CA2089952A1 - Cycloolefin block copolymers and a process for their preparation - Google Patents
Cycloolefin block copolymers and a process for their preparationInfo
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- CA2089952A1 CA2089952A1 CA002089952A CA2089952A CA2089952A1 CA 2089952 A1 CA2089952 A1 CA 2089952A1 CA 002089952 A CA002089952 A CA 002089952A CA 2089952 A CA2089952 A CA 2089952A CA 2089952 A1 CA2089952 A1 CA 2089952A1
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- monomer
- cycloolefin
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
Abstract:
Cycloolefin block copolymers and a process for their preparation Cycloolefin block copolymers, which in particular are suitable as phase promoters, are preferably obtained by copolymerization of polycyclic olefins, such as norbor-nene, with acyclic olefins, such as ethylene, by, at a molecular weight distribution Mw/Mn of the polymer block forming of less than 2, changing the reaction conditions one or more times in such a way that the monomer/co-monomer ratio changes by at least 10 % or a further polymerizable monomer is metered into the monomer or the monomers.
Cycloolefin block copolymers and a process for their preparation Cycloolefin block copolymers, which in particular are suitable as phase promoters, are preferably obtained by copolymerization of polycyclic olefins, such as norbor-nene, with acyclic olefins, such as ethylene, by, at a molecular weight distribution Mw/Mn of the polymer block forming of less than 2, changing the reaction conditions one or more times in such a way that the monomer/co-monomer ratio changes by at least 10 % or a further polymerizable monomer is metered into the monomer or the monomers.
Description
2089~2 HOECHST AKTIENGESELLSCHAFT ~OE 92/F 045 Dr. SR/rh Description Cycloolefin block copolymers and a process for their preparation ~he invention relates prLmarily to a proce~s for the preparation of cycloolefin blo-k copolymer~, the polymer chain~ being mad~ up of at least two chemically di~ferent blocks and the cycloolefin being polymerized without ring opening. The transition from one block to the next ~an be via an intermediate block, the chaxacteristic feature of which is that in said intermediate block there i~ a continuous, gradual change in the chemical structure from that of the one block towards the chemical struct~re of the next block~
The cycloolefin copolymers which can be prepared by known processes (cf. for example EP-A 407 870) have a random or presumably alternating chain structure. However, these copolymers, which, in principle, are suitable for the preparation of a multiplicity of moldings, as a rule have only low toughness which is expressed, for example, in elongations at break of 5 8 % and in this re~pect are therefore worth improving.
Cycloolefin copolymers which have hiyh heat distortion resistance al~o have relatively high melt vi~co~ity.
Block copolymers based on 1-olefins are de~cribed in the application WO 91/12285.
One method for improving the toughness o~ a poly~r i~ to mix the corresponding polymer with a so-calle~ flexible phase, a polymer which h~ a diEtinctly lower glass transition temperature. Because of the co~tent of flexible component, mixtures of this type in principle also have lower melt viscosity~
:
i , .
The cycloolefin copolymers which can be prepared by known processes (cf. for example EP-A 407 870) have a random or presumably alternating chain structure. However, these copolymers, which, in principle, are suitable for the preparation of a multiplicity of moldings, as a rule have only low toughness which is expressed, for example, in elongations at break of 5 8 % and in this re~pect are therefore worth improving.
Cycloolefin copolymers which have hiyh heat distortion resistance al~o have relatively high melt vi~co~ity.
Block copolymers based on 1-olefins are de~cribed in the application WO 91/12285.
One method for improving the toughness o~ a poly~r i~ to mix the corresponding polymer with a so-calle~ flexible phase, a polymer which h~ a diEtinctly lower glass transition temperature. Because of the co~tent of flexible component, mixtures of this type in principle also have lower melt viscosity~
:
i , .
- 2 _ 2 0 8 9 ~ ~2 It is very frequently found that mixtures of aycloolefin copolymers having very different gla88 transition tempe-ratures are not compatible with one another Incompati-bility is as a rule associated with poor mechanical properties if care i~ not taken that good phase binding results.
A common method for improving pha~e binding i~ the admixture o a polymer phase promoter, the characteri~tic feature of which is that its chain is physically or chemically anchored both in the first and in the ~econd phase (cf. Rub~er Toughened Plastics, Adva~c0s in Chemistry Series, Washington DC, 222, 1989; ppO 3 - 64).
The object on which the invention i5 based was thus to find a phase promoter for cycloolefin copol~mer~ of different glass transition temperatures and a process for its preparation.
It has been found, surprisingly, that when the polymeriz-ation is conducted in a particular way, based on cata-lysis using metallocene catalysts, polymers are formed ~0 which are very suitable as phase promoters and in variol1s cases even facilitate miscibility of different cyclo-olefin copolymers. In this context miscibility signifies that thP finished polymer mixture has a single glass transition temperature or that the gla~ transition temperatures of the mixture are closer together than the glass transition temperatures of the pure components.
Kinetic studies have shown that the polymer material~
prepared according to the invention are cycloolefin block copolymers.
The invention thus relates to a process for the prepara-tion of a cycloolefin block copolymer, wherein 0.1 to 95 % by weight, with respect to the total ~mount of monomers employed, of at least one monomer of the 2~8~2 formulae I, II, III, IV, V o:r VI
/CH\ Rl ¦¦R'-C--R~
\¦ / ~R2 H C f C H
¦IR3 - C - R~ ¦ CH2 ( I I ) .
HC\I ,CH
/ ¦ \ ~ I \ /
llr3--C--R4 ¦R~--C R ¦ ( \ I H ~ \ C H /
H C/ ¦ \C H~ ¦ \C H~l \C H/
I ~S-C--R4 ¦R5--C R ¦ R7- C-R3 ¦ ( I Y) .
R s / I \ / \ /
~!R -C--R4 1 ¦ (V) .
HC\I ~CH /CH
CH CH \R~
~S
f C H \C ~ ~C H \ R 2 ;
2~99~2 in which Rl, R2, R3, R4, R5, R6, R7 and R~ are identical or different and are a hydrogen atom or a Cl-C3-alkyl radical, it being po~sible for the same radicalG in the various formulae to have different meanings, 0 to 95 ~ by weight, with xespect to the total amount of monomers employed, of a cycloolefin of the for~ula VII
CH CH
( V l l ) ( C H 2 ) n in which n is a number from ~ to 10, and 0 to 99 % by weight, with respect to the total amount of monomers employed, of at least one acyclic olein of the formula VIII
R \ / (Ylll), ,C C~
R~l/ `R'2 in which R9, Rl, Rl1 and R12 are identical or different and are a hydrogen atom or a Cl-C~-alkyl radical, are poly-merized at temperatures of -78 to 150C and a pre~ure of OoO1 to 64 bar, ;n the presence of a catalyst which i~
composed of ~ cocatalyst and a metallocene o the ~ormula XI R
/ / R~
R18 Ml (X I ) \ R15 :
. .. ~ : .
:
2~8~2 in which M' is titanium, zirconium, hafnium, va~adium, niobium or tantaluml Rl4 and Rls ar~ identical or different and are a hydrogen atom, a halogen atom, a C,-C,O-alkyl group, a Cl-C10-alkoxy group, a C6-C,O-aryl group, a C6-ClD-aryloxy group, a C2oClO~alkenyl group, a C7-C~O-arylalkyl group, a C7-C~O-alkylaryl group or a Ca-C~D-arylalkenyl group, 0 Rl5 and Rl7 are a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom Ml, Rl2 is R'9 Rl9 R'9 R'5 Rl9 R~9 Rl9 R
2_ , --U 2_ C R 2 2 ~_ --C _ _ o _ U 2 _ --C--C
R~C ~ R2D R20 R2c R20 R~ R~
= BRl9, = AIRl9, -Ge-, -Sn-, -0-~ -S-, = SO, =SO2, = NRl9, = CO, = PRl9, or = P(O)Rl9, where R19, R20 and R2l are identical or different and are a hydrogen atom, a halogen atom, a Cl-ClO-alkyl group, a Cl-C10-fluoroalkyl group, a C6-C10-fluoxsaryl group, a C6-C1O-aryl group, a Cl-C1O-alkoxy group, a C2-C1O-alkenyl group, a C~-C40-arylalkyl group, a Ca-C40-aralkenyl group or a C7-C~O-alkylaryl group, or R'9 and R20, or Rl9 and R2', form a ring, in each ca~e wlth the atom linking them, and M2 is silicon, germanium or ti~, ~nd, in ~ach Gase at ~5 a molecular weight diætribution M~/M~ of le~s than 2, always with respect to the polymer block ~orming, the reaction condition~ are changed in such a way that the monomer/comonomer ratio ~hanges by at lea t 10 % or a further polymeri~able monomer of the formulae I-VIII is metered into the monomer or the monomers.
., , :
- 6 ~ 2 The polymPrization is carried out in such a way that, depending on the number of change~ in the parameters or the monomer composition which are carried out, a two-stage or multi-stage polymerization takes place, it also being possible to polymerize a homopolymer 3equence of one of the monomers of the formulae I to VIII in the first polymeriæation stage.
Alkyl is straight chain or br~nched alkyl.
For the purposes of the invention, the monocyclic olefin VII can also be substitu~ed (for ~xample by alkyl or aryl radicals).
The cycloolefin block copolymers prepared according to the invention are novel and are also a subject of the present invention.
Pure monomers of the formulae I to VIII, preferably monomers of the formulae I to VII and in particular o~
the formulae I or III, or monomer mixtures are used in the first polymerization stage. In all subsequent poly-merization stages only monomer mixtures are used.
The monomer mixtures used in the polymerization are mixtures of one or more eycloolefins, in particular of the formulae I or III, with one or more acyclic olefins VIII or mixtures of cycloole~ins exclusively. The monomer mixture advantageou~ly compri~es 2 monomer~, which ~re preferably a polycyclic olefin of the formula I or III
and an acyclic olefin of the formula VIIIo The formulae I or III in particular represent norbornene or tetracyclododecene respectively, it ~eing po~ible for these to be substituted by (Cl-C6)-alkylv Formula VIII
pre erably represents l-olefins, in particular ethylene or propylene.
.
2~9952 , Cycloolefin block copolymer~ according to the invention which may be mentioned are, in particular, norbor-nene/ethylene block copolymers and tetr~cyclodode-cene/ethylene block copolymer~, in which each polymer ~equence or each polymer block is made up of a copolymer and norbornene (in the case of norbornene/ethylene block copolymers~ or tetracyclododecene (in the case of tetxa-cyclododecene/ethylene block copolymers) ha~ al~o been incorporated at least in one polymerization ~tage. The particularly preferred norbornene/ethylene block copoly-mers are made up of norbornene/ethylene copolymer ~equen-ces of different composition, i.e. they are compo~ed of blocks (polymer segments) which are ~ach norbornene/ethy-lene copolymers.
The cataly6t to be used for the process according to the invention comprises a cocatalyst and at least one metal-locene (transition metal component) of the formula XI
Rls / Rl~
Rla ~,~1/ (X I ) \ Rls Rl7 In formula XI M' iæ a metal selected from the group comprising titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium and hafnium.
The use of zirconi~n is particularly preferredO
Rl4 and Rls are identical or different and are a hydrogen atom, a C,-Cl0-alkyl group, preferably a Cl-C3-alkyl group, a Cl-Cl0-alkoxy group, pr~ferably a Cl-C3-alkoxy group, a C6-C,0-aryl group, preferably a C6-C8-aryl group, a Cc-C,O-aryloxy group, preferably a C6-C8-aryloxy group, a C2-CIo-alkenyl group, preferably a C2-C4-alkenyl group, ~ C,-C~0-arylalkyl group, preferably a C~-C,0-arylalkyl group, a C7-9 5 ~
C40-alkylaryl group, preferably a C7-C12-alkylaryl group, a C8-C40-arylalkenyl group, prefera~ly a Ca-C,2 arylalkenyl group, or a halogen atom, preferably chlorine.
Rl6 and R17 are identical or different and are a mono-S nuclear or polynuclear hydrocarbon radical which can forma r,andwich structure with the central atom Ml. Rl6 and R17 are preferably indenyl, fluorenyl or cyclopentadienyl.
These radicals can be monosubstitu~ed or polysubstituted, in particular by ( C~-C4 ) -alkyl.
Rl8 is a single-membered or multi-membered bridge which links the radicals R~6 and R'7 ~nd iB preferably R'9 Rl9 R 9 R 9 Rl9 Rl9 R~9 Rl9 ~ 2_ 1~ 2_ --U 2--C R 2 2 1-- , --C-- --O--~1 2-- --C--C-- , 2 0 1 2 D I 2 D I 2 0 R ~ D R R
= BR19, = AIRl9, -Ge-, -Sn-~ O-, -S-, = SO, = SO2, = NR'9, , PR or = P(O)R , where R19, R20 and R21 ar~ id ti cal or different and are a hydrogen atom, a haloqen atom, a C1-C10-alkyl qroup, a C1-C10-fluoroalkyl group, a C6-C,0-aryl group, a C1-C10 alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl yroup, a C~-C40-arylalkenyl group or a C7-C40-alkylaryl group, or Rl9 and R20, or R'9 and R2~, form a ring, in each case together with the atoms linking them.
M2 is silicon, germanium or tin, preferably ~ilicon or germanium.
The prsparation of the metallocenes to be u~ed ac~ording to the invention is known (cf. Journal of Organometallic Chem. 288 (1985) 63-67, EP-A 320 762, EP-A 336 128, EP-A 336 127, EP-A 387 690 and BP A 387 691)~
2~9~2 g Metallocenes preferably used are:
rac-dimethylsilyl-bis(1-indenyl)zirconium dichloride, rac-dimethylgermyl-bi~(1-indenyl)zirconium dichloride, rac-phenylmethylsilyl-bis(l-indenyl)zirconium dichloride, rac-phenylvinylsilyl-bis(1-indenyl)zirconi.um dichloride, 1-6ilacyclobutyl-bis(1-indenyl)zirconium di~hloride, rac-diphenylsilyl-bis(l-indenyl)hafnium dichloride, rac-phenylmethylsilyl-bi~(l-indenyl)hafnium dichloride, rac-diphenylsilyl-bis(l-indenyl)zirconium dichloride, rac-ethylene-l,2-bis(l-indenyl)zirconium dichloride, dimethylsilyl-(9-fluorenyl)-(cyclopentadienyl)zirconium dichloride, diphenylsilyl-(9-fluorenyl)-(cyclopentadienyl)zirconium dichloride, diphenylmethylene-(9-fluorenyl)-cyclopentadienylzirconium dichloride, isopropylene-(9-fluoxenyl)-cyclopentadienyl-zixconium dichloride, phenylmethylmethylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride,isopropylene~(9-fluorenyl)-(1-(3-isopropyl)cyclopentadi-enyl)zirconium dichloride, isopropylene-(9-fluorenyl~(1-(3-methyl)cyclopentadienyl)-zirconium dichloride, diphenylmethylene-~9-fluorenyl)(1-t3 methyl)cyclopentadi-enyl)zirconium dichloride, methylphenylmethylene-(9-fluorenyl)(1-(3~methyl)cyclo-pentadienyl)zirconium dichloride, dimethylsilyl-(9-fluorenyl)(1-(3-methyl)-cy~lopentadi-enyl)zirconium dichloride,diphenylsilyl-(9-fluorenyl~ (3-methyl)cyclopentadi-Pnyl)zirconium dichloride/
diphenylmethylene-(9-fluorenyl)tl-l3-tert.-butyl)~yclo-pentadienyl)zirconium dichloride, isopropylene-(9-fluorenyl)(1~(3-tert.-butyl)cyclopen adi~
enyl)zirconium dichloride and analogou6 hafnocenes.
2 ~ 2 Particularly preferred metallocenes areo rac-dimethylsilyl bis(1-indenyl)zirconium dichloride, rac-phenylmethylsilyl-bis(1-indenyl)zirconium dichloride, rac-phenylvinylsilyl-bistl-indenyl)zirconium dichloride, rac-diphenylsilyl-bis(1-indenyl)zirconium dichloride, rac-ethylene-1,2-bis(l-indenyl)zirconium dichloride, dimethylsilyl-t9-fluorenyl)-(cyclopentadienyl)zirconium dichloride, diphenylsilyl-(9-fluorenyl)-(cyclopentadienyl)~irconium dichloride, diphenylmethylene-(9-fluorenyl~-cyclopentadienyl-zirconium dichloride, isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride or phenylmethylmethylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride and analogous hafnocenes.
The cocatalyst used according to the invention iB prefer-ably an aluminoxane of the formula (IX) - Rl3 Rl3--A i--O---A I 0---A l Rl3 ( I X) for the linear type and/or of the formula (X~
O--A 1~
p ~ 2 for the cyclic type, where, in the formulae IXXj and (X), the radicals R13 can be identical or different and are a C,-C6-alkyl group, a ~6-Cl8-aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably 10 to 35.
The radicals R'3 are pref~rably identical and are methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicalR Rl3 are different, they are prefer~bly methyl and hydrogen or alternatively methyl and isobutyl, the hydrogen or isobutyl content preferably bein~ 0~01 -40 % (number of radicals R~3).
The aluminoxane can be prepaxed in various way~ by known processes. One of the methods i8, for example, to react an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (ga~eous, soli~, liquid or bound - for example as water of crystallization) in an inert solvent (such as, fQr example, toluene). In order to prepare an aluminoxane containing different alkyl groups R'3, two different aluminum trialkyls (AIR3 ~ AIR'3) are reacted with water in accordance with the desired composition (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
The precise structure of the aluminoxane is not known~
Irre~pective of the mode of preparation, a varying content of unreacted aluminum starting compound, which is in a free form or in the form of an adduct, i~ common to all aluminoxane solutions.
25 It is possible to preactivate the metallocene with an aluminoxane of the formula (IX~ and/or (X) before it i6 used in the polymerization reactionO The polymeriæation activity is distinctly increased by this mean~.
The preactivation of the transition metal compound is carried out in solution. Preferably, the metallocene is dîssolved in a solution of the aluminoxane in an i~ert - 12 ~ 2 hydrocarbon. A suitable inert hydrocarbon i~ an aliphatic or aromatic hydrocarbon. Toluene is preferably u~ed.
The concentration of the aluminoxane in the solution i5 in the range from about 1 ~ by weight up to the ~atura-tion limit, preferably from 5 to 30 % by weight, in eachcase with respect to the total solution. The metallocene can be used in ~he C~me concentration, but it i8 prefer ably used in an amount of 10-4 - 1 mol p~r ~ol of alumi-noxane. The preactivation time is 5 minut~ to 60 h~ur~, pr~ferably 5 to 60 minute~. ~he preactivation is carried out at a temperature of -78C to 100C, pr~ferably 0 to 70C.
The metallocene itself can also be prepolymerized or applied to a support or enclosed in a prepolymer (for example on the basis of a metallccene-catalyzed prepoly-merization). The (or one of the) olefin(s) used in the polymerization is preferably u ed for the prepolymerization.
Suitable supports are, for example, silica gels, aluminum oxides, solid aluminoxane or other inorganic aupport materials. A polyolefin powder in finely divided form is also a suita~le support material.
According to the invention, compounds of the formulae R,~NH" XBR'4, R,~P~4 XBR',~, R3CBR'4 or BR' 3 can be used a~
suitable cocatalyst~, instead of sr in addition to an aluminoxane. In these formulae x is a number fr~m 1 to 4, pref~rably 3, the radicals R are identical or different, preferably identical, and are C1-C,D alkyl or Cc-C~B-aryl, or 2 radicale R form a ring together with the atom linking them, and the radic~ls R' are identical or different, preferably ide~tical, and are C6-C18-~yl, which can be ~ubstituted by alkyl, haloalkyl or fluorine.
In particular R i8 ethyl, propyl, butyl or phenyl ~nd R' is phenyl, pentafluorophenyl, 3,5-bi~trifluor~methyl--- 2 ~
phenyl, mesityl, xylyl or tolyl (cf. EP-A 277 003, EP-A 277 004 and EP-A 426 638~.
When the abovementioned cocatalysts are u6ed, the actual (active) polymerization cataly~t compri~e~ the reaction product of metallocene and one of the said ~ompounds.
This reaction product is therefore preferably fir~t prepared out~ide the polymerization reactor in a ~eparate step using a suitable solvent.
In principle, any compound which, on the basi~ of its Lewis acidity, i8 able to convert the neutral metallocene into a cation and to sta~ilize the latter ("labile coordination") iB a suitable cocatalyst according to the invention. In addition, the cocatalyst or the anion formed therefrom should not enter into any further reactions with the metallocene cation formed (cf.
EP-A 427 697).
Purification with an aluminum alkyl, for example AlMe3 or AlEt3, is advantageous in order to remove catalyst poi~on~
present in the olefin. This purification can either be carried out in the polymerization system itself, or the olefin i8 brought into contact with the Al compound before it iB added to the polymerization system and then separated off again.
If a small amount of solvent i5 added to the reaction mixture, the solvents u~ed are conventional inert ~ol~
vents, such as, for example, aliphatic or cycloallphatic hydrocarbon6 (for example cyclohexane, dekalin~, yasoline fractions or hydrogenated diesel oil fraction~ or toluene.
The polymerization takes place in dilute ~olution (<30 %
by volume cycloolefin), in concentrated sollltion (>80 %
by volume cycloolefin) or directly in the liquid un~
diluted cycloolefin monomer.
- 14 - 208~52 Depending on the activity of the catalyst and on the desired molecular weight and the desired molecular weight distribution of the par~icular polymer block, the temper ature and reaction time must be matched accordin~ly. The monomer concentration ~nd the nature of the solvent must also be taken into account, especially as the~e para-meters e~sentially determine the relative rates of incorporation of the monomers ~nd thus are deci~ive for the ylass transition temperature and heat dietortion resistance of the polymers.
The lower the polymerization temperature is cho~en within the range from -78 to 150C, preferably between -78 and 80C and particularly preferably between 20 and 80C, the longer can be the polymerization time for virtually the same range of molecular weight distribution MW/M~ for the particular polymer blocks.
If the sudden change in the reaction conditions takes place at a time at which the molecular weight distribu-tion M~/Mn of the polymer block forming is 1, it can reliably be assumed that all of the polymer blocks formed in this polymerization stage possess a cataly~t-active chain end (i.e. the chains are so-called live polymer chains) and thus a further block can be polymerized onto these chain ends by changing the polymerization condi-tions. For thi~ extrema case coupling i~ 100 %, The morethe molecular weight distribution M~/M~ of the polymer blocks ~ormed in a polymerization ~tage deviatq~ from 1, i.e. M~/Mn >1, the greater is the increase in ~he number of catalyst-inactive chain ends (i.e. ~o-called dead chain ends or ~topped chains), which are no longer capable of coupling a further block.
For the process according to the invention for the preparation of block copolymers this siqnifie~ that the more MW/Mn of the polymer block X prepared in the poly merization stage X is in the vicinity of the value 1 at 2089~2 the ~ime at which the change in the reaction parameters takes place the greater will be the proportion of block polymer chains in the finished product at which a chemi-cal coupling between block X and block X+1 ha~ been effected.
With respect to the structural homogeneity or ~urity of the cycloolefin block copolymers this signifies that the time window6 for the individual polymerization ~tages should as far as possible be 80 cho~en that they cor-respond to an M~/M~ of the corresponding polymer blockæ ofvirtually 1, in order to obtain cycloolefin block copoly~
mers of high purity and high structural homogeneityO
If it is also desired to trigger a ~pecific molecular weight of a polymer block, the reaction time must also be adjusted to the desired molecular weight~
The determination of the requisite reaction time beore the reaction conditions are changed, which varie~ depend-ing on the said reaction parameters and the rate of cycloolefin incorporation, is carried out by means of a calibration by simple sampling as de cri~ed in the illustrative embodiments. Diagrams from which the re-quisite times can then be taken (pr ~ rmined) can be plotted from test series. Fig. 3 ~ hich generally shows the dependence of the molecular weight distribution M~
of a polymer block on the reaction time t, i8 an example of such a diagr~m.
With the ex~eption of the first polymerization ~tage in a discuntinuous proce~, the cali~ration to determin~ the reaction time for all polymerization ~tages in discon tinuous and continuous proces3es must be carried out in separate single-stage experiments in which ~ except for the reaction time - the particular rsaction conditions of the corresponding polymerization -~tage are u~ed.
. . .
2 ~ r~ 2 In the case of a copolymerization ~tag~, th~ molar monomer ratio in the reaction medium of cycloolefins to acyclicolefins or of a cycloolefin to the other cycloolefins, if no acyclic olefins are used, i6 then changed accordingly at the time at which the reaction conditions are changed. The change in the monomer ratio should amount to at least 10 %, preferably more than 25 %.
If the first polymerization stage is a homopolymerization (for example polymerization of norbornene), at lea~t a second monomer enters the reaction chamber at the time at which the change is m~de.
During a polymerization stage, or the formatLon of a polymer block, the monomer ratios in the reaction chamber are as a rule kept constant, ~o that chemically uniform polymer blocks are formed. However, it is al90 po~sible continually to change the monomer ratios during a poly-merization stage, which then lead~ to polymer blocks which have a structural gradient along the polymer chain, i.e. the incorporation ratio (for example the ratio between the number of norbornene units and the number of ethylene units in a pdrt of the polymer block) changes continually along the corresponding polymer bloak. In the case of polymer blocks which are made up of more than two types of monomer, this gradient can be aahieved by continually changing the concentration of a ~ingle monomer component. Blocks which have structural gradients can alco be prodllced in those polymerization ~tage~ in which the concentration of several monomer comp~nents is changed continuously at the same time. The re~ulting block copolymers are likewise Gf intere~t and a subject of the present invention.
The changes in the mor.omer ratios o be carried out in the proces~ according to the invention can be achieved, for example, by changing the pressure of the acy~lic ~8~2 olefin, by changing the temperature and thus the 801u-bility of gaseous olefins, by dilution with ~olvents under constant pressure of the acyclic olefin or by metering in a liquid monomer. Several of the ~aid para-meters can also be changed at the same time.
Both sudden and continuous changes of this type in the monomer ratio - and thus the preparation of blo~k copoly-mers according to the invention - ~an be effected both when the reaction is carried out di~continuou~ly and when the reaction is carried out ~ontinuously.
Continuous and multistage polymerization pro~esses are particularly advantageous because they make pos~ible economically advantageous use of the cycloolefin. In addition, in continuous processes the cyclic olefin,~
which can be obtained as residual monomer together with the polymer, can be recovered and recycled to the reac-tion mixture.
When the polymerization is carried out in this way, the block length can be controlled via the throughput and reaction volume of th~ various reaction vessel~ (i.e-.
these two parameters determine the dwell time in the various reaction locations).
An example of a process of this type i8 ~hown diagram-matically by Figures l and 2. Figure 1 ~how~ ~ possible 2; set-up for a simple continuous procedure, whioh can be expanded by further element~ (reaction vessels etcO) if required. ~he symbols have the following me nings:
Parameters: pressures pl and p2i pl>>p2; throughput v;
throttling d; level adju~tment l; 0 Parts: ~tirred vessels R; pump P, tubular reactor K; valves V
a = gaseous olefin or olefin mixture;
b = cycloolefin or cycloolefin solution; cycloolefin mixture or ~olution of cycloolefin mixture ':
--`` 2~`~9~52 c - polymer solution;
k - catalyst;
Pr = product.
Figure 2 shows an example of the variation profile for the reaction conditions to which the re~cting chain end of a block copolymer chain according to the invention can be subjected, assuming two pa~ses through the ~ontinuous reaction cycle which is 6hown diagrammatically in Figure l, start and discharge of the chain taking pla~e in reactor chamber Rl.
The symbols have the following meaning~:
X1 = cycloolefin/1-olefin ratio in reaction chamber Rl X2 = cycloolefin/1-olefin ratio in reaction chamber tl+~tl = dwell time in reaction chambex Rl t2+~t2 = dwell time in reaction chamber R2 +~ = indicates that a dwell time distribution exi6ts and therefore these times vary about a ~tatis-tical average value tl';t2' = dwell time in the tu~es between R1 and R2 or R2 and R1 (in comparison with R1 and R2, the dwell time distributions in these tube lines are narrow and therefore the indication "~t" ha~
been dispensed with here; usually the rate of incorporation of the 1-olsfin i8 yreater than that of the cycloolefin, which then lead~ to a slight change in the monomer ratio in favor of the cycloolefin) fl;f2 ~ r~latively sudden change in the monomer ratio on entering the reaction cha~ber R2 or Rl An installation according to ~igure 1 can be operated either continuously, i.e. by permanent pump transfer oi the reaction ~olution or permanent metering o~ the monomers and discharge of the product ~olution, or ' ''~'~ ` . ..
~ .
- lg- ~9g~2 discontinuously by batchwise pump tran~fer of the entire reaction solution from reactor to reactor.
The discontinuous variant has the advantage that both block length and the number of blocks per polymer chain can be precieely adjusted. In the ca~e of the continuous procedure, the block l~ngth can be accurately controlled, whilst the number of blocks is acce~sible or adjustable as a statistical average over the achieved average molecular weight of the block copolymer and the aLmed-at averaqe molecular weight of the polymer blocks. The prPparation of block copolymers which have ~pecific block chain ends can be effected very accurately using the discontinuous procedure, whereas the continu~us process enables only statistical information in this respect.
It follows that the described change in the reaction conditions (parameters) can be carried out one or more times, which leads to a sequence of two or more different blocks within a pslymer chain. The only condition with which it is necessary to comply is that the particular start of -the reaction ror the formation of a new block is so chosen that the latter takes place at a time at which - according to the calibration - the molecular weight distribution MW/M~ o~ the growing polymer block is stiil ~2, preferably virtually 1. If this condition is complied with, a new block which has a new composition can always be polymerized onto ihe growing polymer chain. These reaction times vary depending o~ the catalyst system used, the reaction temperature and the monomer concentra-tion.
If no further new block is to be polymerized on, the polymerization is completed, i~e~ discharged or ~toppad, under the last chosen reaction conditions.
A discontinuous procedure can also be carried out in one reaction ve~sel in that the change in the r0action conditions and stopping of the reaction are carried out 2 0 ~ 2 successively in one reactor.
In general the following applie~ with respect to the reaction parameters:
If pure open-chain olefin, for example ethylene, is being injected under pressure, pxes~ure~ of between 0.01 and 64 bar, preferably 2 to 40 bar and particularly prefer`ab-ly 4 to 20 bar are used. I, in addition to the open-chain olefin, an inert gas, for example nitrogen or argon, is al~o injected undPr pressure, ~he total pres-sure in the reaction vessel is 4 to 64 bar, preferably 2to 40 bar and particularly preferably 4 to 25 bar. If the cycloolefinic component is in the undiluted iorm, a high rate of incorporation of cycloolefin is also achieved at high pressures.
The metallocene compound is used in a concentration, with respect to the transition metal, of 10~1 to 10-8, prefer-ably 10-3 to 10-6 mol of transition metal per dm3 of reactor volume. The aluminoxane is used in a concentra-tion of 10-5 to 10-1, preferably 10-4 to 2 x 10-2 mol per dm3 of reactor volume, with re~pect to the aluminum content~
In principle, higher concentrations are, howe~er, also possible. The other cocatalysts mentioned are preferably used in approximately equimolar amounts with respect to the metallocene.
Apart from the said, bridged metallocene~, metalloc0nes which have identical or similar non-bridged ligand~ can, in principle, also be used. In the case of the~e me~al-locenes, the reaction times chosen must be distinctly shorter tha~ those for the bridged metallocene~, under comparable xeaction conditions.
When preparing copolymers, the molar ratios of the polycyclic ol~fin to the open-chain olefin (preferably) used can be varied within a wide range. The molar ratios of cycloolefin to open-chain olefin are preferably 2~Y,~9!~, adjusted to 50:1 to 1:50, in particular 20:1 to 1:20.
The cycloolefin block copolymers according to the inven-tion lead to advantageous mechanical property co~ina-tion~ in blends with other cycloolefin copolymer~.
S The following examples are intended to illu~trate the invention in more detail:
Example 1 A clean and dry 1.5 dm3 polymeri~Ation reactor provided with a stirrer was flushed with nitrogen and then with ethylene and filled with 576 ml of an 85 ~ strength by volume solution of norbornene in toluene.
The reactor was then kapt at a temperature of 20C, with stirring, and 2 bar ethylene texcess pre~4ure) wa~ in-jected under pressure.
20 cm3 of a solution of methyl aluminoxane in toluene (MA0 solution) ~10.1 ~ by weight of methyl aluminoxane having a molar mass of 1300 g/mol according to cryoscopic determination) were then metered into the reactor and the mixture was stirred Ior 15 min at 20C, the ethylene pressure being kept at 2 bar by metering in additional ethylene. In parallel, 60 mg of rac-dimethylsilyl-bis(l-indenyl)zirconium dichloride were di~solved in 10 cm3 of a solution of methyl aluminoxane in toluene (~ee above for concentration and quality) and preactivated by leaving to ~tand for 15 minutes. The ~olution of th~
complex was then metered into the reactor. Polymerization was then carried out at 20C, with stirrin~ 1750 rpm), the ethylene pressure bein~ kept at 2 bar by metering in additional ethylene.
After 30 min, 50 ml of the reaction solution were removed via a lock. Immediately after this sampling, the ethylene 2~9~2 pressure was increased to 7 bar in the course of 10 sec and kept at this pressure for 5 min by metering in additional ethylene~ The polymerization was then ~topped ky adding lO ml of water via a lock. ~fter ~ubsequent letti~g-down, the reaction solution was drained into a`
vessel and then added dropwise to 2 d m3 of acetone, the resulting mixture w ~ 9 stirred for 10 min and the ~u~pend ed, polymer solid was filtered off.
20 g of polymer which has a gla6s transîtion temperature of 140C and a vi~cosity number of g5 ml/g and a mole-cular weight distribution M,,,/ Mn Of 1.5 were obtained.
After removal, the 50 ml of sample were treat~d, with stirring, with 0.5 ml of water and then worked up analo-gously to the abovementioned working-up of the reaction solution of the end product. 4.5 g of polymer which has a glass transition temperature of 165C, a visco~ity number of 150 mlig and a molecular weight distribution MW/Mn of 1.3 were isol~ted from the 50 ml of sample.
-Examples 2 - 4 The procedure was analogous to Example 1 but, in deviat-ion therefrom, the condition6 from Table 1 w~re cho~e~.
The resulting polymer properties are summarized in ~ble 2.
Table 1:
_ _ .
Example Nb ~olution PolymorisationPolymerlsation h~ount o~
No. ConC~ntratiDn St~ge 1 Stag ~ 2 ~otallDccno (~ by volum~ Timn Et prn3auro Ti~ ~t pre~ure ~g) ~rlin) j ~bar) ~min) ~oar) 2 24.4 30 1 15 7 ~0.3 3 24.4 30 1 10 7 92.2 4 43.B 30 2 2 6 69.9 _ _ Nb ~ NorbDrn~no ~able 2:
Example5ample ~n~ product No. Vn Tg ¦ Mwt~Vn Tg M~
(ml/g) (C) - (ml/g) (~C) 2 22 167 1.2 10898 1.2 3 27.5 165 1.2 19281 1.6 4 73 173 1.2 107134 1.3 . . _ __ Example 5 A kinetic te6t was carried out analogously to Example 1.
860 cm3 of an 85 % strength by volume solution of norbor-nene in toluene were used for the polymerization. The reactor temperature was 24C and the ethylene sxcess pressure was kept constant at 6 bar. 60 cm3 of a solution of MAO in toluene (10.1 ~ strength by weight) were added and the mixture wa~ stirred for 15 min. 21 mg of rac-dimethylsilyl-bis(1-indenyl)zirconium dichloride were added to 20 cm3 of MAO solution and after preactivation the mixture was injected into the reactor under pre~sure.
Samples (50 cm3 ) were taXen via a iock at the reaction times indicated in Table 3. The polymerization wa~
immediately stopped by adding 4 çm3 of isopropanol. The product was w~shed several times wikh acetone and dilute hydrochloric acid (see Example 1).
The resulting polymer product~ were mea~ured by gel permeation chromatography. The number-average molecular weight (M~) and weight-average molecular weight ~M~) and the inhomogeneity (MW/M~) ar~ given in Table 3. The distribution curves for all samples are shown in Fig. 4.
.
: ~ , ~- 20~3~5~
Table 3:
Sample Reaction M~ Mw M~/Mn No. time/min x 10~3g/molx 10 3g/mol 1 10 21.~ 2~.4 1.10 2 20 37.3 4~.8 1O15 3 30 51.0 62.0 1.22 4 45 73.0 92.0 1.25 83.0 121.0 1.46 6 90 110.0 167O0 1.52 7 120 125.0 217.0 1.74 8 150 153.0 261.~ 1.7l Fig. 4 shows the molecular weight distribution functions obtained by gel permeation chromatography for ~mples Nos. 1 - 8 from Exampla 5 from left to right with in-creasing molecular wei~ht and increasing reactivn time.
Reaction time and average molecular weights (M~, Mw~ are given in Table 3.
The area of the dis~ribution function in Fig. 4 is weighted by the yield.
GPC (gel permeation chromatography) measurements were carried out as follows. A type 150-C ALC/GPC Millipore Waters Chrom. chromato~3raph And a column set comprising 4 Shodex columns of type AT-80 M/S were u~edO The solvent was o-dichlorobenzene.
Further mea~urement parameters were:
Temperature: 135C
30 Flow rate: 0,5 ml/min 5ample amount: 0.4 ml of sample solution Concentration of the sample solution 0.1 g/dl .
2V~9~2 Calibration: according to polyethylene standard Example 6 The procedure wa~ analogous to Example 1 but, in devia~
tion therefrom, the following conditionc were ~ho~en:
- cycloolefin = tetracyclodode~ene - concentration of the cycloolefin solution = 127 g/l - amount of cycloolefin solution = 860 ml - amount of NA0 solution = 100 ml - metallocene = rac-dimethylsilyl-bistl-indenyl~zirconium-dichloride - amount of metallocene = 62 mg - ethylene pressure maintained by additional metering =
3 bar - sampling time = after 20 min - the cycloolefin concentration was changed by adding pure cycloolefin via a lock.
- duration of thP addition operation = 2 ~ec - amount of cycloolefin metered in = 170 g - ethylene pressure after addition = 3 bar - duration of polymerization after m~tering in -- 30 min The resulting polymers are distinguished by:
- amount of resulting end product = 1705 g - amount of polymer from sample ~ 390 mg 25 - gla8s transition temperature of the end product ~ 175C
glass transition temperature o~ the polym~r from sample = 110C
- molecular weight Mn of the end product - 7~,000 g/mol - molecular weight Mn o the polymer ~r~m s~mple -52,000 g/mol - viscosity nu~ber of the end product ~ 105 ml/g - viscosity number of the polymer from ~ample ~ fi6 ml~g - molecular weight distribution Mw~Mn of the end product = 1.9 " 2~9952 - molecular weight distribution ~w/~n of the polymer ~rom sample = 1.4 Comparison example 1 (compari~on example with respect to Example 6 The procedure was as in xamPle_6 but, in deviatio~
therefrom, the addition of the pure cycloolefin wa3 already carried out before the addition of the metallo-cene and thu~ before the start of the polymerization~ The polymerization was stopped after 3 hour~. The re6ulting end product i~ distinguished by the following characteristics:
- glass transition temperature = 151C
- viscosity number = 84 ml~g Example 7 Polymerization experiments were carrie/ ~out in an instal-lation corresponding to that in Fig.~10 The installation was characterized by the following features:
- R1 has a volume of 80 l - R2 comprises a tube in which static mixing elements are ~ixed -- R2 has a volume of 2~0 ml - K is a cooling tube which has a volume of 15 l - P is a gear pump The polymerization was carried out in a~cordan~e with the following concept:
- a olution of cycloolefin in toluene was initially introduced into R1;
- pllmp transfer was carried out using the pump in a~cor-dance with a calibration with constant flow rate;
- the gaseous olefin was introduced at excess pre~ure into the circulation flow immediately upstream of the ~0~9~2 .
~ 27 -static mixer, - in reactor Rl the pressure was kept constant by con-trolled letting-off of gas.
The following polymerization conditions were maintained:
- cycloolefin: norbornene - gaseous olefin: ethylene - metallocene:diphenylmethylene-(9-fluorenyl)cyclopenta-dienylzirconium dichloride - amount of norbornene (liquid) initially introduced =
- amount of toluene initially introduced - 30 1 - amount of MAO solution (MAO solution according to Example 1) initially introduced = 1000 ml - amount of metallocen~ (catalyst preparation according to Example 1) = 200 mg - ethylene excess pressure during the polymerizatioll on the ethylene line = 11 bar - pressure in R2 immediately downstream of th~ static mixing elements = 10.5 bar - pressure in R1 during the polymerization = 2.5 bar - circulation stream during the polymerization = 1500 l/h - polymerization temperature: in R1 = 40C
in R2 = 43C
After the start of the polymerization by addition of the catalyst via a lock, samples were taken regularly at the location in the installation designated by Pr in Fig. 1.
The polymerization was stopped after 50 minut~ Workin~
up of the samples and of the end product was c~rr ed out analogously to Example 1.
The following properties were determined for 8ampl~ and end product:
- 900 ml sample after 10 minutes:
- amount of polymer = 0.5 g - glass transition temperature = 140C
`:
~ 2~9~
- viscosity number = 62 ml~g - 600 ml sample after 20 minutes~
- amount of polymer = 1. 4 g - glass transition temperature = 137C
A common method for improving pha~e binding i~ the admixture o a polymer phase promoter, the characteri~tic feature of which is that its chain is physically or chemically anchored both in the first and in the ~econd phase (cf. Rub~er Toughened Plastics, Adva~c0s in Chemistry Series, Washington DC, 222, 1989; ppO 3 - 64).
The object on which the invention i5 based was thus to find a phase promoter for cycloolefin copol~mer~ of different glass transition temperatures and a process for its preparation.
It has been found, surprisingly, that when the polymeriz-ation is conducted in a particular way, based on cata-lysis using metallocene catalysts, polymers are formed ~0 which are very suitable as phase promoters and in variol1s cases even facilitate miscibility of different cyclo-olefin copolymers. In this context miscibility signifies that thP finished polymer mixture has a single glass transition temperature or that the gla~ transition temperatures of the mixture are closer together than the glass transition temperatures of the pure components.
Kinetic studies have shown that the polymer material~
prepared according to the invention are cycloolefin block copolymers.
The invention thus relates to a process for the prepara-tion of a cycloolefin block copolymer, wherein 0.1 to 95 % by weight, with respect to the total ~mount of monomers employed, of at least one monomer of the 2~8~2 formulae I, II, III, IV, V o:r VI
/CH\ Rl ¦¦R'-C--R~
\¦ / ~R2 H C f C H
¦IR3 - C - R~ ¦ CH2 ( I I ) .
HC\I ,CH
/ ¦ \ ~ I \ /
llr3--C--R4 ¦R~--C R ¦ ( \ I H ~ \ C H /
H C/ ¦ \C H~ ¦ \C H~l \C H/
I ~S-C--R4 ¦R5--C R ¦ R7- C-R3 ¦ ( I Y) .
R s / I \ / \ /
~!R -C--R4 1 ¦ (V) .
HC\I ~CH /CH
CH CH \R~
~S
f C H \C ~ ~C H \ R 2 ;
2~99~2 in which Rl, R2, R3, R4, R5, R6, R7 and R~ are identical or different and are a hydrogen atom or a Cl-C3-alkyl radical, it being po~sible for the same radicalG in the various formulae to have different meanings, 0 to 95 ~ by weight, with xespect to the total amount of monomers employed, of a cycloolefin of the for~ula VII
CH CH
( V l l ) ( C H 2 ) n in which n is a number from ~ to 10, and 0 to 99 % by weight, with respect to the total amount of monomers employed, of at least one acyclic olein of the formula VIII
R \ / (Ylll), ,C C~
R~l/ `R'2 in which R9, Rl, Rl1 and R12 are identical or different and are a hydrogen atom or a Cl-C~-alkyl radical, are poly-merized at temperatures of -78 to 150C and a pre~ure of OoO1 to 64 bar, ;n the presence of a catalyst which i~
composed of ~ cocatalyst and a metallocene o the ~ormula XI R
/ / R~
R18 Ml (X I ) \ R15 :
. .. ~ : .
:
2~8~2 in which M' is titanium, zirconium, hafnium, va~adium, niobium or tantaluml Rl4 and Rls ar~ identical or different and are a hydrogen atom, a halogen atom, a C,-C,O-alkyl group, a Cl-C10-alkoxy group, a C6-C,O-aryl group, a C6-ClD-aryloxy group, a C2oClO~alkenyl group, a C7-C~O-arylalkyl group, a C7-C~O-alkylaryl group or a Ca-C~D-arylalkenyl group, 0 Rl5 and Rl7 are a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom Ml, Rl2 is R'9 Rl9 R'9 R'5 Rl9 R~9 Rl9 R
2_ , --U 2_ C R 2 2 ~_ --C _ _ o _ U 2 _ --C--C
R~C ~ R2D R20 R2c R20 R~ R~
= BRl9, = AIRl9, -Ge-, -Sn-, -0-~ -S-, = SO, =SO2, = NRl9, = CO, = PRl9, or = P(O)Rl9, where R19, R20 and R2l are identical or different and are a hydrogen atom, a halogen atom, a Cl-ClO-alkyl group, a Cl-C10-fluoroalkyl group, a C6-C10-fluoxsaryl group, a C6-C1O-aryl group, a Cl-C1O-alkoxy group, a C2-C1O-alkenyl group, a C~-C40-arylalkyl group, a Ca-C40-aralkenyl group or a C7-C~O-alkylaryl group, or R'9 and R20, or Rl9 and R2', form a ring, in each ca~e wlth the atom linking them, and M2 is silicon, germanium or ti~, ~nd, in ~ach Gase at ~5 a molecular weight diætribution M~/M~ of le~s than 2, always with respect to the polymer block ~orming, the reaction condition~ are changed in such a way that the monomer/comonomer ratio ~hanges by at lea t 10 % or a further polymeri~able monomer of the formulae I-VIII is metered into the monomer or the monomers.
., , :
- 6 ~ 2 The polymPrization is carried out in such a way that, depending on the number of change~ in the parameters or the monomer composition which are carried out, a two-stage or multi-stage polymerization takes place, it also being possible to polymerize a homopolymer 3equence of one of the monomers of the formulae I to VIII in the first polymeriæation stage.
Alkyl is straight chain or br~nched alkyl.
For the purposes of the invention, the monocyclic olefin VII can also be substitu~ed (for ~xample by alkyl or aryl radicals).
The cycloolefin block copolymers prepared according to the invention are novel and are also a subject of the present invention.
Pure monomers of the formulae I to VIII, preferably monomers of the formulae I to VII and in particular o~
the formulae I or III, or monomer mixtures are used in the first polymerization stage. In all subsequent poly-merization stages only monomer mixtures are used.
The monomer mixtures used in the polymerization are mixtures of one or more eycloolefins, in particular of the formulae I or III, with one or more acyclic olefins VIII or mixtures of cycloole~ins exclusively. The monomer mixture advantageou~ly compri~es 2 monomer~, which ~re preferably a polycyclic olefin of the formula I or III
and an acyclic olefin of the formula VIIIo The formulae I or III in particular represent norbornene or tetracyclododecene respectively, it ~eing po~ible for these to be substituted by (Cl-C6)-alkylv Formula VIII
pre erably represents l-olefins, in particular ethylene or propylene.
.
2~9952 , Cycloolefin block copolymer~ according to the invention which may be mentioned are, in particular, norbor-nene/ethylene block copolymers and tetr~cyclodode-cene/ethylene block copolymer~, in which each polymer ~equence or each polymer block is made up of a copolymer and norbornene (in the case of norbornene/ethylene block copolymers~ or tetracyclododecene (in the case of tetxa-cyclododecene/ethylene block copolymers) ha~ al~o been incorporated at least in one polymerization ~tage. The particularly preferred norbornene/ethylene block copoly-mers are made up of norbornene/ethylene copolymer ~equen-ces of different composition, i.e. they are compo~ed of blocks (polymer segments) which are ~ach norbornene/ethy-lene copolymers.
The cataly6t to be used for the process according to the invention comprises a cocatalyst and at least one metal-locene (transition metal component) of the formula XI
Rls / Rl~
Rla ~,~1/ (X I ) \ Rls Rl7 In formula XI M' iæ a metal selected from the group comprising titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium and hafnium.
The use of zirconi~n is particularly preferredO
Rl4 and Rls are identical or different and are a hydrogen atom, a C,-Cl0-alkyl group, preferably a Cl-C3-alkyl group, a Cl-Cl0-alkoxy group, pr~ferably a Cl-C3-alkoxy group, a C6-C,0-aryl group, preferably a C6-C8-aryl group, a Cc-C,O-aryloxy group, preferably a C6-C8-aryloxy group, a C2-CIo-alkenyl group, preferably a C2-C4-alkenyl group, ~ C,-C~0-arylalkyl group, preferably a C~-C,0-arylalkyl group, a C7-9 5 ~
C40-alkylaryl group, preferably a C7-C12-alkylaryl group, a C8-C40-arylalkenyl group, prefera~ly a Ca-C,2 arylalkenyl group, or a halogen atom, preferably chlorine.
Rl6 and R17 are identical or different and are a mono-S nuclear or polynuclear hydrocarbon radical which can forma r,andwich structure with the central atom Ml. Rl6 and R17 are preferably indenyl, fluorenyl or cyclopentadienyl.
These radicals can be monosubstitu~ed or polysubstituted, in particular by ( C~-C4 ) -alkyl.
Rl8 is a single-membered or multi-membered bridge which links the radicals R~6 and R'7 ~nd iB preferably R'9 Rl9 R 9 R 9 Rl9 Rl9 R~9 Rl9 ~ 2_ 1~ 2_ --U 2--C R 2 2 1-- , --C-- --O--~1 2-- --C--C-- , 2 0 1 2 D I 2 D I 2 0 R ~ D R R
= BR19, = AIRl9, -Ge-, -Sn-~ O-, -S-, = SO, = SO2, = NR'9, , PR or = P(O)R , where R19, R20 and R21 ar~ id ti cal or different and are a hydrogen atom, a haloqen atom, a C1-C10-alkyl qroup, a C1-C10-fluoroalkyl group, a C6-C,0-aryl group, a C1-C10 alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl yroup, a C~-C40-arylalkenyl group or a C7-C40-alkylaryl group, or Rl9 and R20, or R'9 and R2~, form a ring, in each case together with the atoms linking them.
M2 is silicon, germanium or tin, preferably ~ilicon or germanium.
The prsparation of the metallocenes to be u~ed ac~ording to the invention is known (cf. Journal of Organometallic Chem. 288 (1985) 63-67, EP-A 320 762, EP-A 336 128, EP-A 336 127, EP-A 387 690 and BP A 387 691)~
2~9~2 g Metallocenes preferably used are:
rac-dimethylsilyl-bis(1-indenyl)zirconium dichloride, rac-dimethylgermyl-bi~(1-indenyl)zirconium dichloride, rac-phenylmethylsilyl-bis(l-indenyl)zirconium dichloride, rac-phenylvinylsilyl-bis(1-indenyl)zirconi.um dichloride, 1-6ilacyclobutyl-bis(1-indenyl)zirconium di~hloride, rac-diphenylsilyl-bis(l-indenyl)hafnium dichloride, rac-phenylmethylsilyl-bi~(l-indenyl)hafnium dichloride, rac-diphenylsilyl-bis(l-indenyl)zirconium dichloride, rac-ethylene-l,2-bis(l-indenyl)zirconium dichloride, dimethylsilyl-(9-fluorenyl)-(cyclopentadienyl)zirconium dichloride, diphenylsilyl-(9-fluorenyl)-(cyclopentadienyl)zirconium dichloride, diphenylmethylene-(9-fluorenyl)-cyclopentadienylzirconium dichloride, isopropylene-(9-fluoxenyl)-cyclopentadienyl-zixconium dichloride, phenylmethylmethylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride,isopropylene~(9-fluorenyl)-(1-(3-isopropyl)cyclopentadi-enyl)zirconium dichloride, isopropylene-(9-fluorenyl~(1-(3-methyl)cyclopentadienyl)-zirconium dichloride, diphenylmethylene-~9-fluorenyl)(1-t3 methyl)cyclopentadi-enyl)zirconium dichloride, methylphenylmethylene-(9-fluorenyl)(1-(3~methyl)cyclo-pentadienyl)zirconium dichloride, dimethylsilyl-(9-fluorenyl)(1-(3-methyl)-cy~lopentadi-enyl)zirconium dichloride,diphenylsilyl-(9-fluorenyl~ (3-methyl)cyclopentadi-Pnyl)zirconium dichloride/
diphenylmethylene-(9-fluorenyl)tl-l3-tert.-butyl)~yclo-pentadienyl)zirconium dichloride, isopropylene-(9-fluorenyl)(1~(3-tert.-butyl)cyclopen adi~
enyl)zirconium dichloride and analogou6 hafnocenes.
2 ~ 2 Particularly preferred metallocenes areo rac-dimethylsilyl bis(1-indenyl)zirconium dichloride, rac-phenylmethylsilyl-bis(1-indenyl)zirconium dichloride, rac-phenylvinylsilyl-bistl-indenyl)zirconium dichloride, rac-diphenylsilyl-bis(1-indenyl)zirconium dichloride, rac-ethylene-1,2-bis(l-indenyl)zirconium dichloride, dimethylsilyl-t9-fluorenyl)-(cyclopentadienyl)zirconium dichloride, diphenylsilyl-(9-fluorenyl)-(cyclopentadienyl)~irconium dichloride, diphenylmethylene-(9-fluorenyl~-cyclopentadienyl-zirconium dichloride, isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride or phenylmethylmethylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride and analogous hafnocenes.
The cocatalyst used according to the invention iB prefer-ably an aluminoxane of the formula (IX) - Rl3 Rl3--A i--O---A I 0---A l Rl3 ( I X) for the linear type and/or of the formula (X~
O--A 1~
p ~ 2 for the cyclic type, where, in the formulae IXXj and (X), the radicals R13 can be identical or different and are a C,-C6-alkyl group, a ~6-Cl8-aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably 10 to 35.
The radicals R'3 are pref~rably identical and are methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicalR Rl3 are different, they are prefer~bly methyl and hydrogen or alternatively methyl and isobutyl, the hydrogen or isobutyl content preferably bein~ 0~01 -40 % (number of radicals R~3).
The aluminoxane can be prepaxed in various way~ by known processes. One of the methods i8, for example, to react an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (ga~eous, soli~, liquid or bound - for example as water of crystallization) in an inert solvent (such as, fQr example, toluene). In order to prepare an aluminoxane containing different alkyl groups R'3, two different aluminum trialkyls (AIR3 ~ AIR'3) are reacted with water in accordance with the desired composition (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
The precise structure of the aluminoxane is not known~
Irre~pective of the mode of preparation, a varying content of unreacted aluminum starting compound, which is in a free form or in the form of an adduct, i~ common to all aluminoxane solutions.
25 It is possible to preactivate the metallocene with an aluminoxane of the formula (IX~ and/or (X) before it i6 used in the polymerization reactionO The polymeriæation activity is distinctly increased by this mean~.
The preactivation of the transition metal compound is carried out in solution. Preferably, the metallocene is dîssolved in a solution of the aluminoxane in an i~ert - 12 ~ 2 hydrocarbon. A suitable inert hydrocarbon i~ an aliphatic or aromatic hydrocarbon. Toluene is preferably u~ed.
The concentration of the aluminoxane in the solution i5 in the range from about 1 ~ by weight up to the ~atura-tion limit, preferably from 5 to 30 % by weight, in eachcase with respect to the total solution. The metallocene can be used in ~he C~me concentration, but it i8 prefer ably used in an amount of 10-4 - 1 mol p~r ~ol of alumi-noxane. The preactivation time is 5 minut~ to 60 h~ur~, pr~ferably 5 to 60 minute~. ~he preactivation is carried out at a temperature of -78C to 100C, pr~ferably 0 to 70C.
The metallocene itself can also be prepolymerized or applied to a support or enclosed in a prepolymer (for example on the basis of a metallccene-catalyzed prepoly-merization). The (or one of the) olefin(s) used in the polymerization is preferably u ed for the prepolymerization.
Suitable supports are, for example, silica gels, aluminum oxides, solid aluminoxane or other inorganic aupport materials. A polyolefin powder in finely divided form is also a suita~le support material.
According to the invention, compounds of the formulae R,~NH" XBR'4, R,~P~4 XBR',~, R3CBR'4 or BR' 3 can be used a~
suitable cocatalyst~, instead of sr in addition to an aluminoxane. In these formulae x is a number fr~m 1 to 4, pref~rably 3, the radicals R are identical or different, preferably identical, and are C1-C,D alkyl or Cc-C~B-aryl, or 2 radicale R form a ring together with the atom linking them, and the radic~ls R' are identical or different, preferably ide~tical, and are C6-C18-~yl, which can be ~ubstituted by alkyl, haloalkyl or fluorine.
In particular R i8 ethyl, propyl, butyl or phenyl ~nd R' is phenyl, pentafluorophenyl, 3,5-bi~trifluor~methyl--- 2 ~
phenyl, mesityl, xylyl or tolyl (cf. EP-A 277 003, EP-A 277 004 and EP-A 426 638~.
When the abovementioned cocatalysts are u6ed, the actual (active) polymerization cataly~t compri~e~ the reaction product of metallocene and one of the said ~ompounds.
This reaction product is therefore preferably fir~t prepared out~ide the polymerization reactor in a ~eparate step using a suitable solvent.
In principle, any compound which, on the basi~ of its Lewis acidity, i8 able to convert the neutral metallocene into a cation and to sta~ilize the latter ("labile coordination") iB a suitable cocatalyst according to the invention. In addition, the cocatalyst or the anion formed therefrom should not enter into any further reactions with the metallocene cation formed (cf.
EP-A 427 697).
Purification with an aluminum alkyl, for example AlMe3 or AlEt3, is advantageous in order to remove catalyst poi~on~
present in the olefin. This purification can either be carried out in the polymerization system itself, or the olefin i8 brought into contact with the Al compound before it iB added to the polymerization system and then separated off again.
If a small amount of solvent i5 added to the reaction mixture, the solvents u~ed are conventional inert ~ol~
vents, such as, for example, aliphatic or cycloallphatic hydrocarbon6 (for example cyclohexane, dekalin~, yasoline fractions or hydrogenated diesel oil fraction~ or toluene.
The polymerization takes place in dilute ~olution (<30 %
by volume cycloolefin), in concentrated sollltion (>80 %
by volume cycloolefin) or directly in the liquid un~
diluted cycloolefin monomer.
- 14 - 208~52 Depending on the activity of the catalyst and on the desired molecular weight and the desired molecular weight distribution of the par~icular polymer block, the temper ature and reaction time must be matched accordin~ly. The monomer concentration ~nd the nature of the solvent must also be taken into account, especially as the~e para-meters e~sentially determine the relative rates of incorporation of the monomers ~nd thus are deci~ive for the ylass transition temperature and heat dietortion resistance of the polymers.
The lower the polymerization temperature is cho~en within the range from -78 to 150C, preferably between -78 and 80C and particularly preferably between 20 and 80C, the longer can be the polymerization time for virtually the same range of molecular weight distribution MW/M~ for the particular polymer blocks.
If the sudden change in the reaction conditions takes place at a time at which the molecular weight distribu-tion M~/Mn of the polymer block forming is 1, it can reliably be assumed that all of the polymer blocks formed in this polymerization stage possess a cataly~t-active chain end (i.e. the chains are so-called live polymer chains) and thus a further block can be polymerized onto these chain ends by changing the polymerization condi-tions. For thi~ extrema case coupling i~ 100 %, The morethe molecular weight distribution M~/M~ of the polymer blocks ~ormed in a polymerization ~tage deviatq~ from 1, i.e. M~/Mn >1, the greater is the increase in ~he number of catalyst-inactive chain ends (i.e. ~o-called dead chain ends or ~topped chains), which are no longer capable of coupling a further block.
For the process according to the invention for the preparation of block copolymers this siqnifie~ that the more MW/Mn of the polymer block X prepared in the poly merization stage X is in the vicinity of the value 1 at 2089~2 the ~ime at which the change in the reaction parameters takes place the greater will be the proportion of block polymer chains in the finished product at which a chemi-cal coupling between block X and block X+1 ha~ been effected.
With respect to the structural homogeneity or ~urity of the cycloolefin block copolymers this signifies that the time window6 for the individual polymerization ~tages should as far as possible be 80 cho~en that they cor-respond to an M~/M~ of the corresponding polymer blockæ ofvirtually 1, in order to obtain cycloolefin block copoly~
mers of high purity and high structural homogeneityO
If it is also desired to trigger a ~pecific molecular weight of a polymer block, the reaction time must also be adjusted to the desired molecular weight~
The determination of the requisite reaction time beore the reaction conditions are changed, which varie~ depend-ing on the said reaction parameters and the rate of cycloolefin incorporation, is carried out by means of a calibration by simple sampling as de cri~ed in the illustrative embodiments. Diagrams from which the re-quisite times can then be taken (pr ~ rmined) can be plotted from test series. Fig. 3 ~ hich generally shows the dependence of the molecular weight distribution M~
of a polymer block on the reaction time t, i8 an example of such a diagr~m.
With the ex~eption of the first polymerization ~tage in a discuntinuous proce~, the cali~ration to determin~ the reaction time for all polymerization ~tages in discon tinuous and continuous proces3es must be carried out in separate single-stage experiments in which ~ except for the reaction time - the particular rsaction conditions of the corresponding polymerization -~tage are u~ed.
. . .
2 ~ r~ 2 In the case of a copolymerization ~tag~, th~ molar monomer ratio in the reaction medium of cycloolefins to acyclicolefins or of a cycloolefin to the other cycloolefins, if no acyclic olefins are used, i6 then changed accordingly at the time at which the reaction conditions are changed. The change in the monomer ratio should amount to at least 10 %, preferably more than 25 %.
If the first polymerization stage is a homopolymerization (for example polymerization of norbornene), at lea~t a second monomer enters the reaction chamber at the time at which the change is m~de.
During a polymerization stage, or the formatLon of a polymer block, the monomer ratios in the reaction chamber are as a rule kept constant, ~o that chemically uniform polymer blocks are formed. However, it is al90 po~sible continually to change the monomer ratios during a poly-merization stage, which then lead~ to polymer blocks which have a structural gradient along the polymer chain, i.e. the incorporation ratio (for example the ratio between the number of norbornene units and the number of ethylene units in a pdrt of the polymer block) changes continually along the corresponding polymer bloak. In the case of polymer blocks which are made up of more than two types of monomer, this gradient can be aahieved by continually changing the concentration of a ~ingle monomer component. Blocks which have structural gradients can alco be prodllced in those polymerization ~tage~ in which the concentration of several monomer comp~nents is changed continuously at the same time. The re~ulting block copolymers are likewise Gf intere~t and a subject of the present invention.
The changes in the mor.omer ratios o be carried out in the proces~ according to the invention can be achieved, for example, by changing the pressure of the acy~lic ~8~2 olefin, by changing the temperature and thus the 801u-bility of gaseous olefins, by dilution with ~olvents under constant pressure of the acyclic olefin or by metering in a liquid monomer. Several of the ~aid para-meters can also be changed at the same time.
Both sudden and continuous changes of this type in the monomer ratio - and thus the preparation of blo~k copoly-mers according to the invention - ~an be effected both when the reaction is carried out di~continuou~ly and when the reaction is carried out ~ontinuously.
Continuous and multistage polymerization pro~esses are particularly advantageous because they make pos~ible economically advantageous use of the cycloolefin. In addition, in continuous processes the cyclic olefin,~
which can be obtained as residual monomer together with the polymer, can be recovered and recycled to the reac-tion mixture.
When the polymerization is carried out in this way, the block length can be controlled via the throughput and reaction volume of th~ various reaction vessel~ (i.e-.
these two parameters determine the dwell time in the various reaction locations).
An example of a process of this type i8 ~hown diagram-matically by Figures l and 2. Figure 1 ~how~ ~ possible 2; set-up for a simple continuous procedure, whioh can be expanded by further element~ (reaction vessels etcO) if required. ~he symbols have the following me nings:
Parameters: pressures pl and p2i pl>>p2; throughput v;
throttling d; level adju~tment l; 0 Parts: ~tirred vessels R; pump P, tubular reactor K; valves V
a = gaseous olefin or olefin mixture;
b = cycloolefin or cycloolefin solution; cycloolefin mixture or ~olution of cycloolefin mixture ':
--`` 2~`~9~52 c - polymer solution;
k - catalyst;
Pr = product.
Figure 2 shows an example of the variation profile for the reaction conditions to which the re~cting chain end of a block copolymer chain according to the invention can be subjected, assuming two pa~ses through the ~ontinuous reaction cycle which is 6hown diagrammatically in Figure l, start and discharge of the chain taking pla~e in reactor chamber Rl.
The symbols have the following meaning~:
X1 = cycloolefin/1-olefin ratio in reaction chamber Rl X2 = cycloolefin/1-olefin ratio in reaction chamber tl+~tl = dwell time in reaction chambex Rl t2+~t2 = dwell time in reaction chamber R2 +~ = indicates that a dwell time distribution exi6ts and therefore these times vary about a ~tatis-tical average value tl';t2' = dwell time in the tu~es between R1 and R2 or R2 and R1 (in comparison with R1 and R2, the dwell time distributions in these tube lines are narrow and therefore the indication "~t" ha~
been dispensed with here; usually the rate of incorporation of the 1-olsfin i8 yreater than that of the cycloolefin, which then lead~ to a slight change in the monomer ratio in favor of the cycloolefin) fl;f2 ~ r~latively sudden change in the monomer ratio on entering the reaction cha~ber R2 or Rl An installation according to ~igure 1 can be operated either continuously, i.e. by permanent pump transfer oi the reaction ~olution or permanent metering o~ the monomers and discharge of the product ~olution, or ' ''~'~ ` . ..
~ .
- lg- ~9g~2 discontinuously by batchwise pump tran~fer of the entire reaction solution from reactor to reactor.
The discontinuous variant has the advantage that both block length and the number of blocks per polymer chain can be precieely adjusted. In the ca~e of the continuous procedure, the block l~ngth can be accurately controlled, whilst the number of blocks is acce~sible or adjustable as a statistical average over the achieved average molecular weight of the block copolymer and the aLmed-at averaqe molecular weight of the polymer blocks. The prPparation of block copolymers which have ~pecific block chain ends can be effected very accurately using the discontinuous procedure, whereas the continu~us process enables only statistical information in this respect.
It follows that the described change in the reaction conditions (parameters) can be carried out one or more times, which leads to a sequence of two or more different blocks within a pslymer chain. The only condition with which it is necessary to comply is that the particular start of -the reaction ror the formation of a new block is so chosen that the latter takes place at a time at which - according to the calibration - the molecular weight distribution MW/M~ o~ the growing polymer block is stiil ~2, preferably virtually 1. If this condition is complied with, a new block which has a new composition can always be polymerized onto ihe growing polymer chain. These reaction times vary depending o~ the catalyst system used, the reaction temperature and the monomer concentra-tion.
If no further new block is to be polymerized on, the polymerization is completed, i~e~ discharged or ~toppad, under the last chosen reaction conditions.
A discontinuous procedure can also be carried out in one reaction ve~sel in that the change in the r0action conditions and stopping of the reaction are carried out 2 0 ~ 2 successively in one reactor.
In general the following applie~ with respect to the reaction parameters:
If pure open-chain olefin, for example ethylene, is being injected under pressure, pxes~ure~ of between 0.01 and 64 bar, preferably 2 to 40 bar and particularly prefer`ab-ly 4 to 20 bar are used. I, in addition to the open-chain olefin, an inert gas, for example nitrogen or argon, is al~o injected undPr pressure, ~he total pres-sure in the reaction vessel is 4 to 64 bar, preferably 2to 40 bar and particularly preferably 4 to 25 bar. If the cycloolefinic component is in the undiluted iorm, a high rate of incorporation of cycloolefin is also achieved at high pressures.
The metallocene compound is used in a concentration, with respect to the transition metal, of 10~1 to 10-8, prefer-ably 10-3 to 10-6 mol of transition metal per dm3 of reactor volume. The aluminoxane is used in a concentra-tion of 10-5 to 10-1, preferably 10-4 to 2 x 10-2 mol per dm3 of reactor volume, with re~pect to the aluminum content~
In principle, higher concentrations are, howe~er, also possible. The other cocatalysts mentioned are preferably used in approximately equimolar amounts with respect to the metallocene.
Apart from the said, bridged metallocene~, metalloc0nes which have identical or similar non-bridged ligand~ can, in principle, also be used. In the case of the~e me~al-locenes, the reaction times chosen must be distinctly shorter tha~ those for the bridged metallocene~, under comparable xeaction conditions.
When preparing copolymers, the molar ratios of the polycyclic ol~fin to the open-chain olefin (preferably) used can be varied within a wide range. The molar ratios of cycloolefin to open-chain olefin are preferably 2~Y,~9!~, adjusted to 50:1 to 1:50, in particular 20:1 to 1:20.
The cycloolefin block copolymers according to the inven-tion lead to advantageous mechanical property co~ina-tion~ in blends with other cycloolefin copolymer~.
S The following examples are intended to illu~trate the invention in more detail:
Example 1 A clean and dry 1.5 dm3 polymeri~Ation reactor provided with a stirrer was flushed with nitrogen and then with ethylene and filled with 576 ml of an 85 ~ strength by volume solution of norbornene in toluene.
The reactor was then kapt at a temperature of 20C, with stirring, and 2 bar ethylene texcess pre~4ure) wa~ in-jected under pressure.
20 cm3 of a solution of methyl aluminoxane in toluene (MA0 solution) ~10.1 ~ by weight of methyl aluminoxane having a molar mass of 1300 g/mol according to cryoscopic determination) were then metered into the reactor and the mixture was stirred Ior 15 min at 20C, the ethylene pressure being kept at 2 bar by metering in additional ethylene. In parallel, 60 mg of rac-dimethylsilyl-bis(l-indenyl)zirconium dichloride were di~solved in 10 cm3 of a solution of methyl aluminoxane in toluene (~ee above for concentration and quality) and preactivated by leaving to ~tand for 15 minutes. The ~olution of th~
complex was then metered into the reactor. Polymerization was then carried out at 20C, with stirrin~ 1750 rpm), the ethylene pressure bein~ kept at 2 bar by metering in additional ethylene.
After 30 min, 50 ml of the reaction solution were removed via a lock. Immediately after this sampling, the ethylene 2~9~2 pressure was increased to 7 bar in the course of 10 sec and kept at this pressure for 5 min by metering in additional ethylene~ The polymerization was then ~topped ky adding lO ml of water via a lock. ~fter ~ubsequent letti~g-down, the reaction solution was drained into a`
vessel and then added dropwise to 2 d m3 of acetone, the resulting mixture w ~ 9 stirred for 10 min and the ~u~pend ed, polymer solid was filtered off.
20 g of polymer which has a gla6s transîtion temperature of 140C and a vi~cosity number of g5 ml/g and a mole-cular weight distribution M,,,/ Mn Of 1.5 were obtained.
After removal, the 50 ml of sample were treat~d, with stirring, with 0.5 ml of water and then worked up analo-gously to the abovementioned working-up of the reaction solution of the end product. 4.5 g of polymer which has a glass transition temperature of 165C, a visco~ity number of 150 mlig and a molecular weight distribution MW/Mn of 1.3 were isol~ted from the 50 ml of sample.
-Examples 2 - 4 The procedure was analogous to Example 1 but, in deviat-ion therefrom, the condition6 from Table 1 w~re cho~e~.
The resulting polymer properties are summarized in ~ble 2.
Table 1:
_ _ .
Example Nb ~olution PolymorisationPolymerlsation h~ount o~
No. ConC~ntratiDn St~ge 1 Stag ~ 2 ~otallDccno (~ by volum~ Timn Et prn3auro Ti~ ~t pre~ure ~g) ~rlin) j ~bar) ~min) ~oar) 2 24.4 30 1 15 7 ~0.3 3 24.4 30 1 10 7 92.2 4 43.B 30 2 2 6 69.9 _ _ Nb ~ NorbDrn~no ~able 2:
Example5ample ~n~ product No. Vn Tg ¦ Mwt~Vn Tg M~
(ml/g) (C) - (ml/g) (~C) 2 22 167 1.2 10898 1.2 3 27.5 165 1.2 19281 1.6 4 73 173 1.2 107134 1.3 . . _ __ Example 5 A kinetic te6t was carried out analogously to Example 1.
860 cm3 of an 85 % strength by volume solution of norbor-nene in toluene were used for the polymerization. The reactor temperature was 24C and the ethylene sxcess pressure was kept constant at 6 bar. 60 cm3 of a solution of MAO in toluene (10.1 ~ strength by weight) were added and the mixture wa~ stirred for 15 min. 21 mg of rac-dimethylsilyl-bis(1-indenyl)zirconium dichloride were added to 20 cm3 of MAO solution and after preactivation the mixture was injected into the reactor under pre~sure.
Samples (50 cm3 ) were taXen via a iock at the reaction times indicated in Table 3. The polymerization wa~
immediately stopped by adding 4 çm3 of isopropanol. The product was w~shed several times wikh acetone and dilute hydrochloric acid (see Example 1).
The resulting polymer product~ were mea~ured by gel permeation chromatography. The number-average molecular weight (M~) and weight-average molecular weight ~M~) and the inhomogeneity (MW/M~) ar~ given in Table 3. The distribution curves for all samples are shown in Fig. 4.
.
: ~ , ~- 20~3~5~
Table 3:
Sample Reaction M~ Mw M~/Mn No. time/min x 10~3g/molx 10 3g/mol 1 10 21.~ 2~.4 1.10 2 20 37.3 4~.8 1O15 3 30 51.0 62.0 1.22 4 45 73.0 92.0 1.25 83.0 121.0 1.46 6 90 110.0 167O0 1.52 7 120 125.0 217.0 1.74 8 150 153.0 261.~ 1.7l Fig. 4 shows the molecular weight distribution functions obtained by gel permeation chromatography for ~mples Nos. 1 - 8 from Exampla 5 from left to right with in-creasing molecular wei~ht and increasing reactivn time.
Reaction time and average molecular weights (M~, Mw~ are given in Table 3.
The area of the dis~ribution function in Fig. 4 is weighted by the yield.
GPC (gel permeation chromatography) measurements were carried out as follows. A type 150-C ALC/GPC Millipore Waters Chrom. chromato~3raph And a column set comprising 4 Shodex columns of type AT-80 M/S were u~edO The solvent was o-dichlorobenzene.
Further mea~urement parameters were:
Temperature: 135C
30 Flow rate: 0,5 ml/min 5ample amount: 0.4 ml of sample solution Concentration of the sample solution 0.1 g/dl .
2V~9~2 Calibration: according to polyethylene standard Example 6 The procedure wa~ analogous to Example 1 but, in devia~
tion therefrom, the following conditionc were ~ho~en:
- cycloolefin = tetracyclodode~ene - concentration of the cycloolefin solution = 127 g/l - amount of cycloolefin solution = 860 ml - amount of NA0 solution = 100 ml - metallocene = rac-dimethylsilyl-bistl-indenyl~zirconium-dichloride - amount of metallocene = 62 mg - ethylene pressure maintained by additional metering =
3 bar - sampling time = after 20 min - the cycloolefin concentration was changed by adding pure cycloolefin via a lock.
- duration of thP addition operation = 2 ~ec - amount of cycloolefin metered in = 170 g - ethylene pressure after addition = 3 bar - duration of polymerization after m~tering in -- 30 min The resulting polymers are distinguished by:
- amount of resulting end product = 1705 g - amount of polymer from sample ~ 390 mg 25 - gla8s transition temperature of the end product ~ 175C
glass transition temperature o~ the polym~r from sample = 110C
- molecular weight Mn of the end product - 7~,000 g/mol - molecular weight Mn o the polymer ~r~m s~mple -52,000 g/mol - viscosity nu~ber of the end product ~ 105 ml/g - viscosity number of the polymer from ~ample ~ fi6 ml~g - molecular weight distribution Mw~Mn of the end product = 1.9 " 2~9952 - molecular weight distribution ~w/~n of the polymer ~rom sample = 1.4 Comparison example 1 (compari~on example with respect to Example 6 The procedure was as in xamPle_6 but, in deviatio~
therefrom, the addition of the pure cycloolefin wa3 already carried out before the addition of the metallo-cene and thu~ before the start of the polymerization~ The polymerization was stopped after 3 hour~. The re6ulting end product i~ distinguished by the following characteristics:
- glass transition temperature = 151C
- viscosity number = 84 ml~g Example 7 Polymerization experiments were carrie/ ~out in an instal-lation corresponding to that in Fig.~10 The installation was characterized by the following features:
- R1 has a volume of 80 l - R2 comprises a tube in which static mixing elements are ~ixed -- R2 has a volume of 2~0 ml - K is a cooling tube which has a volume of 15 l - P is a gear pump The polymerization was carried out in a~cordan~e with the following concept:
- a olution of cycloolefin in toluene was initially introduced into R1;
- pllmp transfer was carried out using the pump in a~cor-dance with a calibration with constant flow rate;
- the gaseous olefin was introduced at excess pre~ure into the circulation flow immediately upstream of the ~0~9~2 .
~ 27 -static mixer, - in reactor Rl the pressure was kept constant by con-trolled letting-off of gas.
The following polymerization conditions were maintained:
- cycloolefin: norbornene - gaseous olefin: ethylene - metallocene:diphenylmethylene-(9-fluorenyl)cyclopenta-dienylzirconium dichloride - amount of norbornene (liquid) initially introduced =
- amount of toluene initially introduced - 30 1 - amount of MAO solution (MAO solution according to Example 1) initially introduced = 1000 ml - amount of metallocen~ (catalyst preparation according to Example 1) = 200 mg - ethylene excess pressure during the polymerizatioll on the ethylene line = 11 bar - pressure in R2 immediately downstream of th~ static mixing elements = 10.5 bar - pressure in R1 during the polymerization = 2.5 bar - circulation stream during the polymerization = 1500 l/h - polymerization temperature: in R1 = 40C
in R2 = 43C
After the start of the polymerization by addition of the catalyst via a lock, samples were taken regularly at the location in the installation designated by Pr in Fig. 1.
The polymerization was stopped after 50 minut~ Workin~
up of the samples and of the end product was c~rr ed out analogously to Example 1.
The following properties were determined for 8ampl~ and end product:
- 900 ml sample after 10 minutes:
- amount of polymer = 0.5 g - glass transition temperature = 140C
`:
~ 2~9~
- viscosity number = 62 ml~g - 600 ml sample after 20 minutes~
- amount of polymer = 1. 4 g - glass transition temperature = 137C
5 - viscosity number = lO9 ml/g - end product after 50 minutes:
- amount of polymer - 15 g in 1 1 of polymerization solution - glass transit' on temperature = 134C
10 - viscosity number = 160 ml/g Example 8 Two polymer blends were prepared by mixing 5 % strength toluene solutions of the components and then precipita ting in acetone and drying the precipitated powder. The 15 following compositions were ~elected:
E~lend I: 3 parts of component A + 3 part~ of component B ~ 1 part of component C
Blend II: 3 part6 of component A + 3 parts oiE component B
2 0 Component A is a norbornene-ethylene copolymer poly-merized in one stage and having a gla~ tran~ition temperature of 102 C and a viscosity number of 52 ml/g.
The catalyst u~ed for its polymerization wa~ diphenyl-methyl- t 9~f luorenyl ) -cyclopentadienylzirco~ium 25 dichloride.
Component B iB a norbornene-ethylene copolymer poly-merized in one stage and having a glass tran~ition temperature of 178C and a vi~rosity number of 48 ml~O
~he catalyst used for its polymerization was diphenyl-30 methyl- ( 9-fluorenyl)-cyclopentadienylzirconium dichloride .
Component C is a block copolymer which was prepar~d by a process according to Example 1 but, in deviation there-from, the following condition~ were chosen:
- amount of norbornene solution = 860 ml - amount of MAO solution = 60 ml - metallocene = diphenylmethylene-(9-fluorenyl)-cyclo-pentadienylzirconium dichloride - amount of metallocene = 20 mg - ethylene pre~sure maintained by additional metering =
- amount of polymer - 15 g in 1 1 of polymerization solution - glass transit' on temperature = 134C
10 - viscosity number = 160 ml/g Example 8 Two polymer blends were prepared by mixing 5 % strength toluene solutions of the components and then precipita ting in acetone and drying the precipitated powder. The 15 following compositions were ~elected:
E~lend I: 3 parts of component A + 3 part~ of component B ~ 1 part of component C
Blend II: 3 part6 of component A + 3 parts oiE component B
2 0 Component A is a norbornene-ethylene copolymer poly-merized in one stage and having a gla~ tran~ition temperature of 102 C and a viscosity number of 52 ml/g.
The catalyst u~ed for its polymerization wa~ diphenyl-methyl- t 9~f luorenyl ) -cyclopentadienylzirco~ium 25 dichloride.
Component B iB a norbornene-ethylene copolymer poly-merized in one stage and having a glass tran~ition temperature of 178C and a vi~rosity number of 48 ml~O
~he catalyst used for its polymerization was diphenyl-30 methyl- ( 9-fluorenyl)-cyclopentadienylzirconium dichloride .
Component C is a block copolymer which was prepar~d by a process according to Example 1 but, in deviation there-from, the following condition~ were chosen:
- amount of norbornene solution = 860 ml - amount of MAO solution = 60 ml - metallocene = diphenylmethylene-(9-fluorenyl)-cyclo-pentadienylzirconium dichloride - amount of metallocene = 20 mg - ethylene pre~sure maintained by additional metering =
6 bar - sampling time = after 25 min - time over which the ethylene pressure was changed -20 sec - second ethylene pressure maintained by additional metering of ethylene = 12 bar - duration of polymerization at the second ethylene pressure = 2.5 min The resulting polymers are distinguished by:
- amount of resulting end product = 13.5 g - amount of polymer from sample = 370 mg - glass transition temperature of the end product ~ 1269C
- glass transition temperature of the polymer ~rom sample = 143C
- molecular weight Mn of the end product = 155,000 g/mol - molecular weight Mn of the polymer from sample =
90,000 g/mol - viscosity number of the end product = 176 ml/g - viscosity number of the polymer from sample ~ 114 ml/g - molecular weight distribution ~w/Mn of the end product = 1.8 molecular weight distribution Mw/Mn of the pol~mer from sample - 1.3 Aft~r drying in an oven at 80C for 18 hours, pressed sheets were produced from both blends at 240GC, 100 bar compression pressure and a pres~ing time of 15 minutes.
The sheets have a diameter of 60 mm and a thickness of 20~52 1 mm. Samples, which were used to determine the gla~5 transition tempera~ure, were taken from these sh~ets.
The following glass transition temperatures were measured:
Blend I: first glass transition temperature = 121~C
~econd ylass transition temperature ~ 163C
Blend II: irst glagB transition temperature z 105C
aecond glass transition temperature = 165~C
As the glaQs transition temperatures confirmt b~th blends are two-phase. The increase in the fixst glas~ transition temperature in the case of blend I compared with the first glass txansition temperature in the case of blend II apparently shows that the corresponding phase has, as a result of the addition of the block copolymer, clearly approached the phase which i6 characterized by the second glass transition temp~rature, i.e. the two pha~es become more compatible.
Example 9 The procedure was analogous to Example 8, the component~
being polymerized using rac-dimethylsilyl-bi~ inden-yl)zirconium dichloride. Deviating from Example 8, the following characteri~tics apply:
- component A: glass transition temperature = 75~C
viscosity num~er = 97 ml/g 5 - component ~: gla s transition temperature ~ 165~C
viscosity number = 58 ml/g - component C is a block copol~m r prepared according to - 31 ~ 2 Example 2.
- blend I haæ a single glass transition temperature of 108C.
- blend II: fir~t glass transition temperatur~ c 88~C
5second glass transition temp~rature ~ 142C
Example 10 The procedure was analogous to Example 8, the components being polymerized using rac-dimethyl~ilyl-bis(l-indenyl)æirconium dichloride. Deviating from Example 8, the following characteristics apply:
- Blend I: 5 parts of component A + 12 parts of com-ponent B + 3 parts of component C
- ~lend II: 5 parts of component A ~ 12 parts of com~
ponent B
5 - componenk A: glass transition temperature - 15C
viscosity number = 145 ml/g - component B~ glass transition temperature - 179C
viscosity number = 112 ml/g - component C is a block copolymer prepared according to Example 2 but, in deviation therefrom, the following data pply:
- time for the e~ond polymerization stage ~ 3 min - Et pressure in the second polymerization stage 8 14 bar - Vn of the end product = 180 ml/g 5 - the end product has two glas~ tran~ition temperature~:
first glass transition temperature = 48a~
æecond glass transition temperature = 148C
- Mw/Mn of the end product - 1.9 ' .
. .
~: .
- 32 - 2~ 2 - Blend I: fir~t glaPs transition temperature ~ 30gC
~econd glass txan~ition tempera~ure - 156C
- Blend II: first glass tran~ition temperature = 18C
second glass tran3ition temperature - 173C
Whereas the pressed plates from blend I had a translucent appearance, the pre3sed plate6 from blend II were opaque.
Dumbbell test pieces for mechanical testi~g were produced from a further portion of the blends prepared.
Determination of the notched impact strength carried out on the correspondin~ dumbbell test pieces in acaordance with ISO 180/A gave the following value~ at a test temperature of 60C:
Blend I: 6.3 kJ/m2 Blend II: 4.2 kJ/m2
- amount of resulting end product = 13.5 g - amount of polymer from sample = 370 mg - glass transition temperature of the end product ~ 1269C
- glass transition temperature of the polymer ~rom sample = 143C
- molecular weight Mn of the end product = 155,000 g/mol - molecular weight Mn of the polymer from sample =
90,000 g/mol - viscosity number of the end product = 176 ml/g - viscosity number of the polymer from sample ~ 114 ml/g - molecular weight distribution ~w/Mn of the end product = 1.8 molecular weight distribution Mw/Mn of the pol~mer from sample - 1.3 Aft~r drying in an oven at 80C for 18 hours, pressed sheets were produced from both blends at 240GC, 100 bar compression pressure and a pres~ing time of 15 minutes.
The sheets have a diameter of 60 mm and a thickness of 20~52 1 mm. Samples, which were used to determine the gla~5 transition tempera~ure, were taken from these sh~ets.
The following glass transition temperatures were measured:
Blend I: first glass transition temperature = 121~C
~econd ylass transition temperature ~ 163C
Blend II: irst glagB transition temperature z 105C
aecond glass transition temperature = 165~C
As the glaQs transition temperatures confirmt b~th blends are two-phase. The increase in the fixst glas~ transition temperature in the case of blend I compared with the first glass txansition temperature in the case of blend II apparently shows that the corresponding phase has, as a result of the addition of the block copolymer, clearly approached the phase which i6 characterized by the second glass transition temp~rature, i.e. the two pha~es become more compatible.
Example 9 The procedure was analogous to Example 8, the component~
being polymerized using rac-dimethylsilyl-bi~ inden-yl)zirconium dichloride. Deviating from Example 8, the following characteri~tics apply:
- component A: glass transition temperature = 75~C
viscosity num~er = 97 ml/g 5 - component ~: gla s transition temperature ~ 165~C
viscosity number = 58 ml/g - component C is a block copol~m r prepared according to - 31 ~ 2 Example 2.
- blend I haæ a single glass transition temperature of 108C.
- blend II: fir~t glass transition temperatur~ c 88~C
5second glass transition temp~rature ~ 142C
Example 10 The procedure was analogous to Example 8, the components being polymerized using rac-dimethyl~ilyl-bis(l-indenyl)æirconium dichloride. Deviating from Example 8, the following characteristics apply:
- Blend I: 5 parts of component A + 12 parts of com-ponent B + 3 parts of component C
- ~lend II: 5 parts of component A ~ 12 parts of com~
ponent B
5 - componenk A: glass transition temperature - 15C
viscosity number = 145 ml/g - component B~ glass transition temperature - 179C
viscosity number = 112 ml/g - component C is a block copolymer prepared according to Example 2 but, in deviation therefrom, the following data pply:
- time for the e~ond polymerization stage ~ 3 min - Et pressure in the second polymerization stage 8 14 bar - Vn of the end product = 180 ml/g 5 - the end product has two glas~ tran~ition temperature~:
first glass transition temperature = 48a~
æecond glass transition temperature = 148C
- Mw/Mn of the end product - 1.9 ' .
. .
~: .
- 32 - 2~ 2 - Blend I: fir~t glaPs transition temperature ~ 30gC
~econd glass txan~ition tempera~ure - 156C
- Blend II: first glass tran~ition temperature = 18C
second glass tran3ition temperature - 173C
Whereas the pressed plates from blend I had a translucent appearance, the pre3sed plate6 from blend II were opaque.
Dumbbell test pieces for mechanical testi~g were produced from a further portion of the blends prepared.
Determination of the notched impact strength carried out on the correspondin~ dumbbell test pieces in acaordance with ISO 180/A gave the following value~ at a test temperature of 60C:
Blend I: 6.3 kJ/m2 Blend II: 4.2 kJ/m2
Claims (13)
1. A process for the preparation of a cycloolefin block copolymer, wherein 0.1 to 95 % by weight, with respect to the total amount of monomers employed, of at least one monomer of the formulae I, II, III, IV, V or VI
(I) , (II), (III), (IV), (V) , (VI), in which R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1-C8-alkyl radical, it being possible for the same radicals in the various formulae to have different meanings, 0 to 95 % by weight, with respect to the total amount of monomers employed, of a cycloolefin of the formula VII
(VII), in which n is a number from 2 to 10, and 0 to 99 % by weight, with respect to the total amount of monomers employed, of at least one acyclic olefin of the formula VIII
(VIII), in which R9, R10, R11 and R12 are identical or different and are a hydrogen atom or a C1-C8-a1ky1 radical, are polymerized at temperatures of -78 to 150°C and a pressure of 0.01 to 64 bar, in the presence of a cata-lyst which is composed of a cocatalyst and a metallocene of the formula XI
(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-al-koxy 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, R15 and R17 are a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M1, R18 is ,,,,,, = BR19, = AIR19, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =
NR19, = CO, = PR1, or = P(O)R19, where R19, R20 and R21 are identical or different and are a hydrogen atom, 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-aralkenyl group or a C7-C40-alkylaryl group, or R19 and R20, or R19 and R21, form a ring, in each case with the atoms linking them, and M2 is silicon, germanium or tin, and, in each case at a molecular weight distribution Mw/Mn of less than 2, always with respect to the polymer block forming, the reaction conditions are changed one or more times in such a way that the monomer/comonomer ratio changes by at least 10 % or a further polyme-rizable monomer of the formulae I-VIII is metered into the monomer or the monomers.
(I) , (II), (III), (IV), (V) , (VI), in which R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1-C8-alkyl radical, it being possible for the same radicals in the various formulae to have different meanings, 0 to 95 % by weight, with respect to the total amount of monomers employed, of a cycloolefin of the formula VII
(VII), in which n is a number from 2 to 10, and 0 to 99 % by weight, with respect to the total amount of monomers employed, of at least one acyclic olefin of the formula VIII
(VIII), in which R9, R10, R11 and R12 are identical or different and are a hydrogen atom or a C1-C8-a1ky1 radical, are polymerized at temperatures of -78 to 150°C and a pressure of 0.01 to 64 bar, in the presence of a cata-lyst which is composed of a cocatalyst and a metallocene of the formula XI
(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-al-koxy 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, R15 and R17 are a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M1, R18 is ,,,,,, = BR19, = AIR19, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =
NR19, = CO, = PR1, or = P(O)R19, where R19, R20 and R21 are identical or different and are a hydrogen atom, 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-aralkenyl group or a C7-C40-alkylaryl group, or R19 and R20, or R19 and R21, form a ring, in each case with the atoms linking them, and M2 is silicon, germanium or tin, and, in each case at a molecular weight distribution Mw/Mn of less than 2, always with respect to the polymer block forming, the reaction conditions are changed one or more times in such a way that the monomer/comonomer ratio changes by at least 10 % or a further polyme-rizable monomer of the formulae I-VIII is metered into the monomer or the monomers.
2. The process as claimed in claim 1, wherein a compound of the formula I or of the formula III and a compound of the formula VIII are block-copolymerized.
3. The process as claimed in claim 1 or 2, wherein the compound of the formula I used is norbornene.
4. The process as claimed in one or more of claims 1-3, wherein the compound of the formula III used is tetracyclododecene.
5. The process as claimed in one or more of claims 1-4, wherein the compound o the formula VIII used is ethylene or propylene.
6. The process as claimed in one or more of claims 1-5, wherein a norbornene/ethylene block copolymer is prepared.
7. The process as claimed in one or more of claims 1-6, wherein the monomer composition of the reaction medium is continuously changed during at least one polymerization stage.
8. The process as claimed in claim 1, wherein a monomer is used in the first polymerization stage.
9. The process as claimed in claim 8, wherein the monomer used in the first polymerization stage is a compound of the formulae I-VII.
10. The process as claimed in one or more of claims 1-9, wherein the cocatalyst used is an aluminoxane of the formula (IX) (IX) for the linear type and/or of the formula (X) (X) for the cyclic type, where, in the formulae (IX) and (X), the radicals R13 are identical or different and are a C1-C6 alkyl group, a C6-C18-aryl group, benzyl or hydrogen, and p is an integer from 2 to 50.
11. A cycloolefin block copolymer which can be prepared as claimed in one or more of claims 1-10.
12. The use of a cycloolefin block copolymer as claimed in claim 11 as a phase promoter.
13. The use of a cycloolefin block copolymer as claimed in claim 11 as a blending component in polymer blends with cycloolefin copolymers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4205416 | 1992-02-22 | ||
| DEP4205416.8 | 1992-02-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2089952A1 true CA2089952A1 (en) | 1993-08-23 |
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ID=6452320
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002089952A Abandoned CA2089952A1 (en) | 1992-02-22 | 1993-02-19 | Cycloolefin block copolymers and a process for their preparation |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0560090B1 (en) |
| JP (1) | JPH05339327A (en) |
| KR (1) | KR930017929A (en) |
| AT (1) | ATE165849T1 (en) |
| AU (1) | AU3375793A (en) |
| CA (1) | CA2089952A1 (en) |
| DE (1) | DE59308488D1 (en) |
| ES (1) | ES2118148T3 (en) |
| TW (1) | TW312695B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI945959A (en) * | 1993-12-21 | 1995-06-22 | Hoechst Ag | Metallocenes and their use as catalysts |
| EP0691366B1 (en) * | 1994-07-08 | 1999-03-10 | Tokuyama Corporation | Stretched polypropylene film |
| JP3404906B2 (en) * | 1994-08-12 | 2003-05-12 | 東ソー株式会社 | Method for producing olefin copolymer |
| DE19546500A1 (en) * | 1995-12-13 | 1997-06-19 | Hoechst Ag | Production of cyclo-olefin copolymers e.g. for pipes |
| JP3588213B2 (en) * | 1996-12-26 | 2004-11-10 | ティコナ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Toner for developing electrostatic images containing polyolefin resin having cyclic structure |
| JP3434218B2 (en) * | 1998-11-02 | 2003-08-04 | ティコナ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Toner for developing electrostatic images |
| JP3449935B2 (en) * | 1999-01-11 | 2003-09-22 | 株式会社巴川製紙所 | Dry toner for electrophotography |
| KR100544525B1 (en) * | 2000-08-11 | 2006-01-23 | 히다치 가세고교 가부시끼가이샤 | Process for the production of block copolymers, block copolymers produced by the process, and use of the copolymers |
| DE60229330D1 (en) | 2001-07-23 | 2008-11-27 | Ricoh Kk | Oil-free toner |
| JP3863744B2 (en) | 2001-08-31 | 2006-12-27 | 株式会社巴川製紙所 | Toner for recycling system and toner recycling developing method using the same |
| JP3880359B2 (en) | 2001-10-05 | 2007-02-14 | 株式会社巴川製紙所 | Full color toner for oilless fixing |
| JP3863054B2 (en) | 2002-04-15 | 2006-12-27 | 株式会社巴川製紙所 | Toner for electrostatic image development |
| JP3942520B2 (en) | 2002-09-30 | 2007-07-11 | 株式会社巴川製紙所 | Toner for electrophotography and image forming method using the same |
| JP2004359798A (en) * | 2003-06-04 | 2004-12-24 | Mitsui Chemicals Inc | Olefinic polymer and manufacturing process therefor |
| JP4097581B2 (en) * | 2003-08-22 | 2008-06-11 | 三井化学株式会社 | Propylene copolymer |
| JP4570585B2 (en) | 2006-05-02 | 2010-10-27 | シャープ株式会社 | Electrophotographic capsule toner |
| US9594320B2 (en) | 2014-06-25 | 2017-03-14 | Canon Kabushiki Kaisha | Toner and method of producing the toner |
| JP6550275B2 (en) * | 2015-06-15 | 2019-07-24 | 東京応化工業株式会社 | Composition for nanoimprinting, cured product, pattern forming method and article comprising pattern |
| EP3604434B1 (en) * | 2017-03-30 | 2024-04-17 | Mitsui Chemicals, Inc. | Cyclic olefin resin composition for molding, molded body, and resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3835044A1 (en) * | 1988-10-14 | 1990-04-19 | Hoechst Ag | Process for the preparation of cycloolefin polymers |
| DE3942365A1 (en) * | 1989-12-21 | 1991-06-27 | Hoechst Ag | METHOD FOR PRODUCING A POLYPROPYLENE MOLDING MATERIAL |
| TW206240B (en) * | 1990-02-13 | 1993-05-21 | Mitsui Petroleum Chemicals Ind |
-
1993
- 1993-02-09 TW TW082100888A patent/TW312695B/zh active
- 1993-02-17 EP EP93102454A patent/EP0560090B1/en not_active Expired - Lifetime
- 1993-02-17 ES ES93102454T patent/ES2118148T3/en not_active Expired - Lifetime
- 1993-02-17 AT AT93102454T patent/ATE165849T1/en not_active IP Right Cessation
- 1993-02-17 DE DE59308488T patent/DE59308488D1/en not_active Expired - Fee Related
- 1993-02-19 AU AU33757/93A patent/AU3375793A/en not_active Abandoned
- 1993-02-19 JP JP5030022A patent/JPH05339327A/en active Pending
- 1993-02-19 CA CA002089952A patent/CA2089952A1/en not_active Abandoned
- 1993-02-22 KR KR1019930002425A patent/KR930017929A/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| ATE165849T1 (en) | 1998-05-15 |
| EP0560090B1 (en) | 1998-05-06 |
| JPH05339327A (en) | 1993-12-21 |
| DE59308488D1 (en) | 1998-06-10 |
| AU3375793A (en) | 1993-08-26 |
| EP0560090A1 (en) | 1993-09-15 |
| TW312695B (en) | 1997-08-11 |
| KR930017929A (en) | 1993-09-20 |
| ES2118148T3 (en) | 1998-09-16 |
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