CA2061869A1 - Cycloolefin (co)polymers with a narrow molecular weight distribution and a process for the preparation thereof - Google Patents
Cycloolefin (co)polymers with a narrow molecular weight distribution and a process for the preparation thereofInfo
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- CA2061869A1 CA2061869A1 CA002061869A CA2061869A CA2061869A1 CA 2061869 A1 CA2061869 A1 CA 2061869A1 CA 002061869 A CA002061869 A CA 002061869A CA 2061869 A CA2061869 A CA 2061869A CA 2061869 A1 CA2061869 A1 CA 2061869A1
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- Prior art keywords
- group
- polymerization
- cycloolefin
- molecular weight
- formula
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Classifications
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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
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Abstract
Abstract of the disclosure Cycloolefin (co)polymers with a narrow molecular weight distribution and a process for the preparation thereof Polymers of polycyclic olefins such as, for example, norbornene or tetracyclododecene, or copolymers of polycyclic olefins with cycloolefins and/or 1-olefins with a very narrow molecular weight distribution are obtained without ring opening by a polymerization in which a catalyst which is composed of an aluminoxane and of a stereorigid, chiral metallocene compound of an element of groups IVb to VIb is used, and in which the reaction is stopped at a time when the molecular weight distribution Mw/Mn of the polymer formed is < 2.
Description
HOECHST AKTIENGESELLSCHAFT HOE 91/F 062 ~L6 Description Cycloolefin (co)polymer~ with a narrow molecular weight di~tribution and a process for the preparation thereof The invention relates primarily to a process for the preparation of homo- and copolymers of polycyclic olef~ns with a very narrow molecular weight di~ribution, in which no ring opening takes place.
It i~ known that polycyclic olefin~ can be polymerized u~ing v_riou~ Ziegler eataly~t~. Depending on the eata-lyst, the polymerization tAke~ plaee via ring opening(cf. US 4 178 424) or opening of the double bond (cf.
EP-A 156 464, ~P-A 283 164).
The di~advant~ge of a ring-opening polymerization i~ that the re~ulting polymer contain~ double bonds which may lead to ero~ nking of ehain~ and thus eonsiderably re~trlet the proee~ability of the material by extru~ion or in~eetlon molding.
Polymerlzatlon wlth openlng of the double bond ha~ a relatlvely low polymerlzatlon rate (reaetlon rate) in the ea~e of eyelie olefln~.
When polymer~ are proees~ed by in~eetion molding or when polymer filament~ are ~tretehed, it i8 a great advantage for the moleeular weight di~tributlon of the polymer~ to be a~ narrow a~ po~lble.
It iB known that the moleeular weight diotribution~
aehleved ln ree-radi¢al polymerizations a~ well a~ in ela~leal Ziegler polymerization are broad, i.e. that Mw/Mn 1~ dl~tinetly l_rger than 2. A moleeul_r weight di~tributlon Mw/Mn ~ 2 ean be _ehieved in the polymerization of olefins earried out u~ing metallocene eataly~t~. However, even narrower molecular weight distributions would be desirable for specific 2 2061~69 applications (for example precision in~ection molding).
The ob~ect was therefore to prepare, using a proces~
which i~ as straightforward as pos~ible, polycycloolefins and cycloolefin copolymers with a distribution which is as narrow a~ possible.
It has been found, surpri~ingly, that polycycloolefins and cycloolefin copolymers with molecular weight di~-tributions Mw/Mn ~ 2 can be obtained by using specific metallocene catalyst~ in combination with particular polymerization conditlon~ such as concentration and temperature, and, in particular, by the choice of par-ticular polymerization times.
This finding is extremely ~urprising because all the theoretical treatmenta of Ziegler polymerization hitherto di~closed permit a distribution Mw/Mn = 2 a~ a minimum.
Narrower di~tribution~ a~ have been found according to the invention indicate that most of the polymer chains are a~embled throughout the polymerization time, i.e.
polymerisation may, under certain condltlons, take place in a v0ry ~imllar manner to a living polymerization as 1 kn~wn, for example, ~or the anionlc polymerlzatlon o~
~tyrene.
The invention therefore relates to a proce~ for the preparation of a cycloolefin polymer or copolymer wlth a narrow molecular weight di~tribution ~Mw/Mn) by polymerization of 0.1 to 100~ by weight, ba~ed on the total amount of the monomer~, of ~t lea~t one monomer of the formulae I, II, III, IV, V or VI
~ H ~ ~ R
HC CH
¦¦ R3-l ~-~4 HC i _ C~
~ C~ 2 _ 3 _ 2~ 69 XC ¦ CH
¦¦ R3-C-R4 ¦ C~2 ~II), ~C--¦ --CH~ ¦ --CH~
¦¦ R3-C_R4 ¦R5-C-R6 ¦ ~555), HC ¦ ~, CH ¦ ~ CH
HC ¦ CH ¦ Cll ~ ¦ CX
¦¦ ~3-C-R4 ¦ R5-C-R6 ¦ R7-C-R3 ¦ (~V), HC ¦ C~ I ~CH~ ¦ C~
~ I CX ~ ~CX
¦¦ P.3-C-R4 l l IV) XC--CX~ CX~ --}~,2 ~6 ~ CH~
¦¦ R3-C-R4 l l R7-C-R3 ¦ ~V~), :
` - 4 - 2061~69 in which Rl, R2, R3, R', Rs, R6, R7 and R~ are identical or different and are a hydrogen atom or a C,-C~-alkyl radi-cal, it being possible for identical radicals in the different formulae to have a different meaning, 0 to 99.9~ by weight, based on the total amount of the monomers, of a cycloolefin of the formula VII
(CX2)n (VII), in which n ie ~ number from 2 to 10, and 0 to 99.9% by weight, based on the total amount of the monomere, of at lea~t one acyclic l-olefin of the formula VIII
/C_C\ (V~i), Ril R12 ln whlch R', Rl, Rll and Rl2 are identical or d~fforent ~nd are a hydrogen atom or a Cl-C,-alXyl radicsl, at tempera-turee from -78 to 150-C and undex a pre~ure o from 0.01 to 64 bar, in the preeence of a c~talyst which ie com-poeed of ~n ~luminox~ne of the formuls IX
~ Al - ~ Al ~SX) R13~ n ~ R13 for the linear type snd/or of the formula X
~ 5 ~ 2~ 9 ¦-R13 _ -Al - o - ~X) _ ~2 for the cyclic type, where the radicals Rl3 in the for-mulae IX and X are identical or different and are a Cl-C6-alkyl group or phenyl or benzyl, and n iB an integer from 0 to 50, and of a metallocene of the formula XI
/, R14 R18 M1~ ~XI) \' R15 in which M1 i~ tltanium, zirconlum, hafnium, vanadium, niobium or tantalum, 10 Rl4 and R1~ are identlcal or different and are a hydrogen atom, a halogen atam, ~ C1-C1O-alkyl group, a Cl-C1O-alkoxy group, a C~-C1O-aryl group, a Ca-Clo~
aryloxy group, a C2-C1O-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C0-C40-arylalkenyl gxoup, R16 and R17 sre a mono- or polynuclear hydrocarbon radical which with the central atom M1 can form a sand-wich ~tructure, ~,19 ~,,19 ~19 Rl9 R19 ,R~ Rl9 ~ 19 Rl~ i8 -M2- _M2_M2,, ,M2.caZ~ C-, ,o-~2-, C_C-R20 ~,20 R20 ~20 R20 1~20 R20 RZ0' =BRl9 =AlRl9, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, 2~61~69 =NR~9, =CO, =PRl9 or =P(O)R'9, where Rl9, R20 and R2l are identical or different and are a hydrogan atom, a halogen atom, a Cl-C1O-alkyl group, a Cl-C1O-fluoralkyl group, a C6-C1O-fluoraryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C1O-alkenyl group, a C,-C,0-arylalkyl group, a C~-C40-arylalkenyl group or a C7-CsO-alkylaryl group, or R19 and R20 or R19 and R21 each form a ring with the stom~ ~oining them, and M2 is ~ilicon, germanium or tin, which comprises ~topping the polymerization at a time when Mw/Mn c 2.
In thie connection alkyl i~ etraight-chain or branched alkyl.
The monocyclic olefin VII can al~o be substituted for the purposes of the invention (for example by alkyl or aryl radicals).
The cycloolefln (co)polymer~ wlth Mw/Mn ~ 2 which are prepared accerding to the invention are novel nnd the preeent in~ention likewise relates to them.
In the procee~ according to the invention, at leaet one polycyclic olefin of the ~ormul~e I, II, III, IV, V or VI, preférably n cycloolefin of the formul~e I or III, in which Rl, R2, R3, R~, R5, F~, R7 and R~ are ident~cal or different and are a hydrogen atom or a C1-Ca-alXyl radi-cal, it being poseible for identical r~d~c~le in the different formulae to have a different me~ning, is polymerized.
Where appropriate, a monocyclic olef$n of the formula VII
in which n is a nu~ber from 2 to 10 ~e aleo used. Another comonomer is an acyclic 1-olefin of the formula VIII in which R9, Rl, R11 and Rl2 are identical or different and are a hydrogen atom or a C1-Ca-alkyl radical. Ethylene or propylene are preferred.
Copolymers of polycyclic olefin~, preferably of the - 7 - 2~6~ ~69 formulae I and III, with the acyclic olefins VIII are particularly prepared.
Particularly preferred cycloolefins are norbornene and tetracyclododecene, it being possible for these to be ~ub~tituted by (Cl-C6)-alkyl. They are preferably eopolymerized with ethylene; ethylene/norbornene eopolymers have partieular importanee.
The polyeyelic olefin (I to VI) i8 employed in an amount of 0.1 to 100% by weiqht and the monoeyelie olefin (VII) i~ employed in an amount of 0 to 99.9~ by weight, in each ca~e ba~ed on the total amount of the monomers.
The concentration of the open-ehaln olefin i~ determined by the solubility of the open-chain olefin in the reac-tion medium under the given pre~ure and at the given tempèrature.
By polyeyelie olefin~, monoeyelie olefin~ and open-chain olefln~ are al~o meant mixture~ of two or more olefin~ of the partieular type. Thi~ mean~ that beeide~ polyeyelic homopolymer~ and bieopolymer~ lt i~ also po~ible to prepare ter- and multieopolymers by the proee~o aeoording to the inventlon. Copolymer~ of the eyeloolefino VII with the aeyelle olefln~ VIII ean al~o be obtained advanta-geou~ly by the proeea~ de w ribed. The preferred eycloole-fin VII i~ eyelopentene, whieh ean be sub~tituted.
The eataly~t to be u~ed for the proee~ aeeordlng to the lnventlon io eompo~ed of an aluminoxane and of at lea~t one metalloeene (tran~ltlon metal eomponent) of the formula XI
/ ' R14 ~18 Ml ~ ~X~) ~ 5 - 8 - 2~ 69 Ml in the formula XI i8 a metal from the group comprising titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium and hafnium. Zirconium i6 particularly preferably used.
R" and R~s are identical or different and are a hydrogen atom, a C1-C,O-, pxeferably C,-C3-alkyl group, a Cl-C,O-, preferably Cl-C3-alkoxy group, a C6-C10-, preferably C6-C8-aryl group, a C6-ClO-, preferably C6-C8-aryloxy group, a C2-C1O-, preferably C2-C~-alkenyl group, a C7-C~o-~ prefer-ably C7-C,O-arylalkyl group, a C7-c~o-~ preferably C7-Cl2-alkylaryl group, a C8-C~O-, preferably C~-Cl2-ar~lalkenyl group or a halogen atom, preferably chlorine.
R16 and R17 are identical or different and are a mano- or polynuclear hydrocarbon radical which with the central atom M1 can ~orm a ~andwich ~tructure. R16 i8 prefersbly fluorenyl and R17 i~ preferably cyclopentadienyl.
Rl8 i~ a linker which ha~ one or more members and which link~ the radlcale R15 and R17 and i~ preferably Rl9 Rl9 ~19 ~19 ~ 19 ~19 ~19 -M2- , -M2- M2- , .M2-C~21-, -C- , ~O_ 2_ , .C _ _ , ~20 R20 R20 ~20 ~20 ~20 R20 ~20 ~BR19, -A~R19, -Ge-, -Sn-, -O-, -S-, ~SO, ~SO2, ~NR19, -CO, -PR19 or -P(o)R~9, where R19, R20 and R21 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-slkyl group, a C1-C1O-fluoralkyl group, a C~-C10-aryl group, a C1-C10-alkoxy group, a C~-C1O-alkenyl group, a C7-C~0-arylalkyl group, a C8-C~0-arylalkenyl group or a C7-C~0-slkylaryl group, or R19 and R20 or R19 and R21 each form, together with the atoms connecting them, a ring.
N2 i~ ~ilicon, germanium or tin, preferably ~ilicon or germanium.
The bridged metallocenes can be prepared as ~hown in the g following known reaction scheme:
H2R~ ~ ButylLI ~ HR~U
X - R" - X
H2R" + ButylLi -- HR~'U
HR" - R" - R'7H t 2-BL~
LiR"- R~- R'7U I M'CI, E~.16 ~1~ ~Ml~ (X~ ) ~ ,~' ~c~
~ R17' or - 10 - 2~ 9 H2R" + Bu~ylU-- HR"Li Rl9 ,~20 16 ~R17 C ~, HR r,~ ~ R19R20C
R~ 8 b, H20 . ~L16 2 Sutylr.
r ~ 71 rlg~2C~l6~i2 MlC14 Rl9 / ' Cl R20 \l ~Cl !14~1 Rl~ ~ R16 R~/Rl Rl~l R~ Rl (X~ ) ~20\ ' ~Cl R20~ 5 R17 ~17 11 206~69 The above reaction scheme al~o applies when R19 = R20 and/or R14 = R15 ~cf. Journal of Organometallic Chem. 288 (1985) 63-67 and EP-A 320 762).
Metallocenes which are preferably employed are:
rac-dimethylsilyl-bis(l-indenyl)zirconium dichlorlde, rac-dimethylgermyl-bis(l-indenyl)zirconium dichloride, rac-phenylmethylsilyl-bis(l-indenyl)zirconium dichloride, rac-phenylvinylsilyl-bis(l-indenyl)zirconium dichloride, 1-silacyclobutyl-bis(l-indenyl)zirconium dichloride, rac-diphenylsilyl-bis(1-indenyl)hafnium dichloride, r~c-phenylmethyl~ilyl-bi~(l-indenyl)hafnium dichloride, r~c-d~phenyloilyl-bi~(l-indenyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride, i~opropylene(9-fluorenyl)cyclopentadienylzirconium dichloride.
Particularly preferred in this connection ares rac-dimethylsilyl-bis(l-indenyl)zirconium dichloride, raa-phenylmethyl~ilyl-b~ -indenyl)zirconium dichloride, rac-phenylvinyl~ilyl-bis(1-indenyl)zirconium dichloride, r~c-diphenyl~ilyl-bi~(l-indenyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)cyclopentadienylzirconlum dichloride, i~opropylene(9-fluorenyl)cyclopentadienylzirconium dichloride or phenylmethylmethylene(9-fluorenyl)cyclopentadienylzir-conium dichloride.
The cocatnly~t i~ ~n aluminoxane of the formula IX for the linear type and/or of the formula X for the cyclic type. The radical~ R13 in the~e formulae can be itentical or different and ~re a C,_CG_a1kY1 group, preferably methyl, ethyl or isobutyl, butyl or neopentyl, or phenyl or benzyl. Methyl iB part~cularly preferred. n is nn integer from O to 50, preferably 5 to 40.
The aluminoxane can be prepared in a variety of ways by - 12 - 20~1~69 known processes. One of the methods i~, for example, to react an aluminum-hydrocarbon compound and/or a hydrido-aluminum-hydrocarbon compound with water (gaseous, solid, liquid or bound - for example n~ water of cryst~lliza-S tion) in an inert solvent (such a~, for example,toluene). To prepare an aluminoxane with different alkyl groups R~3, two different aluminum trialkyls (AlR3 1 AlR~3) appropriate for the required composition are re~cted with water (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
The exac~ structure of the aluminoxAnee is unknown.
Irre~pective of the mode of preparation, it is common to all aluminoxane ~olutions that the content of unreacted aluminum starting compound, which is present in free form or a8 addùct, varies.
It i~ po~ible for the métallocene to be preactivated with an aluminoxane of the formula ~IX) and/or (X) before u~e in the polymerization reaction. This di~tinctly increa~e~ the polymerization activity.
The preactiv4tion of the tran~ition metal compound 18 carrled out ln ~olutlon. Thi~ preferably entails the metallocene being dissolved in a solutlon of the alumin-oxane in an lnert hydrocarbon. A sultable lnert hydrocar-bon 18 an allphatic or aromatic hydrocarbon. Toluene or cyclohexane are preferably u~ed.
The concentratlon of the aluminoxane ln the ~olution i~
in the range from about 14 by weight to the ~aturation limit, preferably from 5 to 30~ by weiqht, in each ca~e based on the total ~olution. ~he metallocene can be employed in the ~ame aoncentration, but lt i~ preferably employed in an ~mount of 10-~-1 mol per mol of alumln-o~ane. The preactlvation time i~ 5 minute~ to 60 hour~, preferably 5 to 60 minute~. The temperature i~ from -78~C
to lOO-C, preferably O to 70-C.
The metallocene can also be prepolymerized or applied to a support. It is preferable to use the (or one of the) olefin(s~ employed in the polymerization for the pre-polymerization.
Examples of suitable supports are silica gel~, aluminas, solid aluminoxane or other inorganic ~upport materials.
A suitable support material is also a polyolefin powder in finely divided form.
Another po6sible embodiment of the process according to the invention comprises using in place of or in addition to an aluminoxane a salt-like compound of the formula RXNH4XBR'4 or of the formula R3PHBR'4 as cocataly~t. In this, x is 1, 2 or 3, R is alkyl or aryl, identical or different, and R~ is aryl which can also be fluorinated or partially fluorinated. In this case, the catalyst is composed of the product of the reaction of a metallocene with one of the ~aid compounds (cf. ~P-A 277 004).
Any solvent added in a relatively small amount to the reaction mixture is one of the conventional inert sol--vents such as, for ~xample, aliphatic or cycloaliphatichydrocarbons ~for example ryclohexane), petroleum spirit or hydrogenated diesel oil fractions or toluene.
The polymerization takes place in dilute solution (< 80~
by volume cycloolefin), in concentrated solution (> 80%
by volume cycloolefin) or directly in the undiluted liquid cycloolefin monomer.
~he temperature and the reaction time must be appro-priately suited to one another depending on the activity o~ the cataly~t, the required molecular weight and the raquired molecular weight distribution. The concentration of the monomers and the nature of the solvent mu~t also be taken into account in this, e~pecially since these parameter~ essentially determine the relative incor-poration rates of the monomers and thu~ are crucial for ..
2~6~.g69 the qlas~ tran~ition temperature and heat distortion temperature of the polymers.
The lower the temperature chosen within the range from -78 to 150C, preferably between -78 and 70C, and particularly preferably between -78 and 40C, the longer it is po~sible for the polymerization time to be for the ~ame breadth of molecular weight distribution Mw/Nn (cf.
Tab. 2). Preferred molecular weight distributions are Mw/Nn < 1.7, in particular Mw/Mn s 1.4.
If it is also wished to aim at a particular molecular weight, it is nece~sary for the reaction t~me also to be ad~u~ted to suit the required molecular weight.
The reaction time required until the reaction i8 ~topped, which ~aries depending on the said reaction parameters and the cycloolefin incorporation rate, is determined by ~traightforward s~mpling a8 described in the exemplary embodiment~. It 1~ possible from serie~ of experiments to con~truct dlagr~m~ rom whlch the required times can then be t~ken (predetermlned) (cf. Flg. 1).
In order to achieve narrow molecular weight distributlons there mu~t be substantlal omission of tran~fer reagent~
such a8, for example, hydrogen. It is pos~ible to control the molecular weight via the reaction time.
If pure open-chain olefin, for example ethylene, is ~n~ected, pre~suree between 0.01 and 64 bar are employed, preerably 2 to 40 bar and partlcularly preferably 4 to 20 bar. If an inert ga~, for example nitrogen or argon, 18 aloo ln~ected ln addition to the open-chain olein, the total pressure in the re~ction vessel is 4 to 64 bar, preferably 4 to 40 bar and particularly preferably 4 to 25 bar. If the cycloolefinic component is undlluted, a high rate of cycloolefin incorporation is achieYed al~o undex high pres~ure~.
2~61~69 Continuous and multistaqe polymerization processe~ are particularly advantageous because they make economic use of the cycloolefin possible. It is also possible in continuous processes for the polycyclic olefin which can result as residual monomer together with the polymer to be recovered and returned to the reaction mixture.
The metallocene compound i8 used in a concentration, based on the transition metal, of 10-3 to 10-8, preferably 10-~ to 10-6, mol of transition metal per dm3 of reactor volume. The aluminoxane i8 u~ed in a concentration of lO-' to 10-1, preferably 10-4 to 2 x 10-2, mol per dm3 of reactor volume, based on the aluminum content. However, higher concentrations are al~o possible in principle.
Apart from the ~aid bridged metallocenes, it i~ also pos~ible in principle to employ metallocenes with identi-cAl or ~imilar unbridged lig~nds. The ~elect0d react~on times with the~e metallocene~ must be distinctly ~horter than with the bridged metallocenes under comparable reaction conditions.
In the preparatlon of copolymers, the molar ratios of the polycyclic olefln to the open-chain olefin whlch 1~
(preferably) employed can vnry within a wlde range. The molar ratio~ of cycloolefin to open-chain olefin which ~re preferably employed are from 3sl to lOOsl. The ~ncorporation rate of comonomer can be controlled vir-tually as required by the choice of the polymerization temperature, by the concentration of the catalyst com-ponent~ and by the molnr ratlo employed and the pressure of the ga~eou~ open-chain olefin. Incorporation rates between 20 and 75 mol% of the cyclic components are preferred, and incorporation rates between 35 and 65 mol~
of the cyclic components are particularly preferred.
It i~ posslble with the described process to prepare amorphous copolymers. The copolymers are tran~parent.
They are soluble, for example, in decahydronaphthalene at 135 C and in toluene at room temperature The polymers~
according to the invention are thermopla~ts Negligible breakdown or viscosity buildup has been found both on extrusion and on in~ection molding The materials prepared accordinq to the invention ar~
~uitable for the production of ~haped article~, particu-larly for the production of extruded articles ~uch as ~heet~, tube~, pipe~, rod~ and filaments and for the production of in~ection-molded articles of any required shape and ~ize An important property of the material~
according to the invention i~, besides the ~atisfactory flow~bility of the melt, their transparency Thi~ mean~
th~t the optical ~pplication~ of the extruded or in~ec-tion-molded articles made from the~e material~ have particularly great importance The refractive index, determined with an Abbe refr~ctometer ~nd mixed light, of the re~ction product~ described in the following ex~mples lo ln the range between 1 520 and 1 555 Since the refractlve index 1~ very clooe to that of arown gla~s (n - 1 51), the producto ~ccordlng to the invention can be w ed ao qla~ ~ub~titute in variou~ ~pplic~tions ~uch ao, for x~mple, len~e~, pri~m~, backing pl~tes and oh -to for optic~l data otore~, for videodlok~, for compact dloko, ao coverlng and focuoing plateo for ~olar cell~, ao covering ~nd diffu~ing pl~te~ for power optic~, ao light waveguides ln the form of ~iber~ or ~heet~
The polymero according to the inventlon can a1BO be employed for produclng polymer blends The blends can be produced ln the melt or ln solution The blends have a comblnatlon of the propertie~ of the components which i~
beneficial in each caoe for p~rticul~r application~ The following polymers c~n be employed for blends with the polymers accordlng to the invention~
polyethylene, polypropylene, (ethylene/propylene) copolymers, polybutylene, poly(4-methyl-1-pentene), polyisoprene, polyisobutylene, natural rubber, - 17 - 20~1869 poly(methylmethacrylate), other polymethacrylates, polyacrylate~, (acrylate/methacrylate) copolymers, polystyrene, (styrene/acrylonitrile) copolymers, bisphenol A polycarbonate, other polycarbonates, aromatic polye~ter carbonates, polyethylene terephthalate, poly-butylene terephthalate, amorphous polyarylates, nylon 6, nylon 66, other polyamides, polyaramides, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinylidene fluoride and cycloolefin (co)polymers with molecular weight distribution Nw/~n 2 2 It is al80 possible to blend a plurality of polymers aeeording to the invention together to achieve partieular melting properties The glass transition temperatures (Tg) stated in the following exomple~ were determined by DSC (differential ~canning ealorimetry) at a heating rate of 20 C/min The ~tated vi~eo~ity numbers were mea~ured by the DIN 53 728 method Th- mol-eular weight di~tribution (Mw/Mn) and the mol-cular weight (Mw) of the reactlon produet~ were determined by gel permeatlon chromatography ~xomple 1 A cl-an and dry 1 5 dm3 polymerization reaetor with ~tirrer wa~ flu-hed with nitrogon and then with ethylene and charged with 576 ml of an 85 percent by volume ~olution of norbornene ln toluene While ~tirring, the reaetor wa~ then malntained at a temperature of 70 C, and 6 bar of ethylene (gage pres-~ure) were in~eeted Then 20 em3 of a ~olution of methylalumlnoxane ln toluene (MAO ~olution) (10 1~ by weight methylalumlnoxane wlth molecular weight 1,300 g/mol determlned by eryoscopy) were metered into the reaetor, and the m~xture was 2~61869 stirred at ~O-C for 15 min, during which the ethylene pre~sure wa~ maintained at 6 bar by subsequent metering.
In parallel with thi~, 60 mg of rac-dimethylsilyl-bis(l-indenyl)zirconium dichloride were dis~olved in 10 cm3 of S a 601ution of methylaluminoxane in toluene (~ee above for concentration and characteristics) and preactivated by being left to ~and for 15 minutes. The ~olution of the complex was then metered into the reactor. While stirring (750 rpm), polymerization was then carried out at 70C, maintaining the ethylene pressure at 6 bar by subsequent metering.
50 ml ~ample~ were t~ken from the reaction medium through an alr lock at intervals of 15 min after addition of the oataly~t.
The ~ample~ were rapidly di~charged into a stirred vessel containing 100 cm3 of isopropanol (~topper; ~toppage of the reactlon). The mlxture was added dropwi~e to 2 dm3 of acetone, ~tirred for 10 min and then the ~u~pended polymeric ~olld w~ filtered off.
The filtered-off polymer wa~ then added to 2 dm3 of a mlxture of 2 p~rt~ of 3-norm~l hydrochloric acld and one part of ethanol, and thi~ su~pen~lon wa~ ~tlrred ~or 2 hour~. The polymer wa~ then flltered off agaln, w~hed wlth watér to neutrality and dried at 80-C under 0.2 b~r for 15 hour~.
The propertie~ o f the ~ample~ are ~hown in Table 1 ~nd Flg~. 1 to 4. The~e dl~tlnctly ~how, ln Flg~. 1 (o~mple A) -4 ~mple D), the change ln the molecul~r welght MW
(increa~e) ~nd in the molecular welght dl~trlbutlon (broadening) a8 the reaction time lncrease~.
2~86~
Table 1 , . . . _.
Sample Time after Glass transition cat. addition temperature MW M~/Mn (min) (-C) (g~mol) L
A 15 162 2.06 x lO~ 1.7 _ B 30 161 3.25 x 10~ 2.2 C 45 159 3.95 x 10~ 2.2 . l D 60 158 4.57 x 10~ 2 5 ~xample 2 The process wa~ carried out in analogy to Example 1, but the following parameters were changeds Reaction tempernture~ 20C
Amount of catalystt 240 mg ~mplingt every 10 minutes ~he properties of the samples are shown in Table 2.
2 ~ 9 Table 2 . ~ ..
Sample Time after Glas~ transition cat. addition temperature MW Mw/
i (min) (C) (g/mol) l E 10 140 1.67 x 104 1.1 I . _ ~ 1 20 143 2.83 x 10' 1.1 G 30 143 3.99 x 10' 1.1 i ~ 1 40 1 144 4.88 x 104 1.
Example 3 54 g of a polymer were prepared in analogy to Example 1 but differing from Example 1 in the ~election of the following polymerizatlon condltlonst - concentration of the norbornene solution employed t 27%;
- ethylene pre~ures 3 bar;
- cataly~t~ fluorenyl-cyclopentadlenyl-diphenyl-carbyl-z~rconium dichloride;
- amount of catalysts 10 mg;
- amount of methylaluminoxane ~olutions 20 ml~
- reaction times 30 min.
~he re~ulting polymer ha~ a gla~s tran~ition temperature of 141C, a Mw of 1.63 x 105 and a molecular weight di~tribution ~w/Mn of 2Ø
~x~mple 4 The polymerlzation was carried out in analogy to Example 1. 40 cm3 of NAO solution with 500 mg of - 21 - 2 ~6 1869 rac-dimethylsilyl-bi~(l-indenyl)zirconiumdichloridewere employed as catalyst solution. Polymerization was carried out at 6-C under an ethylene gauge pressure of 4 bar for 30 min. It wa~ possible to obtain 3.8 g of product. The glass transition temperature was 122-C. A molecular weight ~w of 2,540 g/mol and a molecular weight distribu-tion Mw~Mn of 1.15 were found by GPC (in analogy to ~xample 1 + 2).
Example 5 The polymerization was carried out in an~logy to ~xample 4. Polymerization wa~ carried out at 20~C and under an ethylene gauge pressure of 6 bar for 10 min. 10.4 g of product were isolated. The gla~ transition temperature wa~ 142-C. The molecular weight Mw was 7,240 g/mol and the molecular weight dlstribution Mw/Mn wa8 1.10.
~xample 6 2.4 g of a polymer according to Example 3 and 0.6 g of a polymer according to Ex~mple 4 were di~olved ln 147 g of toluene and then preclpltated by ~low dropwl~e addition to acetone. The preclpltated material wa~ then drled ln a drylng oven at 80-C for one day. The polymer blend obtalned ln thl~ way had a glass transition temperature of 138-C measured by DSC wlth a heating rate of 20'C/minute.
Example 7 48 g of a polymer accordlng to Example 3 snd 12 g of a polymer according to ~xample 5 were mixed and kneaded ln a Rheomix 600 measuring kneader supplied by Haake at a speed of 60 revolutlons per mlnute at 225~C for 15 mlnutes. The blend obtained ln this way was tran~parent and had a glaes transition temperature of 141-C mea~ured by DSC with a heating rate of 20-C/minute.
- 22 - 20~69 Example 8 Circular compressed disks with a diameter of 25 mm were produced from the materials according to Examples 3, 6 and 7 by compression at 225C for 15 minutes. All the compres~ed disk~ were colorless and transparent. To evaluate and compare the proce~sability of the6e material~, the compressed disks obtained in this way were used to determine the viscosity ETA. The apparatus used for this was a Rheometric~ dynamic spectrometer RDS 2.
The mea~urements were carried out with disk-disk geometry at 270C and at two frequencies. The re~ults of the measurement~ are compiled in Table 3.
Table 3~
, ., Sample identificntion Vi~cosity ETA (Pa.~) ~ccording to Example No. Frequency 1 Frequency 2 1 rad/~ 10 rad/~
It i~ known that polycyclic olefin~ can be polymerized u~ing v_riou~ Ziegler eataly~t~. Depending on the eata-lyst, the polymerization tAke~ plaee via ring opening(cf. US 4 178 424) or opening of the double bond (cf.
EP-A 156 464, ~P-A 283 164).
The di~advant~ge of a ring-opening polymerization i~ that the re~ulting polymer contain~ double bonds which may lead to ero~ nking of ehain~ and thus eonsiderably re~trlet the proee~ability of the material by extru~ion or in~eetlon molding.
Polymerlzatlon wlth openlng of the double bond ha~ a relatlvely low polymerlzatlon rate (reaetlon rate) in the ea~e of eyelie olefln~.
When polymer~ are proees~ed by in~eetion molding or when polymer filament~ are ~tretehed, it i8 a great advantage for the moleeular weight di~tributlon of the polymer~ to be a~ narrow a~ po~lble.
It iB known that the moleeular weight diotribution~
aehleved ln ree-radi¢al polymerizations a~ well a~ in ela~leal Ziegler polymerization are broad, i.e. that Mw/Mn 1~ dl~tinetly l_rger than 2. A moleeul_r weight di~tributlon Mw/Mn ~ 2 ean be _ehieved in the polymerization of olefins earried out u~ing metallocene eataly~t~. However, even narrower molecular weight distributions would be desirable for specific 2 2061~69 applications (for example precision in~ection molding).
The ob~ect was therefore to prepare, using a proces~
which i~ as straightforward as pos~ible, polycycloolefins and cycloolefin copolymers with a distribution which is as narrow a~ possible.
It has been found, surpri~ingly, that polycycloolefins and cycloolefin copolymers with molecular weight di~-tributions Mw/Mn ~ 2 can be obtained by using specific metallocene catalyst~ in combination with particular polymerization conditlon~ such as concentration and temperature, and, in particular, by the choice of par-ticular polymerization times.
This finding is extremely ~urprising because all the theoretical treatmenta of Ziegler polymerization hitherto di~closed permit a distribution Mw/Mn = 2 a~ a minimum.
Narrower di~tribution~ a~ have been found according to the invention indicate that most of the polymer chains are a~embled throughout the polymerization time, i.e.
polymerisation may, under certain condltlons, take place in a v0ry ~imllar manner to a living polymerization as 1 kn~wn, for example, ~or the anionlc polymerlzatlon o~
~tyrene.
The invention therefore relates to a proce~ for the preparation of a cycloolefin polymer or copolymer wlth a narrow molecular weight di~tribution ~Mw/Mn) by polymerization of 0.1 to 100~ by weight, ba~ed on the total amount of the monomer~, of ~t lea~t one monomer of the formulae I, II, III, IV, V or VI
~ H ~ ~ R
HC CH
¦¦ R3-l ~-~4 HC i _ C~
~ C~ 2 _ 3 _ 2~ 69 XC ¦ CH
¦¦ R3-C-R4 ¦ C~2 ~II), ~C--¦ --CH~ ¦ --CH~
¦¦ R3-C_R4 ¦R5-C-R6 ¦ ~555), HC ¦ ~, CH ¦ ~ CH
HC ¦ CH ¦ Cll ~ ¦ CX
¦¦ ~3-C-R4 ¦ R5-C-R6 ¦ R7-C-R3 ¦ (~V), HC ¦ C~ I ~CH~ ¦ C~
~ I CX ~ ~CX
¦¦ P.3-C-R4 l l IV) XC--CX~ CX~ --}~,2 ~6 ~ CH~
¦¦ R3-C-R4 l l R7-C-R3 ¦ ~V~), :
` - 4 - 2061~69 in which Rl, R2, R3, R', Rs, R6, R7 and R~ are identical or different and are a hydrogen atom or a C,-C~-alkyl radi-cal, it being possible for identical radicals in the different formulae to have a different meaning, 0 to 99.9~ by weight, based on the total amount of the monomers, of a cycloolefin of the formula VII
(CX2)n (VII), in which n ie ~ number from 2 to 10, and 0 to 99.9% by weight, based on the total amount of the monomere, of at lea~t one acyclic l-olefin of the formula VIII
/C_C\ (V~i), Ril R12 ln whlch R', Rl, Rll and Rl2 are identical or d~fforent ~nd are a hydrogen atom or a Cl-C,-alXyl radicsl, at tempera-turee from -78 to 150-C and undex a pre~ure o from 0.01 to 64 bar, in the preeence of a c~talyst which ie com-poeed of ~n ~luminox~ne of the formuls IX
~ Al - ~ Al ~SX) R13~ n ~ R13 for the linear type snd/or of the formula X
~ 5 ~ 2~ 9 ¦-R13 _ -Al - o - ~X) _ ~2 for the cyclic type, where the radicals Rl3 in the for-mulae IX and X are identical or different and are a Cl-C6-alkyl group or phenyl or benzyl, and n iB an integer from 0 to 50, and of a metallocene of the formula XI
/, R14 R18 M1~ ~XI) \' R15 in which M1 i~ tltanium, zirconlum, hafnium, vanadium, niobium or tantalum, 10 Rl4 and R1~ are identlcal or different and are a hydrogen atom, a halogen atam, ~ C1-C1O-alkyl group, a Cl-C1O-alkoxy group, a C~-C1O-aryl group, a Ca-Clo~
aryloxy group, a C2-C1O-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C0-C40-arylalkenyl gxoup, R16 and R17 sre a mono- or polynuclear hydrocarbon radical which with the central atom M1 can form a sand-wich ~tructure, ~,19 ~,,19 ~19 Rl9 R19 ,R~ Rl9 ~ 19 Rl~ i8 -M2- _M2_M2,, ,M2.caZ~ C-, ,o-~2-, C_C-R20 ~,20 R20 ~20 R20 1~20 R20 RZ0' =BRl9 =AlRl9, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, 2~61~69 =NR~9, =CO, =PRl9 or =P(O)R'9, where Rl9, R20 and R2l are identical or different and are a hydrogan atom, a halogen atom, a Cl-C1O-alkyl group, a Cl-C1O-fluoralkyl group, a C6-C1O-fluoraryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C1O-alkenyl group, a C,-C,0-arylalkyl group, a C~-C40-arylalkenyl group or a C7-CsO-alkylaryl group, or R19 and R20 or R19 and R21 each form a ring with the stom~ ~oining them, and M2 is ~ilicon, germanium or tin, which comprises ~topping the polymerization at a time when Mw/Mn c 2.
In thie connection alkyl i~ etraight-chain or branched alkyl.
The monocyclic olefin VII can al~o be substituted for the purposes of the invention (for example by alkyl or aryl radicals).
The cycloolefln (co)polymer~ wlth Mw/Mn ~ 2 which are prepared accerding to the invention are novel nnd the preeent in~ention likewise relates to them.
In the procee~ according to the invention, at leaet one polycyclic olefin of the ~ormul~e I, II, III, IV, V or VI, preférably n cycloolefin of the formul~e I or III, in which Rl, R2, R3, R~, R5, F~, R7 and R~ are ident~cal or different and are a hydrogen atom or a C1-Ca-alXyl radi-cal, it being poseible for identical r~d~c~le in the different formulae to have a different me~ning, is polymerized.
Where appropriate, a monocyclic olef$n of the formula VII
in which n is a nu~ber from 2 to 10 ~e aleo used. Another comonomer is an acyclic 1-olefin of the formula VIII in which R9, Rl, R11 and Rl2 are identical or different and are a hydrogen atom or a C1-Ca-alkyl radical. Ethylene or propylene are preferred.
Copolymers of polycyclic olefin~, preferably of the - 7 - 2~6~ ~69 formulae I and III, with the acyclic olefins VIII are particularly prepared.
Particularly preferred cycloolefins are norbornene and tetracyclododecene, it being possible for these to be ~ub~tituted by (Cl-C6)-alkyl. They are preferably eopolymerized with ethylene; ethylene/norbornene eopolymers have partieular importanee.
The polyeyelic olefin (I to VI) i8 employed in an amount of 0.1 to 100% by weiqht and the monoeyelie olefin (VII) i~ employed in an amount of 0 to 99.9~ by weight, in each ca~e ba~ed on the total amount of the monomers.
The concentration of the open-ehaln olefin i~ determined by the solubility of the open-chain olefin in the reac-tion medium under the given pre~ure and at the given tempèrature.
By polyeyelie olefin~, monoeyelie olefin~ and open-chain olefln~ are al~o meant mixture~ of two or more olefin~ of the partieular type. Thi~ mean~ that beeide~ polyeyelic homopolymer~ and bieopolymer~ lt i~ also po~ible to prepare ter- and multieopolymers by the proee~o aeoording to the inventlon. Copolymer~ of the eyeloolefino VII with the aeyelle olefln~ VIII ean al~o be obtained advanta-geou~ly by the proeea~ de w ribed. The preferred eycloole-fin VII i~ eyelopentene, whieh ean be sub~tituted.
The eataly~t to be u~ed for the proee~ aeeordlng to the lnventlon io eompo~ed of an aluminoxane and of at lea~t one metalloeene (tran~ltlon metal eomponent) of the formula XI
/ ' R14 ~18 Ml ~ ~X~) ~ 5 - 8 - 2~ 69 Ml in the formula XI i8 a metal from the group comprising titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium and hafnium. Zirconium i6 particularly preferably used.
R" and R~s are identical or different and are a hydrogen atom, a C1-C,O-, pxeferably C,-C3-alkyl group, a Cl-C,O-, preferably Cl-C3-alkoxy group, a C6-C10-, preferably C6-C8-aryl group, a C6-ClO-, preferably C6-C8-aryloxy group, a C2-C1O-, preferably C2-C~-alkenyl group, a C7-C~o-~ prefer-ably C7-C,O-arylalkyl group, a C7-c~o-~ preferably C7-Cl2-alkylaryl group, a C8-C~O-, preferably C~-Cl2-ar~lalkenyl group or a halogen atom, preferably chlorine.
R16 and R17 are identical or different and are a mano- or polynuclear hydrocarbon radical which with the central atom M1 can ~orm a ~andwich ~tructure. R16 i8 prefersbly fluorenyl and R17 i~ preferably cyclopentadienyl.
Rl8 i~ a linker which ha~ one or more members and which link~ the radlcale R15 and R17 and i~ preferably Rl9 Rl9 ~19 ~19 ~ 19 ~19 ~19 -M2- , -M2- M2- , .M2-C~21-, -C- , ~O_ 2_ , .C _ _ , ~20 R20 R20 ~20 ~20 ~20 R20 ~20 ~BR19, -A~R19, -Ge-, -Sn-, -O-, -S-, ~SO, ~SO2, ~NR19, -CO, -PR19 or -P(o)R~9, where R19, R20 and R21 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-slkyl group, a C1-C1O-fluoralkyl group, a C~-C10-aryl group, a C1-C10-alkoxy group, a C~-C1O-alkenyl group, a C7-C~0-arylalkyl group, a C8-C~0-arylalkenyl group or a C7-C~0-slkylaryl group, or R19 and R20 or R19 and R21 each form, together with the atoms connecting them, a ring.
N2 i~ ~ilicon, germanium or tin, preferably ~ilicon or germanium.
The bridged metallocenes can be prepared as ~hown in the g following known reaction scheme:
H2R~ ~ ButylLI ~ HR~U
X - R" - X
H2R" + ButylLi -- HR~'U
HR" - R" - R'7H t 2-BL~
LiR"- R~- R'7U I M'CI, E~.16 ~1~ ~Ml~ (X~ ) ~ ,~' ~c~
~ R17' or - 10 - 2~ 9 H2R" + Bu~ylU-- HR"Li Rl9 ,~20 16 ~R17 C ~, HR r,~ ~ R19R20C
R~ 8 b, H20 . ~L16 2 Sutylr.
r ~ 71 rlg~2C~l6~i2 MlC14 Rl9 / ' Cl R20 \l ~Cl !14~1 Rl~ ~ R16 R~/Rl Rl~l R~ Rl (X~ ) ~20\ ' ~Cl R20~ 5 R17 ~17 11 206~69 The above reaction scheme al~o applies when R19 = R20 and/or R14 = R15 ~cf. Journal of Organometallic Chem. 288 (1985) 63-67 and EP-A 320 762).
Metallocenes which are preferably employed are:
rac-dimethylsilyl-bis(l-indenyl)zirconium dichlorlde, rac-dimethylgermyl-bis(l-indenyl)zirconium dichloride, rac-phenylmethylsilyl-bis(l-indenyl)zirconium dichloride, rac-phenylvinylsilyl-bis(l-indenyl)zirconium dichloride, 1-silacyclobutyl-bis(l-indenyl)zirconium dichloride, rac-diphenylsilyl-bis(1-indenyl)hafnium dichloride, r~c-phenylmethyl~ilyl-bi~(l-indenyl)hafnium dichloride, r~c-d~phenyloilyl-bi~(l-indenyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride, i~opropylene(9-fluorenyl)cyclopentadienylzirconium dichloride.
Particularly preferred in this connection ares rac-dimethylsilyl-bis(l-indenyl)zirconium dichloride, raa-phenylmethyl~ilyl-b~ -indenyl)zirconium dichloride, rac-phenylvinyl~ilyl-bis(1-indenyl)zirconium dichloride, r~c-diphenyl~ilyl-bi~(l-indenyl)zirconium dichloride, diphenylmethylene(9-fluorenyl)cyclopentadienylzirconlum dichloride, i~opropylene(9-fluorenyl)cyclopentadienylzirconium dichloride or phenylmethylmethylene(9-fluorenyl)cyclopentadienylzir-conium dichloride.
The cocatnly~t i~ ~n aluminoxane of the formula IX for the linear type and/or of the formula X for the cyclic type. The radical~ R13 in the~e formulae can be itentical or different and ~re a C,_CG_a1kY1 group, preferably methyl, ethyl or isobutyl, butyl or neopentyl, or phenyl or benzyl. Methyl iB part~cularly preferred. n is nn integer from O to 50, preferably 5 to 40.
The aluminoxane can be prepared in a variety of ways by - 12 - 20~1~69 known processes. One of the methods i~, for example, to react an aluminum-hydrocarbon compound and/or a hydrido-aluminum-hydrocarbon compound with water (gaseous, solid, liquid or bound - for example n~ water of cryst~lliza-S tion) in an inert solvent (such a~, for example,toluene). To prepare an aluminoxane with different alkyl groups R~3, two different aluminum trialkyls (AlR3 1 AlR~3) appropriate for the required composition are re~cted with water (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
The exac~ structure of the aluminoxAnee is unknown.
Irre~pective of the mode of preparation, it is common to all aluminoxane ~olutions that the content of unreacted aluminum starting compound, which is present in free form or a8 addùct, varies.
It i~ po~ible for the métallocene to be preactivated with an aluminoxane of the formula ~IX) and/or (X) before u~e in the polymerization reaction. This di~tinctly increa~e~ the polymerization activity.
The preactiv4tion of the tran~ition metal compound 18 carrled out ln ~olutlon. Thi~ preferably entails the metallocene being dissolved in a solutlon of the alumin-oxane in an lnert hydrocarbon. A sultable lnert hydrocar-bon 18 an allphatic or aromatic hydrocarbon. Toluene or cyclohexane are preferably u~ed.
The concentratlon of the aluminoxane ln the ~olution i~
in the range from about 14 by weight to the ~aturation limit, preferably from 5 to 30~ by weiqht, in each ca~e based on the total ~olution. ~he metallocene can be employed in the ~ame aoncentration, but lt i~ preferably employed in an ~mount of 10-~-1 mol per mol of alumln-o~ane. The preactlvation time i~ 5 minute~ to 60 hour~, preferably 5 to 60 minute~. The temperature i~ from -78~C
to lOO-C, preferably O to 70-C.
The metallocene can also be prepolymerized or applied to a support. It is preferable to use the (or one of the) olefin(s~ employed in the polymerization for the pre-polymerization.
Examples of suitable supports are silica gel~, aluminas, solid aluminoxane or other inorganic ~upport materials.
A suitable support material is also a polyolefin powder in finely divided form.
Another po6sible embodiment of the process according to the invention comprises using in place of or in addition to an aluminoxane a salt-like compound of the formula RXNH4XBR'4 or of the formula R3PHBR'4 as cocataly~t. In this, x is 1, 2 or 3, R is alkyl or aryl, identical or different, and R~ is aryl which can also be fluorinated or partially fluorinated. In this case, the catalyst is composed of the product of the reaction of a metallocene with one of the ~aid compounds (cf. ~P-A 277 004).
Any solvent added in a relatively small amount to the reaction mixture is one of the conventional inert sol--vents such as, for ~xample, aliphatic or cycloaliphatichydrocarbons ~for example ryclohexane), petroleum spirit or hydrogenated diesel oil fractions or toluene.
The polymerization takes place in dilute solution (< 80~
by volume cycloolefin), in concentrated solution (> 80%
by volume cycloolefin) or directly in the undiluted liquid cycloolefin monomer.
~he temperature and the reaction time must be appro-priately suited to one another depending on the activity o~ the cataly~t, the required molecular weight and the raquired molecular weight distribution. The concentration of the monomers and the nature of the solvent mu~t also be taken into account in this, e~pecially since these parameter~ essentially determine the relative incor-poration rates of the monomers and thu~ are crucial for ..
2~6~.g69 the qlas~ tran~ition temperature and heat distortion temperature of the polymers.
The lower the temperature chosen within the range from -78 to 150C, preferably between -78 and 70C, and particularly preferably between -78 and 40C, the longer it is po~sible for the polymerization time to be for the ~ame breadth of molecular weight distribution Mw/Nn (cf.
Tab. 2). Preferred molecular weight distributions are Mw/Nn < 1.7, in particular Mw/Mn s 1.4.
If it is also wished to aim at a particular molecular weight, it is nece~sary for the reaction t~me also to be ad~u~ted to suit the required molecular weight.
The reaction time required until the reaction i8 ~topped, which ~aries depending on the said reaction parameters and the cycloolefin incorporation rate, is determined by ~traightforward s~mpling a8 described in the exemplary embodiment~. It 1~ possible from serie~ of experiments to con~truct dlagr~m~ rom whlch the required times can then be t~ken (predetermlned) (cf. Flg. 1).
In order to achieve narrow molecular weight distributlons there mu~t be substantlal omission of tran~fer reagent~
such a8, for example, hydrogen. It is pos~ible to control the molecular weight via the reaction time.
If pure open-chain olefin, for example ethylene, is ~n~ected, pre~suree between 0.01 and 64 bar are employed, preerably 2 to 40 bar and partlcularly preferably 4 to 20 bar. If an inert ga~, for example nitrogen or argon, 18 aloo ln~ected ln addition to the open-chain olein, the total pressure in the re~ction vessel is 4 to 64 bar, preferably 4 to 40 bar and particularly preferably 4 to 25 bar. If the cycloolefinic component is undlluted, a high rate of cycloolefin incorporation is achieYed al~o undex high pres~ure~.
2~61~69 Continuous and multistaqe polymerization processe~ are particularly advantageous because they make economic use of the cycloolefin possible. It is also possible in continuous processes for the polycyclic olefin which can result as residual monomer together with the polymer to be recovered and returned to the reaction mixture.
The metallocene compound i8 used in a concentration, based on the transition metal, of 10-3 to 10-8, preferably 10-~ to 10-6, mol of transition metal per dm3 of reactor volume. The aluminoxane i8 u~ed in a concentration of lO-' to 10-1, preferably 10-4 to 2 x 10-2, mol per dm3 of reactor volume, based on the aluminum content. However, higher concentrations are al~o possible in principle.
Apart from the ~aid bridged metallocenes, it i~ also pos~ible in principle to employ metallocenes with identi-cAl or ~imilar unbridged lig~nds. The ~elect0d react~on times with the~e metallocene~ must be distinctly ~horter than with the bridged metallocenes under comparable reaction conditions.
In the preparatlon of copolymers, the molar ratios of the polycyclic olefln to the open-chain olefin whlch 1~
(preferably) employed can vnry within a wlde range. The molar ratio~ of cycloolefin to open-chain olefin which ~re preferably employed are from 3sl to lOOsl. The ~ncorporation rate of comonomer can be controlled vir-tually as required by the choice of the polymerization temperature, by the concentration of the catalyst com-ponent~ and by the molnr ratlo employed and the pressure of the ga~eou~ open-chain olefin. Incorporation rates between 20 and 75 mol% of the cyclic components are preferred, and incorporation rates between 35 and 65 mol~
of the cyclic components are particularly preferred.
It i~ posslble with the described process to prepare amorphous copolymers. The copolymers are tran~parent.
They are soluble, for example, in decahydronaphthalene at 135 C and in toluene at room temperature The polymers~
according to the invention are thermopla~ts Negligible breakdown or viscosity buildup has been found both on extrusion and on in~ection molding The materials prepared accordinq to the invention ar~
~uitable for the production of ~haped article~, particu-larly for the production of extruded articles ~uch as ~heet~, tube~, pipe~, rod~ and filaments and for the production of in~ection-molded articles of any required shape and ~ize An important property of the material~
according to the invention i~, besides the ~atisfactory flow~bility of the melt, their transparency Thi~ mean~
th~t the optical ~pplication~ of the extruded or in~ec-tion-molded articles made from the~e material~ have particularly great importance The refractive index, determined with an Abbe refr~ctometer ~nd mixed light, of the re~ction product~ described in the following ex~mples lo ln the range between 1 520 and 1 555 Since the refractlve index 1~ very clooe to that of arown gla~s (n - 1 51), the producto ~ccordlng to the invention can be w ed ao qla~ ~ub~titute in variou~ ~pplic~tions ~uch ao, for x~mple, len~e~, pri~m~, backing pl~tes and oh -to for optic~l data otore~, for videodlok~, for compact dloko, ao coverlng and focuoing plateo for ~olar cell~, ao covering ~nd diffu~ing pl~te~ for power optic~, ao light waveguides ln the form of ~iber~ or ~heet~
The polymero according to the inventlon can a1BO be employed for produclng polymer blends The blends can be produced ln the melt or ln solution The blends have a comblnatlon of the propertie~ of the components which i~
beneficial in each caoe for p~rticul~r application~ The following polymers c~n be employed for blends with the polymers accordlng to the invention~
polyethylene, polypropylene, (ethylene/propylene) copolymers, polybutylene, poly(4-methyl-1-pentene), polyisoprene, polyisobutylene, natural rubber, - 17 - 20~1869 poly(methylmethacrylate), other polymethacrylates, polyacrylate~, (acrylate/methacrylate) copolymers, polystyrene, (styrene/acrylonitrile) copolymers, bisphenol A polycarbonate, other polycarbonates, aromatic polye~ter carbonates, polyethylene terephthalate, poly-butylene terephthalate, amorphous polyarylates, nylon 6, nylon 66, other polyamides, polyaramides, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinylidene fluoride and cycloolefin (co)polymers with molecular weight distribution Nw/~n 2 2 It is al80 possible to blend a plurality of polymers aeeording to the invention together to achieve partieular melting properties The glass transition temperatures (Tg) stated in the following exomple~ were determined by DSC (differential ~canning ealorimetry) at a heating rate of 20 C/min The ~tated vi~eo~ity numbers were mea~ured by the DIN 53 728 method Th- mol-eular weight di~tribution (Mw/Mn) and the mol-cular weight (Mw) of the reactlon produet~ were determined by gel permeatlon chromatography ~xomple 1 A cl-an and dry 1 5 dm3 polymerization reaetor with ~tirrer wa~ flu-hed with nitrogon and then with ethylene and charged with 576 ml of an 85 percent by volume ~olution of norbornene ln toluene While ~tirring, the reaetor wa~ then malntained at a temperature of 70 C, and 6 bar of ethylene (gage pres-~ure) were in~eeted Then 20 em3 of a ~olution of methylalumlnoxane ln toluene (MAO ~olution) (10 1~ by weight methylalumlnoxane wlth molecular weight 1,300 g/mol determlned by eryoscopy) were metered into the reaetor, and the m~xture was 2~61869 stirred at ~O-C for 15 min, during which the ethylene pre~sure wa~ maintained at 6 bar by subsequent metering.
In parallel with thi~, 60 mg of rac-dimethylsilyl-bis(l-indenyl)zirconium dichloride were dis~olved in 10 cm3 of S a 601ution of methylaluminoxane in toluene (~ee above for concentration and characteristics) and preactivated by being left to ~and for 15 minutes. The ~olution of the complex was then metered into the reactor. While stirring (750 rpm), polymerization was then carried out at 70C, maintaining the ethylene pressure at 6 bar by subsequent metering.
50 ml ~ample~ were t~ken from the reaction medium through an alr lock at intervals of 15 min after addition of the oataly~t.
The ~ample~ were rapidly di~charged into a stirred vessel containing 100 cm3 of isopropanol (~topper; ~toppage of the reactlon). The mlxture was added dropwi~e to 2 dm3 of acetone, ~tirred for 10 min and then the ~u~pended polymeric ~olld w~ filtered off.
The filtered-off polymer wa~ then added to 2 dm3 of a mlxture of 2 p~rt~ of 3-norm~l hydrochloric acld and one part of ethanol, and thi~ su~pen~lon wa~ ~tlrred ~or 2 hour~. The polymer wa~ then flltered off agaln, w~hed wlth watér to neutrality and dried at 80-C under 0.2 b~r for 15 hour~.
The propertie~ o f the ~ample~ are ~hown in Table 1 ~nd Flg~. 1 to 4. The~e dl~tlnctly ~how, ln Flg~. 1 (o~mple A) -4 ~mple D), the change ln the molecul~r welght MW
(increa~e) ~nd in the molecular welght dl~trlbutlon (broadening) a8 the reaction time lncrease~.
2~86~
Table 1 , . . . _.
Sample Time after Glass transition cat. addition temperature MW M~/Mn (min) (-C) (g~mol) L
A 15 162 2.06 x lO~ 1.7 _ B 30 161 3.25 x 10~ 2.2 C 45 159 3.95 x 10~ 2.2 . l D 60 158 4.57 x 10~ 2 5 ~xample 2 The process wa~ carried out in analogy to Example 1, but the following parameters were changeds Reaction tempernture~ 20C
Amount of catalystt 240 mg ~mplingt every 10 minutes ~he properties of the samples are shown in Table 2.
2 ~ 9 Table 2 . ~ ..
Sample Time after Glas~ transition cat. addition temperature MW Mw/
i (min) (C) (g/mol) l E 10 140 1.67 x 104 1.1 I . _ ~ 1 20 143 2.83 x 10' 1.1 G 30 143 3.99 x 10' 1.1 i ~ 1 40 1 144 4.88 x 104 1.
Example 3 54 g of a polymer were prepared in analogy to Example 1 but differing from Example 1 in the ~election of the following polymerizatlon condltlonst - concentration of the norbornene solution employed t 27%;
- ethylene pre~ures 3 bar;
- cataly~t~ fluorenyl-cyclopentadlenyl-diphenyl-carbyl-z~rconium dichloride;
- amount of catalysts 10 mg;
- amount of methylaluminoxane ~olutions 20 ml~
- reaction times 30 min.
~he re~ulting polymer ha~ a gla~s tran~ition temperature of 141C, a Mw of 1.63 x 105 and a molecular weight di~tribution ~w/Mn of 2Ø
~x~mple 4 The polymerlzation was carried out in analogy to Example 1. 40 cm3 of NAO solution with 500 mg of - 21 - 2 ~6 1869 rac-dimethylsilyl-bi~(l-indenyl)zirconiumdichloridewere employed as catalyst solution. Polymerization was carried out at 6-C under an ethylene gauge pressure of 4 bar for 30 min. It wa~ possible to obtain 3.8 g of product. The glass transition temperature was 122-C. A molecular weight ~w of 2,540 g/mol and a molecular weight distribu-tion Mw~Mn of 1.15 were found by GPC (in analogy to ~xample 1 + 2).
Example 5 The polymerization was carried out in an~logy to ~xample 4. Polymerization wa~ carried out at 20~C and under an ethylene gauge pressure of 6 bar for 10 min. 10.4 g of product were isolated. The gla~ transition temperature wa~ 142-C. The molecular weight Mw was 7,240 g/mol and the molecular weight dlstribution Mw/Mn wa8 1.10.
~xample 6 2.4 g of a polymer according to Example 3 and 0.6 g of a polymer according to Ex~mple 4 were di~olved ln 147 g of toluene and then preclpltated by ~low dropwl~e addition to acetone. The preclpltated material wa~ then drled ln a drylng oven at 80-C for one day. The polymer blend obtalned ln thl~ way had a glass transition temperature of 138-C measured by DSC wlth a heating rate of 20'C/minute.
Example 7 48 g of a polymer accordlng to Example 3 snd 12 g of a polymer according to ~xample 5 were mixed and kneaded ln a Rheomix 600 measuring kneader supplied by Haake at a speed of 60 revolutlons per mlnute at 225~C for 15 mlnutes. The blend obtained ln this way was tran~parent and had a glaes transition temperature of 141-C mea~ured by DSC with a heating rate of 20-C/minute.
- 22 - 20~69 Example 8 Circular compressed disks with a diameter of 25 mm were produced from the materials according to Examples 3, 6 and 7 by compression at 225C for 15 minutes. All the compres~ed disk~ were colorless and transparent. To evaluate and compare the proce~sability of the6e material~, the compressed disks obtained in this way were used to determine the viscosity ETA. The apparatus used for this was a Rheometric~ dynamic spectrometer RDS 2.
The mea~urements were carried out with disk-disk geometry at 270C and at two frequencies. The re~ults of the measurement~ are compiled in Table 3.
Table 3~
, ., Sample identificntion Vi~cosity ETA (Pa.~) ~ccording to Example No. Frequency 1 Frequency 2 1 rad/~ 10 rad/~
3 6.41 x 103 2.63 x 103 6 2.47 x 103 1.09 X 103 _ 1 2.67 x 103 1.15 x 103 l
Claims (6)
1. A process for the preparation of a cycloolefin polymer or copolymer with a narrow molecular weight distribution (Mw/Mn) by polymerization of 0.1 to 100% by weight, based on the total amount of the monomers, 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 identi-cal or different and are a hydrogen atom or a C1-C8-alkyl radical, it being possible for identical radicals in the different formulae to have a dif-ferent meaning, 0 to 99.9% by weight, based on the total amount of the monomers, of a cycloolefin of the formula VII
(VII), in which n is a number from 2 to 10, and 0 to 99.9% by weight, based on the total amount of the monomers, of at least one acyclic 1-olefin of the formula VIII
(VIII), in which R9, R10, R11 and R12 are identical or dif-ferent and are a hydrogen atom or a C1-C8-alkyl radical, at temperatures from -78 to l50°C and under a pressure of from 0.01 to 64 bar, in the presence of a catalyst which is composed of an aluminoxane of the formula IX
(IX) for the linear type and/or of the formula X
(X) for the cyclic type, where the radicals R13 in the formulae IX and X are identical or different and are a C1-C6-alkyl group or phenyl or benzyl, and n is an integer from 0 to 50, and of 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-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R16 and R17 are a mono- or polynuclear hydrocarbon radical which with the centralatom M1 can form a sandwich structure, R18 is , , , , , , =BR19, =AlR19, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR19, =CO, =PR19 or =P(O)R19, where R19, R20 and R21 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoralkyl group, a C6-C10-fluoraryl group, a C1-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R19 and R20 or R19 and R21 each form a ring with the atoms joining them, and M2 is silicon, germanium or tin, which com-prises stopping the polymerization at a time when Mw/Mn < 2.
(I), (II), (III), (IV), (V), (VI), in which R1, R2, R3, R4, R5, R6, R7 and R8 are identi-cal or different and are a hydrogen atom or a C1-C8-alkyl radical, it being possible for identical radicals in the different formulae to have a dif-ferent meaning, 0 to 99.9% by weight, based on the total amount of the monomers, of a cycloolefin of the formula VII
(VII), in which n is a number from 2 to 10, and 0 to 99.9% by weight, based on the total amount of the monomers, of at least one acyclic 1-olefin of the formula VIII
(VIII), in which R9, R10, R11 and R12 are identical or dif-ferent and are a hydrogen atom or a C1-C8-alkyl radical, at temperatures from -78 to l50°C and under a pressure of from 0.01 to 64 bar, in the presence of a catalyst which is composed of an aluminoxane of the formula IX
(IX) for the linear type and/or of the formula X
(X) for the cyclic type, where the radicals R13 in the formulae IX and X are identical or different and are a C1-C6-alkyl group or phenyl or benzyl, and n is an integer from 0 to 50, and of 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-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R16 and R17 are a mono- or polynuclear hydrocarbon radical which with the centralatom M1 can form a sandwich structure, R18 is , , , , , , =BR19, =AlR19, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR19, =CO, =PR19 or =P(O)R19, where R19, R20 and R21 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoralkyl group, a C6-C10-fluoraryl group, a C1-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R19 and R20 or R19 and R21 each form a ring with the atoms joining them, and M2 is silicon, germanium or tin, which com-prises stopping the polymerization at a time when Mw/Mn < 2.
2. The process as claimed in claim 1, wherein the polymerization is stopped at a time when Mw/Mn is ? 1.7.
3. The process as claimed in claim 1 or 2, wherein the polymerization is stopped at a time when Mw/Mn is ? 1.4.
4. A cycloolefin polymer or copolymer which can be prepared by the process as claimed in one or more of claims 1 to 3.
5. A shaped article which can be produced from a cyclo-olefin polymer or copolymer as claimed in claim 4.
6. A polymer blend containing a cycloolefin polymer or copolymer as claimed in claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4106107.1 | 1991-02-27 | ||
| DE4106107 | 1991-02-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2061869A1 true CA2061869A1 (en) | 1992-08-28 |
Family
ID=6425982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002061869A Abandoned CA2061869A1 (en) | 1991-02-27 | 1992-02-26 | Cycloolefin (co)polymers with a narrow molecular weight distribution and a process for the preparation thereof |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5422409A (en) |
| EP (1) | EP0501370B1 (en) |
| JP (1) | JPH059223A (en) |
| KR (1) | KR920016477A (en) |
| AT (1) | ATE173746T1 (en) |
| AU (1) | AU649520B2 (en) |
| CA (1) | CA2061869A1 (en) |
| DE (1) | DE59209568D1 (en) |
| ES (1) | ES2127199T3 (en) |
| ZA (1) | ZA921404B (en) |
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-
1992
- 1992-02-24 EP EP92103051A patent/EP0501370B1/en not_active Expired - Lifetime
- 1992-02-24 DE DE59209568T patent/DE59209568D1/en not_active Expired - Fee Related
- 1992-02-24 ES ES92103051T patent/ES2127199T3/en not_active Expired - Lifetime
- 1992-02-24 AT AT92103051T patent/ATE173746T1/en not_active IP Right Cessation
- 1992-02-25 KR KR1019920002890A patent/KR920016477A/en not_active Application Discontinuation
- 1992-02-26 ZA ZA921404A patent/ZA921404B/en unknown
- 1992-02-26 CA CA002061869A patent/CA2061869A1/en not_active Abandoned
- 1992-02-26 AU AU11216/92A patent/AU649520B2/en not_active Ceased
- 1992-02-27 JP JP4040980A patent/JPH059223A/en active Pending
-
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- 1993-11-22 US US08/156,929 patent/US5422409A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ES2127199T3 (en) | 1999-04-16 |
| KR920016477A (en) | 1992-09-24 |
| ZA921404B (en) | 1992-11-25 |
| US5422409A (en) | 1995-06-06 |
| AU649520B2 (en) | 1994-05-26 |
| EP0501370B1 (en) | 1998-11-25 |
| ATE173746T1 (en) | 1998-12-15 |
| EP0501370A1 (en) | 1992-09-02 |
| DE59209568D1 (en) | 1999-01-07 |
| AU1121692A (en) | 1992-09-03 |
| JPH059223A (en) | 1993-01-19 |
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