therefore interesting materials which should advantageously be usable as thermoplastic molding compo-sitions or in the form of solutions for surface coatings.
However, experiments have shown that such solutions can only be processed at high temperatures, in particular due to their tendency to gel.
The object was therefore to find a process for the preparation of cycloolefin homopolymers and copolymers which, based on the polymerization via the double bond, gives, at a high space-time yield, copolymers which have a high cycloolefin incorporation rate and do not gel in solution at room temperature.
It has been found that this ob ject can be achieved by selecting certain reaction conditions and using certain 2Q5539'~
metallocene catalysts. It is important that the polymeri zation is carried out in the liquid cycloolefin itself or in extremely concentrated cycloolefin solutions, the temperature expediently being above room temperature and the pressure above 1 bar.
The invention thus relates to a process for the preparation of a cycloolefin polymer or copolymer by polymerization of from 0.1 to 100% by weight, based on the total amount of monomers, of at least one monomer of the formula I, II, III, IV, V or VI
~H ' Rl HC' -[ CH
( (I).
HC' IH /CH\ RZ
/ CH ~ /. CHZ
HC I CH
C R4 I CH2 (II).
HC ~ I / CH ,~
CH CHZ
/ CH ' / ~ ' R1 HC I CH , CH~
C R4 I R5 C R6 ~ (III).
HC~ ( / CH ~ I ~ CH 'R2 HC/CH.~ H/. CH ~~ CH_CH/Rx R3~C-R4 ( R5-C"R6 I R~'C'R8 ( (IV).
HC' ~H/CH~'H./~CH' IH/'/~~RZ
205539'7 RS
cx ~H Rl HC / I \ CH / 'CH
R3 C R4 ~ (V).
HC ~ CH CH
~.. R2 ~6 RS
HC~ CH '~/~~~~ CH.~~/R
R3 C R4 ~ I R~'C'RB I (VI), HC' IH/CH' ~ /CH~ ! ~C ~R2 ~6 R
in Which R1, RZ, R3, R4, R5, Re, R' and R8 are identical or different and are a hydrogen atom or a Cl-C8-alkyl radi-cal, it being'possible for identical radicals in the different formulae to hare different meanings, from 0 to 99.9% by weight, based on the total amount of monomers, of a cycloolefin of the formula v~I
CH ~ CH
(CHZ)n (VII), in Which n is a number from 2 to 10, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula to vim Rg R10 'C~C~ (VIII).
Rll in which R°, R1°, R11 and Rlz are identical or different and are a hydrogen atom or a Cl-CB-alkyl radical, at temperatures of from 20 to 150°C and at a pressure of from 0.01 to 64 bar, in the presence of a catalyst which comprises an aluminoxane of the formula IX
~ A1 - O A1 - O Al (IX) R13~ ~. R13 n for the linear type and/or of the formula X
I
A1 - (X) n+2 for the cyclic type, where, in the formulae IX and X, R13 is a C1-C6-alkyl group, phenyl or benzyl, arid n is an integer.
from 2 to 50, and a met:allacene of the f_ormul_a XI
i R14 R18 M1~ (XI ) ~ ~°'' R 15 ~' 17 R
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R14 and R15 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1 C10-alkoxy group, a C~-C1p-aryl group, a C'.6-C10-aryloxy group, a C2-C10-alkenyl group, a C~-C40-aryla.lkyl group, a C~-C40-alkylaryl group, or a Cg-C40-arylalkenyl group, R16 and R1~ are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M1, 20~539'~
The invention thus relates to a process for the preparation of a cycloolefin polymer or copolymer by polymerization of from 0.1 to 100% by weight, based on the total amount of monomers, of at least one monomer of the formula I, II, III, IV, V or VI
~H ' Rl HC' -[ CH
( (I).
HC' IH /CH\ RZ
/ CH ~ /. CHZ
HC I CH
C R4 I CH2 (II).
HC ~ I / CH ,~
CH CHZ
/ CH ' / ~ ' R1 HC I CH , CH~
C R4 I R5 C R6 ~ (III).
HC~ ( / CH ~ I ~ CH 'R2 HC/CH.~ H/. CH ~~ CH_CH/Rx R3~C-R4 ( R5-C"R6 I R~'C'R8 ( (IV).
HC' ~H/CH~'H./~CH' IH/'/~~RZ
205539'7 RS
cx ~H Rl HC / I \ CH / 'CH
R3 C R4 ~ (V).
HC ~ CH CH
~.. R2 ~6 RS
HC~ CH '~/~~~~ CH.~~/R
R3 C R4 ~ I R~'C'RB I (VI), HC' IH/CH' ~ /CH~ ! ~C ~R2 ~6 R
in Which R1, RZ, R3, R4, R5, Re, R' and R8 are identical or different and are a hydrogen atom or a Cl-C8-alkyl radi-cal, it being'possible for identical radicals in the different formulae to hare different meanings, from 0 to 99.9% by weight, based on the total amount of monomers, of a cycloolefin of the formula v~I
CH ~ CH
(CHZ)n (VII), in Which n is a number from 2 to 10, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula to vim Rg R10 'C~C~ (VIII).
Rll in which R°, R1°, R11 and Rlz are identical or different and are a hydrogen atom or a Cl-CB-alkyl radical, at temperatures of from 20 to 150°C and at a pressure of from 0.01 to 64 bar, in the presence of a catalyst which comprises an aluminoxane of the formula IX
~ A1 - O A1 - O Al (IX) R13~ ~. R13 n for the linear type and/or of the formula X
I
A1 - (X) n+2 for the cyclic type, where, in the formulae IX and X, R13 is a C1-C6-alkyl group, phenyl or benzyl, arid n is an integer.
from 2 to 50, and a met:allacene of the f_ormul_a XI
i R14 R18 M1~ (XI ) ~ ~°'' R 15 ~' 17 R
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R14 and R15 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1 C10-alkoxy group, a C~-C1p-aryl group, a C'.6-C10-aryloxy group, a C2-C10-alkenyl group, a C~-C40-aryla.lkyl group, a C~-C40-alkylaryl group, or a Cg-C40-arylalkenyl group, R16 and R1~ are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M1, 20~539'~
R18 is Rl9 R19 Rl9 R19 R19 19 R19 R19 -M2- . -M2~M2_ , -M2-Cg21_, _C- , _p-M2- , ..~iC- .
R20 R20 R20 R20 R20 ~20 R20 R20 =BR ~=A1R19, -Ge-, -Sn-, -O-, -S-, =SO, =SOz, =NR19, =CO, =PRl9 or =P ( 0 ) R18 where R18, Rio and RZ' are identical or different and are a hydrogen atom, a halogen atom, a C1-C1°-alkyl group, a C1-Clo-fluoro-alkyl group, a CB-Cl°-fluoroaryl group, a CB-Cl°-aryl group, a C1-Cl°-alkoxy group, a CZ-C1°-alkenyl group, a C~-C4o-arylalkyl group, a Ce-C4°-arylalkenyl group or a C~-C4°-alkylaryl group, or R1s and R2° or R19 and R21, in each case with the atoms connecting them, form a ring, and MZ is silicon, germanium or tin, which comprises carrying out the polymerization in the liquid cycloolefin monomer or cycloolefin monomer mixture or in an at least 95 percent by volume cycloolefin solution, the substituents R1B and Rl' in the formula KI being different from one another.
The polymerization is preferably carried out in the liquid cycloolefin monomer or cycloolefin monomer mix ture.
In the process according to the invention, at least one polycyclic olefin of the formula I, II, III, IV, V or VI, preferably a cycloolefin of the formula I or ITI, in which R1, RZ, R3, R~, Rs, Re, R' and R8 are identical or different and nre a hydrogen atom or a Cl-Ce-alkyl radi-cal, where identical radicals in the different formulae may have different meanings, is polymerized.
It is also possible to use a monocyclic olefin of the formula VII
20~~~9°~
cx = cx (CH2)n wzI), in which n is a number from 2 to 10. Another comonomer is an acyclic 1-olefin of the formula VIII
~C =C / ' (VIII), R11 ~ R12 in which Rs, Rl°, Rll and R12 are identical or different and are a hydrogen atom or a C1-Ce-alkyl radical. Ethylene or propylene is preferred.
In particular, copolymers of polycyclic olefins, prefer-ably of the formula I or III, with the acyclic olefins VIII are prepared.
Particularly preferred cycloolefins are norbornene and tetracyclododecene, it being possible for these to be substituted by (Cl-CB)-alkyl. They are preferably copoly-merized with ethylene; ethylene-norbornene copolymers are particularly important.
The polycyclic olefin (I to VI) is employed in an amount of from 0.1 to 100% by weight, and the monocyclic olefin (VII) is employed in an amount of from 0 to 99.9% by weight, in each case based on the total amount of monomers.
The concentration of the open-chain olefin arises from the solubility of the open-chain olefin in the reaction medium at the given pressure and given temperature.
Polycyclic olefins, monocyclic olefins and open-chain 205~~9'~
- g -olefins are also taken to mean mixtures of two or more olefins of the respective type. This means that, besides polycyclic homopolymers and bicopolymers, it is also possible to prepare tercopolymers and multicopolymers by the process according to the invention. Copolymers of the cycloolefins VII with the acyclic olefins VIII can also advantageously be obtained by the process described. Of the cycloolefins VII, cyclopentene, which may be substituted, is preferred.
The catalyst to be used for the process according to the invention comprises an aluminoxane and at least one metallocene (transition-metal component) of the formula XI
~ R14 ~'1~
R M
(XI).
~~~R15 \ X17 In the formula XI, Mi is a metal from the group compris-ing titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zircanium or hafnium. Zirconium is particularly preferred.
R1° and Ris are identical or different and are a hydrogen atom, a C1-Clo-, preferably C1-Ca-alkyl group, a Cl-Clo-, preferably Ci-C3-alkoxy group, a CB-Clo-, preferably CB-Ce-aryl group, $ Cs-Clo, preferably Cg-Ce-aryloxy group, a CZ-Clo-, preferably C2-C4-alkenyl group, a C~-Coo-.
preferably C~-Clo-arylalkyl group, a C~-Coo-, preferably C~-Cl2-alkylaryl group, a Ce-C4o-, preferably Ce-C12-aryl-alkenyl group or a halogen atom, preferably chlorine.
R18 and R1' are different and are a monocyclic or poly-cyclic hydrocarbon radical, which can form a sandwich structure with the central atom M1. R1° is preferably fluorenyl and R1' is preferably cyclopentadienyl.
_ g _ R18 is a single- or multimembered br~_dge which links the radicals R16 and R17 and is preferably -M2- ~ ~ 2 ~ 2- ~ 2 21 ~ ~ 2--M -M , -M -CR2 - , -C- , -O-M , -C-C- , =BR19=AlRl9, -Ge--, -Sn-, -O-, -S-, =SC), =502, =NR19, =CO, =PR19 or =P(O)R1'~ where R19, R2p and R21 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C~-C1p-fluoroalkyl group, a C6-Clp-aryl group, a Cl-Clp-alkoxy group, a C2-Cep--alkenyl group, a C7-C4p-arylalkyl group, a Cg-C4p-arylalkenyl group or a C7-C4p-alkylaryl group, or R19 and R2~~ or R1f and R21, in each case together with the atoms connecting them, ferm a ring.
I
R18 is preferably an R19-C-R2p radical and is particularly preferably CH3-C-CH3 or I _~ 1 O .
r~2 is silicon, germanium or tin, preferably silicon or germanium.
The bridged metallocenes can be prepared in accordance with the known reaction scheme below:
H2R16 + ButylLi -~ HRl6Li X _ R18 X
H2R17 + ButylLi -~ HRl7Li HR16 - R18 - R17H + 2-Butyl-Li -LiRl6 - R18 - Rl7Li + M1C14 // I'C1 18 ~ ~ 1/
R M
(XI) ''~'''~ C 1 R17.
2~~~39'~
or H2R16 ø ButylLi -~ HRl6Li , C/ a, IiRh R19R20C
R18 b, H2~ ~R16H
2 ButylLi R19R20C Li2 ~R16 R19 S ~ Cl ,i ' C M1 R20~ ~~ ~Cl Rl4Li Rlg ~ ~ /R14 R19 ~ ~R14 ~C IHl R15L1 'C Ml (XI ) R20~ '; 'wCl ~ R20~ ~ ~ ~R15 The reaction scheme above also applies to the case where Rse s Rzo and/or Rl" ~ Ris ( c f . Journal of Organometallic Chem. 288 (1985) 63-67 and EP-A 320 762).
Preferred metallocenes are:
diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride, isopropylene(9-fluorenyl)cyclopentadienylzirconium ~a~~~97 11 _ dichloride, methyl(phenyl)methylene(9-fluorenyl)cyclopentadienylzir-conium dichloride and diphenylmethylene(9-fluorenyl)cyclopentadienylhafnium dichloride, or mixtures thereof.
Particular preference is given to:
diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride.
The cocatalyst is an aluminoxane of the formula IX .
\A1- 0 A1 - 0 A1/ ( IX) R13 / ~R13 n for the linear type and/or of the formula X
Al - 0 (X) n+2 for the cyclic type. In these formulae, R13 is a C1-Ca-alkyl group, preferably methyl, ethyl, isobutyl, butyl or neopentyl, or phenyl or benzyl. Particular preference is given to methyl. n is an integer from 2 to 50, preferably from 5 to 40. However, the precise structure of the aluminoxane is not known.
The aluminoxane can be prepared in vnrious ways (cf.
8. Pasynkiewicz, Polyhedron $ (1990) 429).
In one of the processes, finely powdered copper sulfate pentahydrate is 8lurried in toluene or a cycloolefin (for example cyclopentene, norbornene or tetracyclododecene), and sufficient trialkylaluminum to give about 1 mol of 294?8-1 CuSO4.5H2o for every 4 aluminum atoms is added in a glass flask under an inert gas at about -20°C or just above the melting point of the cycloolefin. After slow hydrolysis with elimination of alkane, the reaction mixture is left at room temperature for from 24 to 48 hours, during which it may be necessary to cool the mixture so that the temperature does not exceed 30°C. The aluminoxane, dissolved in the toluene or cycloolefin, is subsequently filtered off from the copper sulfate, and the solution is evaporated in vacuo. It is assumed that the low-molecu-lar-weight aluminoxanes condense in this preparation process to form higher oligomers with elimination of trialkylaluminum.
Aluminoxanes are also obtained when trialkylaluminum, preferably trimethylaluminum, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted with aluminum salts, preferably aluminum sulfate, containing water of crystallization at a temperature of from -20 to 100°C. The ratio by volume between the solvent and the alkylaluminum used is from 1:1 to 50:1, preferably 5:1, and the reaction time, which can be monitored through the elimination of the alkane, is from 1 to 200 hours, preferably from 10 to 40 hours.
Of the aluminum salts containing water of crystalliza-tion, those are used, in particular, which have a high content of water of crystallization. Particular preference is given to aluminum sulfate hydrate, in particular the compounds A12(S04)3.1E~H20 and A12(SO4)3.18H2o, having the particularly high water of crystallization content ref.. 16 and 18 mol respectively of H20/mol of Al2(S04)3.
A further variant of the preparation of aluminoxanes is to dissolve trialkylaluminum, preferably trimethyl-aluminum, in the liquid monomer in heptane or toluene in the polymerization reactor, and then to react the alumi-num compound with water.
205539' It is also possible for the aluminoxane to be adsorbed onto a support and then employed as a suspension in supported form. Several support processes are known. For example, slightly moist silica gel can act as a support.
In addition to the above-outlined processes for the preparation of aluminoxanes, there are others which can be used. Irrespective of the type of preparation, a varying content of unreacted trialkylaluminum, which is in free form or as an adduct, is connaon to all the aluminoxane solutions. This content has an as yet not precisely explained effect on the catalytic activity, which varies depending on the metallocene compound employed.
If preactivation of the transition-metal compound is necessary, it is carried out in solution. In this case, the metallocene is preferably dissolved in a solution of the aluminoxane in a hydrocarbon. Suitable hydrocarbons are aliphatic yr aromatic hydrocarbons and cycloolefins, such as, for example, cyclopentene, norbornene or tetra cyclododecene.
Toluene is preferred.
The preactivation can also be carried out in suspensions of supported aluminoxane.
The concentration of the aluminoxane in the solution is in the range from about 1% by weight up to the saturation limit, preferably from 5 to 30% by weight, in each case based on the total solution. The metallocene can be employed in the same concentration, but is preferably employed in an amount of from 10-"-1 mol per mole of aluminoxane. The preactivation time is from 0 to 60 minutes. The preactivation temperature is from 0 to 70°C.
If a small amount of solvent is added to the reaction mixture, the solvent is a customary inert solvent, such 205~39'~
as, for example, an aliphatic or cycloaliphatic hydrocar-bon, a petroleum ether or hydrogenated diesel oil fraction, or toluene.
Polymerization by the process according to the invention offers the advantage of achieving a high space-time yield (reaction rate) and a high cycloolefin incorporation rate . It has been found that increasing the concentration of the open-chain olefin, for example by increasing the partial pressure of this open-chain olefin, allows the reaction rate to be significantly increased. If pure open-chain olefin, for example ethylene, is injected, pressures of between 0.01 and 64 bar, preferably from 2 to 40 bar and particularly preferably from 4 to 20 bar, are employed. If an inert gas, for example nitrogen or argon, is also injected in addition to the open-chain olefin, the total pressure in the reaction vessel is from 2 to 64 bar, preferably from 5 to 64 bar and particularly preferably from 6 to 40 bar. The fact that the cyclo-olefinic component is in undiluted form means that a high cycloolefin incorporation rate is achieved even at high pressures. In addition, the reaction rate can also be increased by increasing the temperature, the upper limit to the temperature range being set by the thermal stabil-ity of the catalyst and the lower limit by the melting point of the cycloolefin at the correspanding pressure.
However, increasing temperature is accompanied by a simultaneous drop in the solubility of the gaseous olefin in the reaction medium and results in an increase in the incorporation rate of the cycloolefin in the copolymer.
In order to obtain constant incorporation rates with incrensing temperature, the pressure of the open-chain and gaseous olefin must be increased correspondingly.
Continuous and multistep polymerization processes are particularly advantageous since they enable efficient use of the cycloolefin. In continuous processes, the poly-cyclic olefin, which can arise as a residual monomer together with the polymer, can also be recovered and recycled into the reaction mixture.
Here, the process according to the invention offers the advantage over polymerization in solution that, due to the absence of a solvent or an extremely low solvent concentration, the technical complexity on recovery of the cycloolefins from the reaction mixture or from a precipitation bath is much lower.
The metallocene compound i.a used in a con~~~at.rat a c~r-_ based on the transition metal, of from l0-3 to l0-7, preferably from 10-4 to 10-6, mol of transition metal per dmWof reactor volume. The al~uminox~ne is used in a con-centration of from 10-4 to LOwl, preferably from 10-4 to 2.10-2 mol per dm3 of reactor volume, based on the aluminum content. 1n t~rinciple, hawever, higher con-centrations are also possible. In order to combine the polymerization properties of different metallocenes, it is possible to employ mixtures of a plurality of metallocenes.
When preparing copolymers, the molar ratios between the polycyclic olefin and the open-chain olefin (preferably) employed can be varied within a broad range. Molar ratios of from 3:1 to 100:1 of cycloolefin to open-chain olefin are preferably employed. The choice of polymerization temperature, the concentration of the catalyst component and the molar ratio employed or the pressure of the gaseous, open-chain olefin allow the incorporation rate of comonomer to be controlled virtually as desired.
Preferred incorporation rates are between 20 and 75 mol-~
of the cyclic component and particularly preferred incor-poration rates are between 35 and 65 mol-~k of the cyclic component.
The mean molecular weight of the copolymer formed can be controlled in a known manner by metering in hydrogen, varying the catalyst concentration or. varying the temper ature.
2~~5~~'~
The polydispersity 1~,/Mn of the copolymers is extremely narrow, with values between 2.0 and 3.5. This results in a property profile of the polymers which makes them particularly suitable for injection molding.
Surprisingly, it has been found that the bulk process according to the invention, for the same incorporation rates and comparable reaction rates, results in higher molecular weights than does conventional solution poly-merization.
If the possibilities of varying the molecular weight are taken into account, the process according to the inven-tion significantly broadens the accessible molecular weight range fox the cycloolefin copolymers.
The preferred catalysts according to the invention result, both in "solution polymerization" and in bulk polymerization, in significantly higher molecular weights than do other metallocene catalysts known hitherto.
The process described allows amorphous copolymers to be pxepared. The copolymers are transparent and hard. They are soluble, for examplQ, in decahydronaphthalene at 135°C and in toluene at room temperature. The polymers according to the invention can be processed as ther moplastics. Both on extrusion and on injection molding, no significant degradation or decrease in viscosity was found.
Surprisingly, it has been found that the cycloolefin copolymers prepared using the process according to the invention - and the preferred metallocenes according to the invention - do not gel in solution at room tempera-ture. They are therefore particularly suitable for coatings, for the production of cast films and for other applications in which cycloolefin solutions must be stored and transported. The flowability of the corres-ponding solutions also has a positive effect on the ~fl~~~~'~
work-up of the polymer solutions after the polymeriza tion. For example, the solution can be filtered more easily; concentration in a thin-film evaporator can be carried out with lower thermal and mechanical stress of the polymer solution.
Furthermore, it has been determined from Nl~t spectra that these cycloolefin copolymers also differ significantly in their microstructure from those which gel in solution.
This difference could be explained by the fact that the catalysts according to the invention polymerize strictly syndiospecifically due to the different R18 and R1' sub-stituents. according to the current state of knowledge, it must be assumed that the cycloolefin copolymers according to the invention contain disyndiotactic cyclo-olefin sequences which enable structures to be differen-tiated by NMR.
The materials prepared according to the invention are particularly suitable for the production of extruded parts, such as films, tubes, pipes, rods and fibers, and for the production of injection moldings of any desired shape and size. An important property of the materials according to the invention is their transparency. The optical applications, in particular, of the extruded or injection-molded parts of these materials thus have considerable importance. The refractive index, determined using an Abbe refractometer and mixed light, of the "
reaction products described in the examples below is in the range from 1.520 to 1.555. Since the refractive index is very close to that of crown glass (n ~ 1.51), the products according to the invention can be used in a variety of ways as a glass substitute, such as, for example, for lenses, prisms, baseplates and films for optical data media, for video disks, for compact disks, as cover and focusing screens for solar cells, as cover and diffusion screens for high-performance ogtics, and as optical waveguides in the form of fibers or films.
~0~53~7 The polymers according to the invention can also be employed for the preparation of polymer alloys. The alloys can be prepared in the melt or in solution. The alloys each have a favorable property combination of the components for certain applications. The following polymers can be employed for alloys containing the polymers according to the invention:
polyethylene, polypropylene, (ethylene-propylene) copoly-mers, polybutylene, poly(4-methyl-1-pentene), polyiso-prone, polyisobutylene, natural rubber, poly(methyl methacrylate), further polymethacrylates, polyacrylates, (acrylate-methacrylate) copolymers, polystyrene, (styrene-acrylonitrile) copolymers, bisphenol A poly-carbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, amorphous polyarylates, nylon 6, nylon 66, further polyamides, polyaramids, polyether ketones, polyoxymethylene, ,polyoxyethylene, polyurethanes, poly-sulfones, polyether sulfones and polyvinylidene fluoride.
The glass transition temperatures (Tg) given in the examples below were determined by DSC (Differential Scanning Calorimetry) at a heating rate of 20'C/min. The viacosities given were determined in accordance with DIN 53 728.
Example 1 A clean and dry 1.5 dm3 polymerization reactor equipped with stirrer was flushed with nitrogen and then with ethylene and charged with 560 g of norbornene melt at 70'C. The reactor was then kept at a temperature of 70°C
with stirring, and 6 bar of ethylene (overpreasure) were injected.
5 cma of a toluene solution of methylaluminoxane (MAO
solution) (10.1% by weight of methylaluminoxane having a molecular weight of 1300 g/mol, determined cryoscopically) were then metered into the reactor, and the mixture was stirred at 70°C for 15 minutes, with the ethylene pressure being kept at 6 bar by re-metering. In parallel, 10.2 mg of diphenylmethylene(9-fluorenyl)-cyclopentadienylzirconium dichloride were dissolved in 5 cm3 of a toluene solution of methylaluminoxane (concentration and quality see above), and the solution was preactivated by standing for 15 minutes. The solution of the complex was then metered into the reactor (in order to reduce the molecular weight, hydrogen can be introduced into the reactor via a lock immediately after the metering-in of the catalyst). The mixture is then polymerized at 70°C for 0.5 hour with stirring (750 rpm), during which the ethylene pressure was kept at 6 bar by re-metering. The reactor contents were then discharged rapidly into a stirred vessel containing 100 cm3 of isopropanol. The mixture was introduced dropwise into 2 dm3 of acetone, the mixture was stirred for 10 minutes, and the suspended polymeric solid was then filtered off.
The polymer filtered off was then introduced into 2 dm3 of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol, and this suspension was stirred for 2 hours. The polymer was then filtered off again, washed with water until neutral and dried for 15 hours at 80'C and 0.2 bar. 40.4 g of product were obtained. A
viscosity of 112 cma/g and a glass transition temperature (Tg) of 183'C were measured on the product.
Examples 2 and 3 The polymerizations were carried out analogously to Example 1, with some conditions, summarized in Table 1, being changed.
205530' Table 1 Ex- Cyclo- Metal- Amount Ethy- Time Yield Visc. Tg ample olefin locene of lane (h) (g) (cm3/g) (°C) (g) metal- pres-s locene sure (mg) (bar) 2 Norbor- B 0.5 10 0.5 37 210 161.5 nene 3 DMON 400 A 10.0 6 0.3 31 135 206.9 A = Diphenylmethylene(9-fluorenyl)cyclopentadienyl-zirconium dichloride B = Isoprapylene(9-fluorenyl)cyclopentadienylzirconium dichloride DMON = Tetracyclododecene Example 4 A clean and dry 75 dm~ polymerization reactor equipped with stirrer was flushed with nitrogen and than with ethylene and charged with 22,000 g of norbornene melt (Nb). The reactor was then heated to a temperature of 70°C with stirring, and 15 bar of ethylene Were injected.
580 cm3 of a toluene solution of methylaluminoxane (10.1 by weight of methylaluminoxane having a molecular weight of 1300 g/mol, determined cryoscopically) were then metered into the reactor, and the mixture was stirred at 70°C for 15 minutes, during wYtich the ethylene pressure Was kept at 15 bar by re-metering. In parallel, 500 mg of metallocene A were dissolved in 500 cm3 of a toluene solution of methylaluminoxane (concentration and guality see above), and the solution was preactivated by standing for 15 minutes. The solution of the complex (catalyst solution) was then metered into the reactor (in order to reduce the molecular weight, hydrogen can be introduced into the reactor via a lock immediately after the _ 21 _ 205539"
metering-in of the catalyst). The mixture was then polymerized at 70°C for 1.3 hours with stirring (750 rpm), during which the ethylene pressure was kept at 15 bar by re-metering. The reactor contents were then discharged rapidly into a stirred vessel containing 200 cm3 of isopropanol (as stopper). The mixture was precipitated in acetone, the precipitate was stirred for minutes, and the suspended polymeric solid was then filtered off.
10 The polymer filtered off was then treated with a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol, and the mixture was stirred for 2 hours. The polymer was then filtered off again, washed with water until neutral and dried for 15 hours at 80°C and 0.2 bar.
5500 g of product were obtained. A viscosity of 163 cm3/g and a glass transition temperature (Tg) of 144°C were measured on the product.
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O (To d' N ~O1~1tt1O~M O
1 H m -1 r1v-W-1r1 r1N N
r1 i~ U
'b t~ p .f. O 'C1 O O O O O O O O
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~
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p a b o w o o m o a o d'~ d'M 10~ N
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I 1 r1 .r ro+~p t~~ 0 0 0 0 0 0 0 o b p ~ p ~ 'n~nm ~nu~
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~ ~ O p ~ N N Ir1N 'O
~ 41~ ~ M "i ' ' ~'1 C .-I_ r ~
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r-1C,' 1 b d p ' ~ U ~ ~ a1GO alchi~
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~ d H ~ ~ ~ n ufo aoo ~;u~ 'd~r prGO. i .-1.'1 r1 N O r-1b R r-1 v V ..
, , o o o o 3 trl H ~ l u n l~. . . h ~ b t e~ r l tr .. p x .. ~
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,$ <v o 0 0 0 0 0 o a ,1,~ .~.I O H ~ 00 000 000 o w ~ ,~t~
4-IQ d d~ d~N d~N N N N O
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4) r1N N N G) r1r-1 ~ W G s3 u1+1 W N p 4 ~ O
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.Gib ltl U O r1N
W H H H w u~ --W o 1~oorn .-i~ .-~*
205539'7 Comparative Example 13 (solution polymerization) A clean and dry 1.5 dm3 polymerization reactor equipped with stirrer was flushed with nitrogen and then with ethylene and charged with a solution of 411 g of norbor-none (Nb) and 86 cm3 of toluene. The reactor was then heated to a temperature of 70°C with stirring and 8 bar of ethylene were injected.
20 cm3 of a toluene solution of methylaluminoxane (10.1%
by Weight of methylaluminoxane having a molecular Weight of 1300 g/mol, determined cryoscopically) were then metered into the reactor, and the mixture was stirred at 70°C for 15 minutes, during which the ethylene pressure was kept at 8 bar by re-metering. In parallel, 71.8 mg of dicyclopentadienylzirconium dichloride were dissolved in 10 cma of a toluene solution of methylaluminoxane (concentration'and quality see above), and the solution was preactivated by standing for 15 minutes. The Solution of the complex was then metered into the reactor. The mixture was then polymerized at 70°C for 2 hours with stirring ( 750 rpm) , during which the ethylene pressure was kept at 8 bar by re-metering. The reactor contents were then discharged rapidly into a stirred vessel containing 100 cma of iaopropanol. The mixture was intro-duced dropwise into 2 dm~ of acetone, the mixture was stirred for 10 minutes, and the suspended polymeric Solid was then filtered off.
The polymer filtered off was then introduced into 2 dm3 of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol, and this suspension was Stirred for 2 hours. The polymer was then filtered off again, washed with water until neutral and dried for 15 hours at 80°C and 0.2 bar. 73.5 g of product were obtained. A
viscosity of 17 cma/g and a glass transition temperature (Tg) of 168.5°C were measured on the product.
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Example 17 20% strength by weight toluene solutions of each of the polymers of Examples 4 and 6 to 9 were prepared in 250 ml flasks at 70°C. The solutions were clear and free-flow-ing. The flowability of the solutions was determined by tilting the flasks. After the solutions had been cooled to room temperature, the flowability was determined as a function of time. All the solutions investigated were still free-flowing after 50 days.
Comparative Example 18 Solutions of various polymers prepared in accordance with Comparative Examples 5 and 13 to 16 were prepared and investigated analogously to Example 17. All the solutions were no longer free-flowing after only 8 hours at room temperature. All the solutions had gelled, ie. they remained shape-stable in the tilt experiment.
Example 19 GPC (Gel Permeation Chromatography) measurements were carried out on various samples. A Millipore Waters Chrom.
type 150-C ALC/GPC chromatograph and a column set comprising 4 Shodex AT-80 M/S columns were used. The solvent was o-dichlorobenzen~.
Other measurement parameters werea Temperature: 135°C
Z5 Flow rate: 0.5 ml/min Amount of sample: 0.4 ml of sample solution Concentration of the sample solutions 0.1 g/dl Calibration: by polyethylene standard The GPC measurement results are as follows:
- 26 - ~0~~~~~
Sample Weight average 1~, No . average M",/M"
g/mol M"
g/mol According to 75,600 37,200 2 Comparative Example 5 According to 391,000 163,000 2.4 Example 7 Example 20 la-C-NMR spectra were recorded for samples from Examples 4 to 7. The samples were dissolved in a mixture of hexachlorobutadiene and tetrachloroethane-d2 and measured using a 400 l~iz NMR instrument. The spectra are repro-duced comparatively in Figure 1. Surprisingly, it can be seen that the structure of the polymers of Examples 4, 6 and 7 differs~significantly from that of Comparative Example 5.
In the case of the metallocene C ( rac-dimethylsilylbis ( 1 indenyl)zirconium dichloride) used in Comparative Example 5, the substituents R1° and Rl' are identical.
Examples 21 - 23 The polymerizations were carried out analogously to Example 1, with some conditions, summarized in Table 4, being changed.
- 27 _ Table 4 Ex- Cyclo- Metal- Amount Ethy- Time Yield Visc. Tg ample olefin locene of lene (h) (g) (cm3/g) (°C) (g) metal- pres-s locene sure (mg) (bar) 21 Norbor- E 1 6 1 36 119 178 none 22 Norbor- F 20 6 3 33 125 183 nene 23 Norbor- G 1 1.5 1 22 40 239 nene E = methyl(phenyl)methylene(9-fluorenyl)cyclopentadienyl zirconium dichloride F ~ diphenylmethylene(9-fluorenyl)cyclopentadienylhafnium dichloride G ' ieopropylene(1-indenyl)cyclopentadienylzirconium dichloride Example 24 (polynorbornene) 800 g of norbornene were liquefied with 25 cm3of a 10.1%
strength by weight toluene solution of methylaluminoxane with warming in a 1.5 dm3 polymerization reactor (see Example 1).
In parallel, 250 mg of diphenylmethylene(9-fluorenyl) cyclopentadienylzirconium dichloride were dissolved in 25 cm3 of a 10.1% strength toluene solution of methylalum inoxane, and the Solution was added to the above melt.
The mixture waS polymerized for 160 hours at 35°C under argon.
The solution was worked up analogously to Example 1.
After drying, 41 g of a colorless powder were obtained.
A viscosity of 44 cm3/g was measured on the product.
Neither a glass state nor a melting point were detectable _ 28 _ 20~539'~
up to 380°C using DSC. Softening was observable at about 400°C under a heating-stage microscope.
13C_NI~t spectrum (analogously to Example 20) showed very broad signals with peak maxima at 31, 40 and 50 ppm.
According to NMR and infra-red spectra, the product contains no double bonds.
Example 25 10-20% strength toluene solutions of the polymer from Example 24 Were prepared, and the solution was coated onto glass plates using a doctor blade. After drying in vacuo (0.2 bar) at 80°C, transparent, colorless films having thicknesses between 1 and 100 ~m wexe obtained.
R20 R20 R20 R20 R20 ~20 R20 R20 =BR ~=A1R19, -Ge-, -Sn-, -O-, -S-, =SO, =SOz, =NR19, =CO, =PRl9 or =P ( 0 ) R18 where R18, Rio and RZ' are identical or different and are a hydrogen atom, a halogen atom, a C1-C1°-alkyl group, a C1-Clo-fluoro-alkyl group, a CB-Cl°-fluoroaryl group, a CB-Cl°-aryl group, a C1-Cl°-alkoxy group, a CZ-C1°-alkenyl group, a C~-C4o-arylalkyl group, a Ce-C4°-arylalkenyl group or a C~-C4°-alkylaryl group, or R1s and R2° or R19 and R21, in each case with the atoms connecting them, form a ring, and MZ is silicon, germanium or tin, which comprises carrying out the polymerization in the liquid cycloolefin monomer or cycloolefin monomer mixture or in an at least 95 percent by volume cycloolefin solution, the substituents R1B and Rl' in the formula KI being different from one another.
The polymerization is preferably carried out in the liquid cycloolefin monomer or cycloolefin monomer mix ture.
In the process according to the invention, at least one polycyclic olefin of the formula I, II, III, IV, V or VI, preferably a cycloolefin of the formula I or ITI, in which R1, RZ, R3, R~, Rs, Re, R' and R8 are identical or different and nre a hydrogen atom or a Cl-Ce-alkyl radi-cal, where identical radicals in the different formulae may have different meanings, is polymerized.
It is also possible to use a monocyclic olefin of the formula VII
20~~~9°~
cx = cx (CH2)n wzI), in which n is a number from 2 to 10. Another comonomer is an acyclic 1-olefin of the formula VIII
~C =C / ' (VIII), R11 ~ R12 in which Rs, Rl°, Rll and R12 are identical or different and are a hydrogen atom or a C1-Ce-alkyl radical. Ethylene or propylene is preferred.
In particular, copolymers of polycyclic olefins, prefer-ably of the formula I or III, with the acyclic olefins VIII are prepared.
Particularly preferred cycloolefins are norbornene and tetracyclododecene, it being possible for these to be substituted by (Cl-CB)-alkyl. They are preferably copoly-merized with ethylene; ethylene-norbornene copolymers are particularly important.
The polycyclic olefin (I to VI) is employed in an amount of from 0.1 to 100% by weight, and the monocyclic olefin (VII) is employed in an amount of from 0 to 99.9% by weight, in each case based on the total amount of monomers.
The concentration of the open-chain olefin arises from the solubility of the open-chain olefin in the reaction medium at the given pressure and given temperature.
Polycyclic olefins, monocyclic olefins and open-chain 205~~9'~
- g -olefins are also taken to mean mixtures of two or more olefins of the respective type. This means that, besides polycyclic homopolymers and bicopolymers, it is also possible to prepare tercopolymers and multicopolymers by the process according to the invention. Copolymers of the cycloolefins VII with the acyclic olefins VIII can also advantageously be obtained by the process described. Of the cycloolefins VII, cyclopentene, which may be substituted, is preferred.
The catalyst to be used for the process according to the invention comprises an aluminoxane and at least one metallocene (transition-metal component) of the formula XI
~ R14 ~'1~
R M
(XI).
~~~R15 \ X17 In the formula XI, Mi is a metal from the group compris-ing titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zircanium or hafnium. Zirconium is particularly preferred.
R1° and Ris are identical or different and are a hydrogen atom, a C1-Clo-, preferably C1-Ca-alkyl group, a Cl-Clo-, preferably Ci-C3-alkoxy group, a CB-Clo-, preferably CB-Ce-aryl group, $ Cs-Clo, preferably Cg-Ce-aryloxy group, a CZ-Clo-, preferably C2-C4-alkenyl group, a C~-Coo-.
preferably C~-Clo-arylalkyl group, a C~-Coo-, preferably C~-Cl2-alkylaryl group, a Ce-C4o-, preferably Ce-C12-aryl-alkenyl group or a halogen atom, preferably chlorine.
R18 and R1' are different and are a monocyclic or poly-cyclic hydrocarbon radical, which can form a sandwich structure with the central atom M1. R1° is preferably fluorenyl and R1' is preferably cyclopentadienyl.
_ g _ R18 is a single- or multimembered br~_dge which links the radicals R16 and R17 and is preferably -M2- ~ ~ 2 ~ 2- ~ 2 21 ~ ~ 2--M -M , -M -CR2 - , -C- , -O-M , -C-C- , =BR19=AlRl9, -Ge--, -Sn-, -O-, -S-, =SC), =502, =NR19, =CO, =PR19 or =P(O)R1'~ where R19, R2p and R21 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C~-C1p-fluoroalkyl group, a C6-Clp-aryl group, a Cl-Clp-alkoxy group, a C2-Cep--alkenyl group, a C7-C4p-arylalkyl group, a Cg-C4p-arylalkenyl group or a C7-C4p-alkylaryl group, or R19 and R2~~ or R1f and R21, in each case together with the atoms connecting them, ferm a ring.
I
R18 is preferably an R19-C-R2p radical and is particularly preferably CH3-C-CH3 or I _~ 1 O .
r~2 is silicon, germanium or tin, preferably silicon or germanium.
The bridged metallocenes can be prepared in accordance with the known reaction scheme below:
H2R16 + ButylLi -~ HRl6Li X _ R18 X
H2R17 + ButylLi -~ HRl7Li HR16 - R18 - R17H + 2-Butyl-Li -LiRl6 - R18 - Rl7Li + M1C14 // I'C1 18 ~ ~ 1/
R M
(XI) ''~'''~ C 1 R17.
2~~~39'~
or H2R16 ø ButylLi -~ HRl6Li , C/ a, IiRh R19R20C
R18 b, H2~ ~R16H
2 ButylLi R19R20C Li2 ~R16 R19 S ~ Cl ,i ' C M1 R20~ ~~ ~Cl Rl4Li Rlg ~ ~ /R14 R19 ~ ~R14 ~C IHl R15L1 'C Ml (XI ) R20~ '; 'wCl ~ R20~ ~ ~ ~R15 The reaction scheme above also applies to the case where Rse s Rzo and/or Rl" ~ Ris ( c f . Journal of Organometallic Chem. 288 (1985) 63-67 and EP-A 320 762).
Preferred metallocenes are:
diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride, isopropylene(9-fluorenyl)cyclopentadienylzirconium ~a~~~97 11 _ dichloride, methyl(phenyl)methylene(9-fluorenyl)cyclopentadienylzir-conium dichloride and diphenylmethylene(9-fluorenyl)cyclopentadienylhafnium dichloride, or mixtures thereof.
Particular preference is given to:
diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride.
The cocatalyst is an aluminoxane of the formula IX .
\A1- 0 A1 - 0 A1/ ( IX) R13 / ~R13 n for the linear type and/or of the formula X
Al - 0 (X) n+2 for the cyclic type. In these formulae, R13 is a C1-Ca-alkyl group, preferably methyl, ethyl, isobutyl, butyl or neopentyl, or phenyl or benzyl. Particular preference is given to methyl. n is an integer from 2 to 50, preferably from 5 to 40. However, the precise structure of the aluminoxane is not known.
The aluminoxane can be prepared in vnrious ways (cf.
8. Pasynkiewicz, Polyhedron $ (1990) 429).
In one of the processes, finely powdered copper sulfate pentahydrate is 8lurried in toluene or a cycloolefin (for example cyclopentene, norbornene or tetracyclododecene), and sufficient trialkylaluminum to give about 1 mol of 294?8-1 CuSO4.5H2o for every 4 aluminum atoms is added in a glass flask under an inert gas at about -20°C or just above the melting point of the cycloolefin. After slow hydrolysis with elimination of alkane, the reaction mixture is left at room temperature for from 24 to 48 hours, during which it may be necessary to cool the mixture so that the temperature does not exceed 30°C. The aluminoxane, dissolved in the toluene or cycloolefin, is subsequently filtered off from the copper sulfate, and the solution is evaporated in vacuo. It is assumed that the low-molecu-lar-weight aluminoxanes condense in this preparation process to form higher oligomers with elimination of trialkylaluminum.
Aluminoxanes are also obtained when trialkylaluminum, preferably trimethylaluminum, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted with aluminum salts, preferably aluminum sulfate, containing water of crystallization at a temperature of from -20 to 100°C. The ratio by volume between the solvent and the alkylaluminum used is from 1:1 to 50:1, preferably 5:1, and the reaction time, which can be monitored through the elimination of the alkane, is from 1 to 200 hours, preferably from 10 to 40 hours.
Of the aluminum salts containing water of crystalliza-tion, those are used, in particular, which have a high content of water of crystallization. Particular preference is given to aluminum sulfate hydrate, in particular the compounds A12(S04)3.1E~H20 and A12(SO4)3.18H2o, having the particularly high water of crystallization content ref.. 16 and 18 mol respectively of H20/mol of Al2(S04)3.
A further variant of the preparation of aluminoxanes is to dissolve trialkylaluminum, preferably trimethyl-aluminum, in the liquid monomer in heptane or toluene in the polymerization reactor, and then to react the alumi-num compound with water.
205539' It is also possible for the aluminoxane to be adsorbed onto a support and then employed as a suspension in supported form. Several support processes are known. For example, slightly moist silica gel can act as a support.
In addition to the above-outlined processes for the preparation of aluminoxanes, there are others which can be used. Irrespective of the type of preparation, a varying content of unreacted trialkylaluminum, which is in free form or as an adduct, is connaon to all the aluminoxane solutions. This content has an as yet not precisely explained effect on the catalytic activity, which varies depending on the metallocene compound employed.
If preactivation of the transition-metal compound is necessary, it is carried out in solution. In this case, the metallocene is preferably dissolved in a solution of the aluminoxane in a hydrocarbon. Suitable hydrocarbons are aliphatic yr aromatic hydrocarbons and cycloolefins, such as, for example, cyclopentene, norbornene or tetra cyclododecene.
Toluene is preferred.
The preactivation can also be carried out in suspensions of supported aluminoxane.
The concentration of the aluminoxane in the solution is in the range from about 1% by weight up to the saturation limit, preferably from 5 to 30% by weight, in each case based on the total solution. The metallocene can be employed in the same concentration, but is preferably employed in an amount of from 10-"-1 mol per mole of aluminoxane. The preactivation time is from 0 to 60 minutes. The preactivation temperature is from 0 to 70°C.
If a small amount of solvent is added to the reaction mixture, the solvent is a customary inert solvent, such 205~39'~
as, for example, an aliphatic or cycloaliphatic hydrocar-bon, a petroleum ether or hydrogenated diesel oil fraction, or toluene.
Polymerization by the process according to the invention offers the advantage of achieving a high space-time yield (reaction rate) and a high cycloolefin incorporation rate . It has been found that increasing the concentration of the open-chain olefin, for example by increasing the partial pressure of this open-chain olefin, allows the reaction rate to be significantly increased. If pure open-chain olefin, for example ethylene, is injected, pressures of between 0.01 and 64 bar, preferably from 2 to 40 bar and particularly preferably from 4 to 20 bar, are employed. If an inert gas, for example nitrogen or argon, is also injected in addition to the open-chain olefin, the total pressure in the reaction vessel is from 2 to 64 bar, preferably from 5 to 64 bar and particularly preferably from 6 to 40 bar. The fact that the cyclo-olefinic component is in undiluted form means that a high cycloolefin incorporation rate is achieved even at high pressures. In addition, the reaction rate can also be increased by increasing the temperature, the upper limit to the temperature range being set by the thermal stabil-ity of the catalyst and the lower limit by the melting point of the cycloolefin at the correspanding pressure.
However, increasing temperature is accompanied by a simultaneous drop in the solubility of the gaseous olefin in the reaction medium and results in an increase in the incorporation rate of the cycloolefin in the copolymer.
In order to obtain constant incorporation rates with incrensing temperature, the pressure of the open-chain and gaseous olefin must be increased correspondingly.
Continuous and multistep polymerization processes are particularly advantageous since they enable efficient use of the cycloolefin. In continuous processes, the poly-cyclic olefin, which can arise as a residual monomer together with the polymer, can also be recovered and recycled into the reaction mixture.
Here, the process according to the invention offers the advantage over polymerization in solution that, due to the absence of a solvent or an extremely low solvent concentration, the technical complexity on recovery of the cycloolefins from the reaction mixture or from a precipitation bath is much lower.
The metallocene compound i.a used in a con~~~at.rat a c~r-_ based on the transition metal, of from l0-3 to l0-7, preferably from 10-4 to 10-6, mol of transition metal per dmWof reactor volume. The al~uminox~ne is used in a con-centration of from 10-4 to LOwl, preferably from 10-4 to 2.10-2 mol per dm3 of reactor volume, based on the aluminum content. 1n t~rinciple, hawever, higher con-centrations are also possible. In order to combine the polymerization properties of different metallocenes, it is possible to employ mixtures of a plurality of metallocenes.
When preparing copolymers, the molar ratios between the polycyclic olefin and the open-chain olefin (preferably) employed can be varied within a broad range. Molar ratios of from 3:1 to 100:1 of cycloolefin to open-chain olefin are preferably employed. The choice of polymerization temperature, the concentration of the catalyst component and the molar ratio employed or the pressure of the gaseous, open-chain olefin allow the incorporation rate of comonomer to be controlled virtually as desired.
Preferred incorporation rates are between 20 and 75 mol-~
of the cyclic component and particularly preferred incor-poration rates are between 35 and 65 mol-~k of the cyclic component.
The mean molecular weight of the copolymer formed can be controlled in a known manner by metering in hydrogen, varying the catalyst concentration or. varying the temper ature.
2~~5~~'~
The polydispersity 1~,/Mn of the copolymers is extremely narrow, with values between 2.0 and 3.5. This results in a property profile of the polymers which makes them particularly suitable for injection molding.
Surprisingly, it has been found that the bulk process according to the invention, for the same incorporation rates and comparable reaction rates, results in higher molecular weights than does conventional solution poly-merization.
If the possibilities of varying the molecular weight are taken into account, the process according to the inven-tion significantly broadens the accessible molecular weight range fox the cycloolefin copolymers.
The preferred catalysts according to the invention result, both in "solution polymerization" and in bulk polymerization, in significantly higher molecular weights than do other metallocene catalysts known hitherto.
The process described allows amorphous copolymers to be pxepared. The copolymers are transparent and hard. They are soluble, for examplQ, in decahydronaphthalene at 135°C and in toluene at room temperature. The polymers according to the invention can be processed as ther moplastics. Both on extrusion and on injection molding, no significant degradation or decrease in viscosity was found.
Surprisingly, it has been found that the cycloolefin copolymers prepared using the process according to the invention - and the preferred metallocenes according to the invention - do not gel in solution at room tempera-ture. They are therefore particularly suitable for coatings, for the production of cast films and for other applications in which cycloolefin solutions must be stored and transported. The flowability of the corres-ponding solutions also has a positive effect on the ~fl~~~~'~
work-up of the polymer solutions after the polymeriza tion. For example, the solution can be filtered more easily; concentration in a thin-film evaporator can be carried out with lower thermal and mechanical stress of the polymer solution.
Furthermore, it has been determined from Nl~t spectra that these cycloolefin copolymers also differ significantly in their microstructure from those which gel in solution.
This difference could be explained by the fact that the catalysts according to the invention polymerize strictly syndiospecifically due to the different R18 and R1' sub-stituents. according to the current state of knowledge, it must be assumed that the cycloolefin copolymers according to the invention contain disyndiotactic cyclo-olefin sequences which enable structures to be differen-tiated by NMR.
The materials prepared according to the invention are particularly suitable for the production of extruded parts, such as films, tubes, pipes, rods and fibers, and for the production of injection moldings of any desired shape and size. An important property of the materials according to the invention is their transparency. The optical applications, in particular, of the extruded or injection-molded parts of these materials thus have considerable importance. The refractive index, determined using an Abbe refractometer and mixed light, of the "
reaction products described in the examples below is in the range from 1.520 to 1.555. Since the refractive index is very close to that of crown glass (n ~ 1.51), the products according to the invention can be used in a variety of ways as a glass substitute, such as, for example, for lenses, prisms, baseplates and films for optical data media, for video disks, for compact disks, as cover and focusing screens for solar cells, as cover and diffusion screens for high-performance ogtics, and as optical waveguides in the form of fibers or films.
~0~53~7 The polymers according to the invention can also be employed for the preparation of polymer alloys. The alloys can be prepared in the melt or in solution. The alloys each have a favorable property combination of the components for certain applications. The following polymers can be employed for alloys containing the polymers according to the invention:
polyethylene, polypropylene, (ethylene-propylene) copoly-mers, polybutylene, poly(4-methyl-1-pentene), polyiso-prone, polyisobutylene, natural rubber, poly(methyl methacrylate), further polymethacrylates, polyacrylates, (acrylate-methacrylate) copolymers, polystyrene, (styrene-acrylonitrile) copolymers, bisphenol A poly-carbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, amorphous polyarylates, nylon 6, nylon 66, further polyamides, polyaramids, polyether ketones, polyoxymethylene, ,polyoxyethylene, polyurethanes, poly-sulfones, polyether sulfones and polyvinylidene fluoride.
The glass transition temperatures (Tg) given in the examples below were determined by DSC (Differential Scanning Calorimetry) at a heating rate of 20'C/min. The viacosities given were determined in accordance with DIN 53 728.
Example 1 A clean and dry 1.5 dm3 polymerization reactor equipped with stirrer was flushed with nitrogen and then with ethylene and charged with 560 g of norbornene melt at 70'C. The reactor was then kept at a temperature of 70°C
with stirring, and 6 bar of ethylene (overpreasure) were injected.
5 cma of a toluene solution of methylaluminoxane (MAO
solution) (10.1% by weight of methylaluminoxane having a molecular weight of 1300 g/mol, determined cryoscopically) were then metered into the reactor, and the mixture was stirred at 70°C for 15 minutes, with the ethylene pressure being kept at 6 bar by re-metering. In parallel, 10.2 mg of diphenylmethylene(9-fluorenyl)-cyclopentadienylzirconium dichloride were dissolved in 5 cm3 of a toluene solution of methylaluminoxane (concentration and quality see above), and the solution was preactivated by standing for 15 minutes. The solution of the complex was then metered into the reactor (in order to reduce the molecular weight, hydrogen can be introduced into the reactor via a lock immediately after the metering-in of the catalyst). The mixture is then polymerized at 70°C for 0.5 hour with stirring (750 rpm), during which the ethylene pressure was kept at 6 bar by re-metering. The reactor contents were then discharged rapidly into a stirred vessel containing 100 cm3 of isopropanol. The mixture was introduced dropwise into 2 dm3 of acetone, the mixture was stirred for 10 minutes, and the suspended polymeric solid was then filtered off.
The polymer filtered off was then introduced into 2 dm3 of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol, and this suspension was stirred for 2 hours. The polymer was then filtered off again, washed with water until neutral and dried for 15 hours at 80'C and 0.2 bar. 40.4 g of product were obtained. A
viscosity of 112 cma/g and a glass transition temperature (Tg) of 183'C were measured on the product.
Examples 2 and 3 The polymerizations were carried out analogously to Example 1, with some conditions, summarized in Table 1, being changed.
205530' Table 1 Ex- Cyclo- Metal- Amount Ethy- Time Yield Visc. Tg ample olefin locene of lane (h) (g) (cm3/g) (°C) (g) metal- pres-s locene sure (mg) (bar) 2 Norbor- B 0.5 10 0.5 37 210 161.5 nene 3 DMON 400 A 10.0 6 0.3 31 135 206.9 A = Diphenylmethylene(9-fluorenyl)cyclopentadienyl-zirconium dichloride B = Isoprapylene(9-fluorenyl)cyclopentadienylzirconium dichloride DMON = Tetracyclododecene Example 4 A clean and dry 75 dm~ polymerization reactor equipped with stirrer was flushed with nitrogen and than with ethylene and charged with 22,000 g of norbornene melt (Nb). The reactor was then heated to a temperature of 70°C with stirring, and 15 bar of ethylene Were injected.
580 cm3 of a toluene solution of methylaluminoxane (10.1 by weight of methylaluminoxane having a molecular weight of 1300 g/mol, determined cryoscopically) were then metered into the reactor, and the mixture was stirred at 70°C for 15 minutes, during wYtich the ethylene pressure Was kept at 15 bar by re-metering. In parallel, 500 mg of metallocene A were dissolved in 500 cm3 of a toluene solution of methylaluminoxane (concentration and guality see above), and the solution was preactivated by standing for 15 minutes. The solution of the complex (catalyst solution) was then metered into the reactor (in order to reduce the molecular weight, hydrogen can be introduced into the reactor via a lock immediately after the _ 21 _ 205539"
metering-in of the catalyst). The mixture was then polymerized at 70°C for 1.3 hours with stirring (750 rpm), during which the ethylene pressure was kept at 15 bar by re-metering. The reactor contents were then discharged rapidly into a stirred vessel containing 200 cm3 of isopropanol (as stopper). The mixture was precipitated in acetone, the precipitate was stirred for minutes, and the suspended polymeric solid was then filtered off.
10 The polymer filtered off was then treated with a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol, and the mixture was stirred for 2 hours. The polymer was then filtered off again, washed with water until neutral and dried for 15 hours at 80°C and 0.2 bar.
5500 g of product were obtained. A viscosity of 163 cm3/g and a glass transition temperature (Tg) of 144°C were measured on the product.
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205539'7 Comparative Example 13 (solution polymerization) A clean and dry 1.5 dm3 polymerization reactor equipped with stirrer was flushed with nitrogen and then with ethylene and charged with a solution of 411 g of norbor-none (Nb) and 86 cm3 of toluene. The reactor was then heated to a temperature of 70°C with stirring and 8 bar of ethylene were injected.
20 cm3 of a toluene solution of methylaluminoxane (10.1%
by Weight of methylaluminoxane having a molecular Weight of 1300 g/mol, determined cryoscopically) were then metered into the reactor, and the mixture was stirred at 70°C for 15 minutes, during which the ethylene pressure was kept at 8 bar by re-metering. In parallel, 71.8 mg of dicyclopentadienylzirconium dichloride were dissolved in 10 cma of a toluene solution of methylaluminoxane (concentration'and quality see above), and the solution was preactivated by standing for 15 minutes. The Solution of the complex was then metered into the reactor. The mixture was then polymerized at 70°C for 2 hours with stirring ( 750 rpm) , during which the ethylene pressure was kept at 8 bar by re-metering. The reactor contents were then discharged rapidly into a stirred vessel containing 100 cma of iaopropanol. The mixture was intro-duced dropwise into 2 dm~ of acetone, the mixture was stirred for 10 minutes, and the suspended polymeric Solid was then filtered off.
The polymer filtered off was then introduced into 2 dm3 of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol, and this suspension was Stirred for 2 hours. The polymer was then filtered off again, washed with water until neutral and dried for 15 hours at 80°C and 0.2 bar. 73.5 g of product were obtained. A
viscosity of 17 cma/g and a glass transition temperature (Tg) of 168.5°C were measured on the product.
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Example 17 20% strength by weight toluene solutions of each of the polymers of Examples 4 and 6 to 9 were prepared in 250 ml flasks at 70°C. The solutions were clear and free-flow-ing. The flowability of the solutions was determined by tilting the flasks. After the solutions had been cooled to room temperature, the flowability was determined as a function of time. All the solutions investigated were still free-flowing after 50 days.
Comparative Example 18 Solutions of various polymers prepared in accordance with Comparative Examples 5 and 13 to 16 were prepared and investigated analogously to Example 17. All the solutions were no longer free-flowing after only 8 hours at room temperature. All the solutions had gelled, ie. they remained shape-stable in the tilt experiment.
Example 19 GPC (Gel Permeation Chromatography) measurements were carried out on various samples. A Millipore Waters Chrom.
type 150-C ALC/GPC chromatograph and a column set comprising 4 Shodex AT-80 M/S columns were used. The solvent was o-dichlorobenzen~.
Other measurement parameters werea Temperature: 135°C
Z5 Flow rate: 0.5 ml/min Amount of sample: 0.4 ml of sample solution Concentration of the sample solutions 0.1 g/dl Calibration: by polyethylene standard The GPC measurement results are as follows:
- 26 - ~0~~~~~
Sample Weight average 1~, No . average M",/M"
g/mol M"
g/mol According to 75,600 37,200 2 Comparative Example 5 According to 391,000 163,000 2.4 Example 7 Example 20 la-C-NMR spectra were recorded for samples from Examples 4 to 7. The samples were dissolved in a mixture of hexachlorobutadiene and tetrachloroethane-d2 and measured using a 400 l~iz NMR instrument. The spectra are repro-duced comparatively in Figure 1. Surprisingly, it can be seen that the structure of the polymers of Examples 4, 6 and 7 differs~significantly from that of Comparative Example 5.
In the case of the metallocene C ( rac-dimethylsilylbis ( 1 indenyl)zirconium dichloride) used in Comparative Example 5, the substituents R1° and Rl' are identical.
Examples 21 - 23 The polymerizations were carried out analogously to Example 1, with some conditions, summarized in Table 4, being changed.
- 27 _ Table 4 Ex- Cyclo- Metal- Amount Ethy- Time Yield Visc. Tg ample olefin locene of lene (h) (g) (cm3/g) (°C) (g) metal- pres-s locene sure (mg) (bar) 21 Norbor- E 1 6 1 36 119 178 none 22 Norbor- F 20 6 3 33 125 183 nene 23 Norbor- G 1 1.5 1 22 40 239 nene E = methyl(phenyl)methylene(9-fluorenyl)cyclopentadienyl zirconium dichloride F ~ diphenylmethylene(9-fluorenyl)cyclopentadienylhafnium dichloride G ' ieopropylene(1-indenyl)cyclopentadienylzirconium dichloride Example 24 (polynorbornene) 800 g of norbornene were liquefied with 25 cm3of a 10.1%
strength by weight toluene solution of methylaluminoxane with warming in a 1.5 dm3 polymerization reactor (see Example 1).
In parallel, 250 mg of diphenylmethylene(9-fluorenyl) cyclopentadienylzirconium dichloride were dissolved in 25 cm3 of a 10.1% strength toluene solution of methylalum inoxane, and the Solution was added to the above melt.
The mixture waS polymerized for 160 hours at 35°C under argon.
The solution was worked up analogously to Example 1.
After drying, 41 g of a colorless powder were obtained.
A viscosity of 44 cm3/g was measured on the product.
Neither a glass state nor a melting point were detectable _ 28 _ 20~539'~
up to 380°C using DSC. Softening was observable at about 400°C under a heating-stage microscope.
13C_NI~t spectrum (analogously to Example 20) showed very broad signals with peak maxima at 31, 40 and 50 ppm.
According to NMR and infra-red spectra, the product contains no double bonds.
Example 25 10-20% strength toluene solutions of the polymer from Example 24 Were prepared, and the solution was coated onto glass plates using a doctor blade. After drying in vacuo (0.2 bar) at 80°C, transparent, colorless films having thicknesses between 1 and 100 ~m wexe obtained.
Claims (6)
1. A process for the preparation of a cycloolefin polymer or copolymer by polymerization of from 0.1 to 100% by weight, based on the total amount of monomers, of at least one monomer of the formula I, II, III, IV, V or VI
in which R1, R2, R3, R4, R5, R6, R7 and R8 are ident-ical or different and are a hydrogen atom or a C1-C8-alkyl radical, it being possible for identical radicals in the different formulae to have differ-ent meanings, from 0 to 99.9% by weight, based on the total amount of monomers, of a cycloolefin of the formula VII
in which n is a number from 2 to 10, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula VIII
in which R9, R10, R11 and R12 are identical or differ-ent and are a hydrogen atom or a C1-C8-alkyl rad-ical, at temperatures of from 20 to 150°C and at a pressure of from 0.01 to 64 bar, in the presence of a catalyst which comprises an aluminoxane of the formula IX
for the linear type and/or of the formula X
for the cyclic type, where, in the formulae IX and X, R13 is a C1-C6-alkyl group, phenyl or benzyl, and n is an integer from 2 to 50, and a metallocene of the formula XI
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R14 and R15 are identical or different and are a hydrogen atom, a halogen 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, or a C8-C40-arylalkenyl group, R16 and R17 are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M1, R18 is =BR19=AlR19, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR19, =CO, =PR19 or =P(O)R19 where R19, R20 and R21 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl 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 R19 and R20 or R19 and R21, in each case with the atoms connecting them, form a ring, and M2 is silicon, germanium or tin, which comprises carrying out the polymerization in the liquid cycloolefin monomer or cycloolefin monomer mixture or in an at least 95 percent by volume cycloolefin solution, the substitutents R16 and R17 in the formula XI being different from one another.
in which R1, R2, R3, R4, R5, R6, R7 and R8 are ident-ical or different and are a hydrogen atom or a C1-C8-alkyl radical, it being possible for identical radicals in the different formulae to have differ-ent meanings, from 0 to 99.9% by weight, based on the total amount of monomers, of a cycloolefin of the formula VII
in which n is a number from 2 to 10, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula VIII
in which R9, R10, R11 and R12 are identical or differ-ent and are a hydrogen atom or a C1-C8-alkyl rad-ical, at temperatures of from 20 to 150°C and at a pressure of from 0.01 to 64 bar, in the presence of a catalyst which comprises an aluminoxane of the formula IX
for the linear type and/or of the formula X
for the cyclic type, where, in the formulae IX and X, R13 is a C1-C6-alkyl group, phenyl or benzyl, and n is an integer from 2 to 50, and a metallocene of the formula XI
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R14 and R15 are identical or different and are a hydrogen atom, a halogen 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, or a C8-C40-arylalkenyl group, R16 and R17 are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M1, R18 is =BR19=AlR19, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR19, =CO, =PR19 or =P(O)R19 where R19, R20 and R21 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl 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 R19 and R20 or R19 and R21, in each case with the atoms connecting them, form a ring, and M2 is silicon, germanium or tin, which comprises carrying out the polymerization in the liquid cycloolefin monomer or cycloolefin monomer mixture or in an at least 95 percent by volume cycloolefin solution, the substitutents R16 and R17 in the formula XI being different from one another.
2. The process as claimed in claim 1, wherein the polymerization is carried out in the liquid cyclo-olefin monomer or cycloolefin monomer mixture.
3. The process as claimed in claim l or 2, wherein the metallocene of the formula XI is diphenylmethylene-(9-fluorenyl)cyclopentadienylzirconium dichloride, isopropylene(9-fluorenyl)cyclopentadienylzirconium dichloride, methyl(phenyl)methylene(9-fluorenyl)-cyclopentadienylzirconium dichloride or diphenyl-methylene(9-fluorenyl)cyclopentadienylhafnium dichloride.
4. The process as claimed in any one of claims 1 to 3, wherein the polycyclic olefin is norbornene or tetracyclododecene.
5. The process as claimed in any one of claims 1 to 4, wherein a copolymer of norbornene and ethylene is prepared.
6. A cycloolefin polymer or copolymer which is prepared by the process as claimed in any one of claims 1 to 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4036264.7 | 1990-11-14 | ||
| DE4036264 | 1990-11-14 |
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| CA002055397A Expired - Lifetime CA2055397C (en) | 1990-11-14 | 1991-11-13 | Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers |
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| Country | Link |
|---|---|
| EP (1) | EP0485893B1 (en) |
| JP (1) | JP3247130B2 (en) |
| KR (1) | KR100230915B1 (en) |
| AT (1) | ATE165372T1 (en) |
| AU (1) | AU641291B2 (en) |
| CA (1) | CA2055397C (en) |
| CS (1) | CS344291A3 (en) |
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| US11577443B2 (en) | 2016-03-11 | 2023-02-14 | Polyplastics USA, Inc | Injection stretch blow-molding (ISBM) enhancement for semi-crystalline polyolefin containers utilizing alicyclic polyolefins |
Families Citing this family (68)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5744664A (en) * | 1990-07-05 | 1998-04-28 | Hoechst Aktiengesellschaft | Cycloolefin copolymers (COCS) as substrate material for liquid-crystal displays |
| ES2127199T3 (en) * | 1991-02-27 | 1999-04-16 | Ticona Gmbh | PROCESS FOR THE PREPARATION OF (CO) CYCLOOLEFIN POLYMERS WITH A NARROW DISTRIBUTION OF MOLECULAR WEIGHTS. |
| EP0594147A1 (en) * | 1992-10-24 | 1994-04-27 | Hoechst Aktiengesellschaft | Cyclo-olefin copolymers as substrate material for liquid crystal displays |
| DE59402624D1 (en) * | 1993-02-12 | 1997-06-12 | Hoechst Ag | Process for the preparation of cycloolefin copolymers |
| US6214951B1 (en) | 1993-02-12 | 2001-04-10 | Hoechst Aktiengesellschaft | Cycloolefin copolymers having high tear strength and low optical attenuation |
| EP0610850A1 (en) * | 1993-02-12 | 1994-08-17 | Hoechst Aktiengesellschaft | Process for preparing cyclo-olefin polymers |
| TW274100B (en) | 1993-02-12 | 1996-04-11 | Hoechst Ag | |
| EP0610843B1 (en) * | 1993-02-12 | 1999-05-19 | Ticona GmbH | Process for preparing cyclo-olefin polymers |
| DE4304309A1 (en) * | 1993-02-12 | 1994-08-18 | Hoechst Ag | Flexible cycloolefin copolymer film |
| DE4304285A1 (en) * | 1993-02-12 | 1994-08-18 | Hoechst Ag | Cycloolefin copolymers with high tear resistance and low optical attenuation |
| TW369545B (en) * | 1993-02-12 | 1999-09-11 | Hoechst Ag | Process for preparing cycloolefin copolymers |
| DE4304291A1 (en) * | 1993-02-12 | 1994-08-18 | Hoechst Ag | Cycloolefin copolymers with low melt viscosity and low optical attenuation |
| DE4304308A1 (en) * | 1993-02-12 | 1994-08-18 | Hoechst Ag | Rigid cycloolefin copolymer film |
| DE4410559A1 (en) * | 1994-03-26 | 1995-09-28 | Hoechst Ag | Oriented polyolefin film with amorphous polymer, process for its production and its use |
| DE4422157A1 (en) * | 1994-06-24 | 1996-01-04 | Hoechst Ag | Process for the preparation of cycloolefin copolymers |
| DE4426184A1 (en) | 1994-07-23 | 1996-01-25 | Hoechst Ag | Non-sealable oriented polyolefin multilayer film, process for its production and its use |
| DE4426185A1 (en) | 1994-07-23 | 1996-01-25 | Hoechst Ag | Sealable oriented polyolefin multilayer film, process for its production and its use |
| DE19536043A1 (en) * | 1995-09-28 | 1997-04-10 | Hoechst Ag | Polyolefin film with cycloolefin polymer, process for its production and its use |
| DE19539093A1 (en) | 1995-10-20 | 1997-04-24 | Hoechst Ag | Metallized polyolefin film |
| DE19917790A1 (en) * | 1999-04-20 | 2000-11-02 | Hoechst Trespaphan Gmbh | Biaxially oriented film for the production of ceramic capacitors |
| DE19929809A1 (en) | 1999-06-30 | 2001-01-04 | Ticona Gmbh | Continuous process for the production of an amorphous polyolefin with a broad molar mass distribution and uniform glass temperature |
| DE10009646A1 (en) * | 2000-03-01 | 2001-09-13 | Ticona Gmbh | Polymer mixture containing amorphous polyolefin, useful for preparing e.g. axially oriented films, has controllable relaxation and shrinkage properties |
| DE10012137A1 (en) | 2000-03-13 | 2001-09-20 | Mitsubishi Polyester Film Gmbh | Translucent biaxially oriented polyester film, e.g. useful for food packaging or printing, includes a layer containing a cycloolefin copolymer |
| DE10022942A1 (en) | 2000-05-11 | 2001-11-15 | Mitsubishi Polyester Film Gmbh | Mat white biaxially oriented polyester film, e.g. useful for food packaging, includes a cycloolefin copolymer |
| DE10026177A1 (en) | 2000-05-26 | 2001-11-29 | Mitsubishi Polyester Film Gmbh | White, high-gloss polyester film containing cycloolefin copolymer (COC), process for its production and its use |
| DE10035328A1 (en) | 2000-07-20 | 2002-01-31 | Mitsubishi Polyester Film Gmbh | Opaque polyester film containing cycloolefin copolymer (COC) with good surface adhesion, process for its production and its use |
| US6696524B2 (en) | 2001-02-20 | 2004-02-24 | E. I. Du Pont De Nemours And Company | Low Tg ethylene-based polymer, cycloolefin polymer blends |
| US6670423B2 (en) | 2001-02-20 | 2003-12-30 | E. I. Du Pont De Nemours And Company | Polar ethylene-based polymer, cycloolefin polymer blends |
| DE10137924B4 (en) | 2001-08-07 | 2005-12-01 | Ticona Gmbh | Long fiber-reinforced polyolefin-plastic structure, process for its preparation and moldings produced therefrom |
| US6713582B2 (en) | 2001-12-14 | 2004-03-30 | Uniroyal Chemical Company, Inc. | Process for the oligomerization of α-olefins having low unsaturation, the resulting polymers, and lubricants containing same |
| AU2002357918A1 (en) * | 2001-12-21 | 2003-07-15 | E.I. Du Pont De Nemours And Company | Multilayer film |
| DE10223662A1 (en) | 2002-05-28 | 2003-12-11 | Mitsubishi Polyester Film Gmbh | Transparent polyester film with improved water vapor barrier, process for its production and its use |
| DE10223663A1 (en) | 2002-05-28 | 2003-12-11 | Mitsubishi Polyester Film Gmbh | Transparent polyester film with improved water vapor barrier, process for its production and its use |
| DE10242730A1 (en) | 2002-09-13 | 2004-03-25 | Ticona Gmbh | A thermally formable thermoplastic polyolefin film useful as a carrier film and having very good thermal formability, good barrier properties against water, and outstanding punching behavior |
| US7144615B2 (en) | 2003-04-22 | 2006-12-05 | Mitsubishi Polyester Film Gmbh | Coextruded, hot-sealable and peelable polyester film, process for its production and its use |
| US7442427B2 (en) | 2003-04-22 | 2008-10-28 | Mitsubishi Polyester Film Gmbh | Coextruded, hot-sealable and peelable polyester film, process for its production and its use |
| US7288312B2 (en) | 2003-04-22 | 2007-10-30 | Mitsubishi Polyester Film Gmbh | Coextruded, hot-sealable and peelable polyester film having low peeling resistance, process for its production and its use |
| US7141293B2 (en) | 2003-04-22 | 2006-11-28 | Mitsubishi Polyester Film Gmbh | Coextruded, hot-sealable and peelable polyester film having high peeling resistance, process for its production and its use |
| US7186452B2 (en) | 2003-04-22 | 2007-03-06 | Mitsubishi Polyester Film Gmbh | Coextruded, hot-sealable and peelable polyester film having high peeling resistance, process for its production and its use |
| US7223459B2 (en) | 2003-04-22 | 2007-05-29 | Mitsubishi Polyester Film Gmbh | Coextruded, hot-sealable and peelable polyester film, process for its production and its use |
| DE10352431A1 (en) | 2003-11-10 | 2005-06-09 | Mitsubishi Polyester Film Gmbh | Peelable polyester film with automatic venting, process for their preparation and their use |
| DE10352432A1 (en) | 2003-11-10 | 2005-06-09 | Mitsubishi Polyester Film Gmbh | White, heat-sealable, peelable polyester film, process for its preparation and its use |
| DE10352430A1 (en) | 2003-11-10 | 2005-06-09 | Mitsubishi Polyester Film Gmbh | Peelable polyester film with improved oxygen barrier, process for its preparation and its use |
| DE10352444A1 (en) | 2003-11-10 | 2005-06-09 | Mitsubishi Polyester Film Gmbh | Adhesion-promoted, heat-sealable and peelable polyester film, process for its preparation and its use |
| US7288316B2 (en) | 2003-11-21 | 2007-10-30 | Topas Advanced Polymers, Inc. | Cycloolefin copolymer heat sealable films |
| JP2004195246A (en) * | 2004-02-13 | 2004-07-15 | Mitsunobu Miyagi | Laser probe |
| ES2397870T3 (en) | 2006-10-05 | 2013-03-12 | Treofan Germany Gmbh & Co. Kg | Opaque film made of PLA simultaneously stretched |
| DE102007006825A1 (en) | 2007-02-07 | 2008-08-14 | Evonik Röhm Gmbh | Plastic mold with anisotropic light scattering |
| DE102007055491A1 (en) | 2007-11-21 | 2009-06-04 | Mitsubishi Polyester Film Gmbh | Low-density polyester film for polar substrates |
| KR101043657B1 (en) * | 2008-09-23 | 2011-06-22 | 김명호 | Apparatus for forming wire products |
| US9021611B2 (en) | 2009-02-18 | 2015-04-28 | Northwestern University | Beam pen lithography |
| WO2011129869A1 (en) | 2010-04-15 | 2011-10-20 | Topas Advanced Polymers, Inc. | Melt blends of amorphous cycloolefin polymers and partially crystalline cycloolefin elastomers with improved toughness |
| DE102010030074A1 (en) | 2010-06-15 | 2011-12-15 | Evonik Degussa Gmbh | Plastic photovoltaic module and method for its production |
| CA2802097C (en) | 2010-07-27 | 2014-06-03 | Exxonmobil Oil Corporation | Film composition and method of making the same |
| WO2013036312A1 (en) | 2011-08-19 | 2013-03-14 | Avery Dennison Corporation | Blends of ethylene copolymers and propylene based plastomers in multilayer films for low noise and rf welding |
| EP2918408A1 (en) | 2011-12-22 | 2015-09-16 | Avery Dennison Corporation | Flexible Barrier Films Containing Cyclic Olefins |
| CN104080603B (en) | 2012-01-31 | 2018-04-06 | 纳幕尔杜邦公司 | Multilayer film comprising cyclic olefine copolymer |
| CN109071850B (en) | 2016-05-12 | 2021-04-27 | 沙特基础工业全球技术有限公司 | Capacitor film with high temperature resistance, manufacturing method thereof and product thereof |
| AR109065A1 (en) | 2016-07-28 | 2018-10-24 | Dow Global Technologies Llc | MULTI-PAPER STRUCTURES, MULTI-PAPER FILMS AND FORMED CONTAINERS FROM THEM |
| US10951875B2 (en) | 2018-07-03 | 2021-03-16 | Raxium, Inc. | Display processing circuitry |
| DE102018215422A1 (en) | 2018-09-11 | 2020-03-12 | Mitsubishi Polyester Film Gmbh | Heat-sealable polyester film for the production of menu trays, processes for their production and their use |
| DE102019200365A1 (en) | 2019-01-14 | 2020-07-16 | Mitsubishi Polyester Film Gmbh | Package made of polyester with a thermoformable bottom film and a sealable and peelable top film, process for their production and their use |
| US11710445B2 (en) | 2019-01-24 | 2023-07-25 | Google Llc | Backplane configurations and operations |
| US11637219B2 (en) | 2019-04-12 | 2023-04-25 | Google Llc | Monolithic integration of different light emitting structures on a same substrate |
| US11238782B2 (en) | 2019-06-28 | 2022-02-01 | Jasper Display Corp. | Backplane for an array of emissive elements |
| US11626062B2 (en) | 2020-02-18 | 2023-04-11 | Google Llc | System and method for modulating an array of emissive elements |
| DE102023100500A1 (en) | 2023-01-11 | 2024-07-11 | Mitsubishi Polyester Film Gmbh | Polyester packaging consisting of thermoformable bottom film and peelable top film, process for its manufacture and its use |
| DE102023100507A1 (en) | 2023-01-11 | 2024-07-11 | Mitsubishi Polyester Film Gmbh | Coextruded, heat-sealable and peelable polyester film, process for its preparation and its use |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5003019A (en) * | 1987-03-02 | 1991-03-26 | Mitsui Petrochemical Industries, Ltd. | Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers |
| DE3726325A1 (en) * | 1987-08-07 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING AN OLEFIN POLYMER |
| EP0358103B1 (en) * | 1988-09-05 | 1993-12-15 | Idemitsu Kosan Company Limited | Method for the preparation of a polymer |
| DE3835044A1 (en) * | 1988-10-14 | 1990-04-19 | Hoechst Ag | Process for the preparation of cycloolefin polymers |
| DE3922546A1 (en) * | 1989-07-08 | 1991-01-17 | Hoechst Ag | METHOD FOR THE PRODUCTION OF CYCLOOLEFINPOLYMERS |
-
1991
- 1991-10-30 TW TW080108552A patent/TW227005B/zh not_active IP Right Cessation
- 1991-11-07 AT AT91119005T patent/ATE165372T1/en not_active IP Right Cessation
- 1991-11-07 EP EP91119005A patent/EP0485893B1/en not_active Expired - Lifetime
- 1991-11-07 DE DE59108971T patent/DE59108971D1/en not_active Expired - Lifetime
- 1991-11-07 ES ES91119005T patent/ES2117632T3/en not_active Expired - Lifetime
- 1991-11-12 HU HU913539A patent/HUT59429A/en unknown
- 1991-11-13 CS CS913442A patent/CS344291A3/en unknown
- 1991-11-13 AU AU87777/91A patent/AU641291B2/en not_active Ceased
- 1991-11-13 NO NO91914439A patent/NO914439L/en unknown
- 1991-11-13 CA CA002055397A patent/CA2055397C/en not_active Expired - Lifetime
- 1991-11-13 ZA ZA918990A patent/ZA918990B/en unknown
- 1991-11-14 JP JP29928391A patent/JP3247130B2/en not_active Expired - Lifetime
- 1991-11-14 KR KR1019910020205A patent/KR100230915B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11577443B2 (en) | 2016-03-11 | 2023-02-14 | Polyplastics USA, Inc | Injection stretch blow-molding (ISBM) enhancement for semi-crystalline polyolefin containers utilizing alicyclic polyolefins |
Also Published As
| Publication number | Publication date |
|---|---|
| AU8777791A (en) | 1992-05-21 |
| ZA918990B (en) | 1992-07-29 |
| JPH04268312A (en) | 1992-09-24 |
| CS344291A3 (en) | 1992-09-16 |
| TW227005B (en) | 1994-07-21 |
| HU913539D0 (en) | 1992-01-28 |
| EP0485893A1 (en) | 1992-05-20 |
| NO914439D0 (en) | 1991-11-13 |
| ES2117632T3 (en) | 1998-08-16 |
| KR100230915B1 (en) | 1999-11-15 |
| AU641291B2 (en) | 1993-09-16 |
| EP0485893B1 (en) | 1998-04-22 |
| ATE165372T1 (en) | 1998-05-15 |
| JP3247130B2 (en) | 2002-01-15 |
| KR920009859A (en) | 1992-06-25 |
| CA2055397A1 (en) | 1992-05-15 |
| DE59108971D1 (en) | 1998-05-28 |
| HUT59429A (en) | 1992-05-28 |
| NO914439L (en) | 1992-05-15 |
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