DE10219991A1 - Polycycloolefin/graft copolymer with partially hydrogenated polydiene as graft base has high molecular weight, narrow molecular weight distribution, good solubility, and good mechanical properties - Google Patents
Polycycloolefin/graft copolymer with partially hydrogenated polydiene as graft base has high molecular weight, narrow molecular weight distribution, good solubility, and good mechanical propertiesInfo
- Publication number
- DE10219991A1 DE10219991A1 DE2002119991 DE10219991A DE10219991A1 DE 10219991 A1 DE10219991 A1 DE 10219991A1 DE 2002119991 DE2002119991 DE 2002119991 DE 10219991 A DE10219991 A DE 10219991A DE 10219991 A1 DE10219991 A1 DE 10219991A1
- Authority
- DE
- Germany
- Prior art keywords
- partially hydrogenated
- polycycloolefin
- range
- molecular weight
- graft
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 24
- 229920003050 poly-cycloolefin Polymers 0.000 title claims abstract description 17
- 238000009826 distribution Methods 0.000 title description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 11
- 150000001925 cycloalkenes Chemical class 0.000 claims description 10
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical group C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 150000002848 norbornenes Chemical class 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- -1 triodide Chemical compound 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002846 norbornadienes Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- WMWDGZLDLRCDRG-UHFFFAOYSA-N 5-hexylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCC)CC1C=C2 WMWDGZLDLRCDRG-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- ZAPKJNQWQKICPZ-UHFFFAOYSA-N ethyl hexanoate nickel(2+) Chemical compound [Ni+2].CCCCCC(=O)OCC ZAPKJNQWQKICPZ-UHFFFAOYSA-N 0.000 description 1
- PERLSLNQWLZSLS-UHFFFAOYSA-N ethyl hexanoate;nickel Chemical compound [Ni].CCCCCC(=O)OCC PERLSLNQWLZSLS-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000005310 oxohalides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- BZBAYMUKLAYQEO-UHFFFAOYSA-N phenylborane Chemical compound BC1=CC=CC=C1 BZBAYMUKLAYQEO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Die Erfindung betrifft Polycycloolefin-Pfropfcopolymere und Verfahren zur Herstellung von Polycycloolefin-Pfropfcopolymeren The invention relates to polycycloolefin graft copolymers and Process for the preparation of polycycloolefin graft copolymers
Die Polymerisation von Norbornen führt je nach Katalysator und Reaktionsmechanismus zu unterschiedlichen Polymeren. Eine Vielzahl von Übergangsmetallverbindungen katalysiert die ringöffnende Methathesepolymerisation (ROMP). Das so hergestellt Polynorbornen enthält ungesättigte C=C-Doppelbindungen in der Polymerkette und besitzt eine niedere Glasübergangstemperatur. Es wird als typisches Elastomer verwendet. The polymerization of norbornene leads depending on the catalyst and Reaction mechanism to different polymers. A The ring-opening catalyzes a large number of transition metal compounds Methathesis polymerization (ROMP). The polynorbornene manufactured in this way contains unsaturated C = C double bonds in the polymer chain and has a low glass transition temperature. It is called typical elastomer used.
Die durch Dichlorethylaluminium initiierte kationische Polymerisation von Norbornen führt zu 2,7-verknüpften Polynorbornen mit niederem Molekulargewicht. The cationic initiated by dichloroethyl aluminum Polymerization of norbornene leads to 2,7-linked polynorbornene low molecular weight.
Im Gegensatz zur ringöffnenden Methathesepolymerisation (ROMP) werden bei der vinylischen Polymerisation Polymere ohne ungesättigte C=C-Doppelbindungen und mit besseren thermischen Eigenschaften erhalten. Als Katalysatoren sind Komplexe des Nickels (EP-A 0445755, US 5,468,819), des Kobalts, Chrom, Zirkonium oder Palladium bekannt. Im allgemeinen werden diese Metallkomplexe durch Methylaluminoxan (MAO) aktiviert. Je nach verwendetem Katalysator können semikristalline und unlöslich Polymere erhalten werden. In contrast to ring-opening methathesis polymerization (ROMP) are polymers without vinyl polymerization unsaturated C = C double bonds and with better thermal Get properties. Complexes of nickel are used as catalysts (EP-A 0445755, US 5,468,819), cobalt, chromium, zirconium or Palladium known. In general, these metal complexes activated by methylaluminoxane (MAO). Depending on the used Catalysts can obtain semi-crystalline and insoluble polymers become.
In Chlorbenzol bei Raumtemperatur lösliches vinylisches Polynorbornen wird in Makromol. Rapid Commun. 20, Seiten 232-235 (1999) beschrieben. Als Katalysator wird ein Nickelphosphoraniminatokomplex/MAO verwendet. Aufgrund der hohen Lewisacidität des MAO sind nachfolgende Umsetzungen mit Verbindungen, die polare Gruppen enthalten, nicht möglich. Vinylic soluble in chlorobenzene at room temperature Polynorbornene is made in Makromol. Rapid Commun. 20, pages 232-235 (1999). As a catalyst Nickel phosphoraniminato complex / MAO used. Due to the high Lewis acidity of the MAO are subsequent reactions with compounds that are polar Groups included, not possible.
Die WO 96/37529 beschreibt ein Verfahren zur Herstellung von Copolymeren aus Norbornen und kationisch polymerisierbaren Monomeren wie Ethylvinylether, Butadien, Isobuten oder Vinylanisol. Die Polymerisation erfolgt in Gegenwart eines Multikomponenten Katalysatorsystems, das ein Übergangsmetallion der Gruppe 8 enthält. Unter anderem wird ein Katalysatorsystem aus Nickelethylhexanoat, Trispentafluorphenylboran und Triethylaluminium verwendet. WO 96/37529 describes a process for the production of Copolymers of norbornene and cationically polymerizable Monomers such as ethyl vinyl ether, butadiene, isobutene or vinyl anisole. The Polymerization takes place in the presence of a multicomponent Catalyst system containing a Group 8 transition metal ion. Among other things, a catalyst system made of nickel ethyl hexanoate, Trispentafluorophenylborane and Triethylaluminium used.
Die Polymerisation von Norbornen mit Nickel(II)- und Palladium(II)-Komplexen werden von Lassalen et al. in Macrom. Rapid Communications 23 (2002), Seiten 16-20 beschrieben. The polymerization of norbornene with nickel (II) - and Palladium (II) complexes are described by Lassalen et al. in Macrom. Rapid Communications 23 (2002), pages 16-20.
Die Herstellung von Polynorbornen und Polynorbornenblockcopolymeren in Gegenwart von Nickel-phosphoraniminato-Komplexen ist in DE 101 02 647 und Polymeric Materials: Science and Engineering 2001, 84, 761 beschrieben. Weiterhin sind Blends, Polymernorbornen-Block- und Pfropfcopolymere aus US 6,294,616 bekannt. Die dort beschriebenen Pfropfcopolymere weisen jedoch niedrige Molekulargewichte oder sehr breite Molekulargewichtsverteilungen auf. Pfropfcopolymere auf Basis von Polybutadien oder Polyisopren mit höheren Molekulargewichten sind in der Regel sehr spröde. The production of polynorbornene and Polynorbornene block copolymers in the presence of nickel-phosphoraniminato complexes is in DE 101 02 647 and Polymeric Materials: Science and Engineering 2001, 84, 761. Furthermore, blends, Polymer norbornene block and graft copolymers are known from US Pat. No. 6,294,616. The However, graft copolymers described there have low Molecular weights or very broad molecular weight distributions. Graft copolymers based on polybutadiene or polyisoprene higher molecular weights are usually very brittle.
Die Aufgabe der vorliegenden Erfindung war es, den genannten Nachteilen abzuhelfen und Polycycloolefinen-Pfropfcopolymere mit hohem Molekulargewicht und enger Molekulargewichtsverteilung bereitzustellen. Desweiteren sollten Propfcopolymere mit verbesserten mechanischen Eigenschaften, sowie Verfahren zu deren Herstellung gefunden werden. The object of the present invention was the above To remedy disadvantages and with polycycloolefin graft copolymers high molecular weight and narrow molecular weight distribution provide. Furthermore, graft copolymers should improved mechanical properties, and methods for their Manufacturing can be found.
Demgemäß werden Polycycloolefin-Pfropfcopolymere gefunden, die als Pfropfgrundlage teilhydrierte Polydiene enthalten. Accordingly, polycycloolefin graft copolymers are found which contain partially hydrogenated polydienes as graft base.
Die erfindungsgemäßen Polycycloolefin-Propfcopolymere weisen bevorzugt ein gewichtsmittleres Molekulargewicht Mw im Bereich von 50.000 bis 2.000.000 und eine Uneinheitlichkeit Mw/Mn von 2,0 oder darunter auf. Besonders bevorzugte Polycycloolefin-Pfropfcopolymere haben einen Anteil an Polycycloolefinblöcken im Bereich von 15-95 Mol-%, insbesondere 25 bis 75 Mol-%, bezogen auf das gesamte Pfropfcopolymer. The polycycloolefin graft copolymers according to the invention preferably have a weight-average molecular weight M w in the range from 50,000 to 2,000,000 and a non-uniformity M w / M n of 2.0 or less. Particularly preferred polycycloolefin graft copolymers have a proportion of polycycloolefin blocks in the range from 15-95 mol%, in particular 25 to 75 mol%, based on the total graft copolymer.
Die erfindungsgemäßen Polycycloolefin-Propfcopolymeren, können durch Polymerisation von Cycloolefinmonomere in Gegenwart von teilhydrierten Polydienen erhalten werden. Dabei werden Polycycloolefinblöcke auf die ungesättigten C=C-Doppelbindungen des teilhydrierten Polydiens gepfropft. Über den Hydriergrad des Polydiens können die Pfropfdichte und somit die mechanischen Eigenschaften des Pfropfcopolymers beeinflußt werden. The polycycloolefin graft copolymers according to the invention can by polymerization of cycloolefin monomers in the presence of partially hydrogenated polydienes can be obtained. In doing so Polycycloolefin blocks on the unsaturated C = C double bonds of grafted partially hydrogenated polydiene. About the degree of hydrogenation of the Polydien can change the density of the graft and thus the mechanical Properties of the graft copolymer can be influenced.
Die teilhydrierten Polydiene weisen bevorzugt einen Hydriergrad im Bereich von 5 bis 95 mol%, insbesondere im Bereich von 45 bis 85 mol%, bezogen auf die ungesättigten Doppelbindungen, auf. The partially hydrogenated polydienes preferably have a degree of hydrogenation in the range from 5 to 95 mol%, in particular in the range from 45 to 85 mol%, based on the unsaturated double bonds.
Teilhydriertes Polybutadien oder teilhydriertes Polyisopren werden bevorzugt als teilhydriertes Polydien eingesetzt. Das teilhydrierte Polydien wird in der Regel in Mengen einsetzt, so dass das molares Verhältnis der ungesättigten C=C-Doppelbindungen im Dien, bezogen auf die Cycloolefinmonomere, im Bereich von 0,5 bis 25 liegt. Partially hydrogenated polybutadiene or partially hydrogenated polyisoprene are preferably used as partially hydrogenated polydiene. The Partially hydrogenated polydiene is usually used in quantities such that the molar ratio of the unsaturated C = C double bonds in the Diene, based on the cycloolefin monomers, in the range from 0.5 to 25 lies.
Die Cycloolefinmonomere werden in der Regel in Gegenwart von Katalysatoren auf Basis von Nickel, wie Nickel-(II)ethylhexanoat und einem Boran, Borat oder Aluminiumtrialkyl als Cokatalysator hergestellt. The cycloolefin monomers are usually in the presence of Nickel-based catalysts, such as nickel (II) ethyl hexanoate and a borane, borate or aluminum trialkyl as a cocatalyst manufactured.
Ein bevorzugter Katalysator enthält einen Nickelphosphoraniminatokomplex der Formel [NiX(NPR3)]4. X steht für ein kovalent gebundenen oder schwach koordinierenden Liganden. Beispiele hierfür sind die Halogenide wie Fluorid, Chlorid, Bromid, Jodid, Triodid, Rhodanid, Cyanid, Bortetrafluoridanion, Oxohalogenide wie Perchlorat, Carboxylate, Formiate, Acetate, Trifluoracetate, Benzoate, Triflate, sowie Alkyloxy- bzw. Aryloxy-, Thio-, Selenato- oder Teluratoliganden mit einem C1- bis C20-Alkyl oder C6- bis C20-Aryl, wie Phenyl, Diphenyl oder Naphthyl. A preferred catalyst contains a nickel phosphoraniminato complex of the formula [NiX (NPR 3 )] 4 . X stands for a covalently bound or weakly coordinating ligand. Examples of these are the halides such as fluoride, chloride, bromide, iodide, triodide, rhodanide, cyanide, boron tetrafluoride anion, oxohalides such as perchlorate, carboxylates, formates, acetates, trifluoroacetates, benzoates, triflates, and also alkyloxy or aryloxy, thio, selenato - or Telurato ligands with a C 1 - to C 20 -alkyl or C 6 - to C 20 -aryl, such as phenyl, diphenyl or naphthyl.
Die an Phosphor gebundenen Reste R können unabhängig voneinander C1- bis C20-Alkyl, C6- bis C20-Aralkyl oder C1- bis C20 -Alkylphosphacyclopentanyl sein. The radicals R bonded to phosphorus can be, independently of one another, C 1 to C 20 alkyl, C 6 to C 20 aralkyl or C 1 to C 20 alkylphosphacyclopentanyl.
Der Katalysator enthält ferner ein Boran oder Borat. Bevorzugt werden Trisperfluorarylborane wie Tris(pentafluorphenyl)boran verwendet. Geeignet sind auch Alkyl- oder Arylborate wie Triphenylmethyliumtetra(phenyl)boran. The catalyst also contains a borane or borate. Prefers become trisperfluoroarylboranes such as tris (pentafluorophenyl) borane used. Alkyl or aryl borates such as are also suitable Triphenylmethyliumtetra (phenyl) borane.
Desweiteren kann der Katalysator in zumeist untergeordneten Mengen ein Aluminiumalkyl, beispielsweise Trimethylaluminium oder Triethylaluminium enthalten. Furthermore, the catalyst can mostly be subordinate Amounts an aluminum alkyl, such as trimethyl aluminum or Triethyl aluminum included.
Bevorzugt liegt das molare Verhältnis Bor/Nickel im Bereich von 1 bis 10, besonders bevorzugt im Bereich von 2 bis 5. Das molare Verhältnis von Aluminium zu Nickel liegt im allgemeinen im Bereich von 0 bis 1, bevorzugt im Bereich von 0,02 bis 0,2. The molar boron / nickel ratio is preferably in the range of 1 to 10, particularly preferably in the range from 2 to 5. The molar The ratio of aluminum to nickel is in general Range from 0 to 1, preferably in the range from 0.02 to 0.2.
Das erfindungsgemäße Verfahren zur Polymerisation von Cycloolefinen kann in Gegenwart des oben beschriebenen Katalysators durchgeführt werden. Das Verfahren kann prinzipiell lösungsmittelfrei durchgeführt werden. Bevorzugt wird die Polymerisation in einem aromatischen Kohlenwasserstoff, beispielsweise Toluol oder Chlorbenzol, als Lösungsmittel durchgeführt. The inventive method for the polymerization of Cycloolefins can be in the presence of the catalyst described above be performed. In principle, the process can be solvent-free be performed. Polymerization in one is preferred aromatic hydrocarbon, for example toluene or Chlorobenzene, carried out as a solvent.
Besonders eignet sich das Verfahren zur Polymerisation von Norbornen oder Norbornenderivaten, zum Beispiel 5-Methyl-2-Norbornen, 5-Hexyl-2-norbornen, 5-Ethylidenyl-2-norbornen, Vinylnorbornen, Dicyclopentadien, Dihydrodicyclopentadien, Tetracyclododecen, Tetracyclododecadien, Dimethyltetracyclododecen, Ethyltetracyclododecen, Ethyltetracyclododecen, Ethylidenyltetracyclododecen, Phenyltetracyclodecen und halogenierte Norbornadiene sowie Norbornadiene mit vollständig halogenierten Alkylgruppen. The process is particularly suitable for the polymerization of Norbornene or norbornene derivatives, for example 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidenyl-2-norbornene, Vinyl norbornene, dicyclopentadiene, dihydrodicyclopentadiene, Tetracyclododecene, tetracyclododecadiene, dimethyltetracyclododecene, Ethyl tetracyclododecene, ethyl tetracyclododecene, Ethylidenyltetracyclododecen, Phenyltetracyclodecen and halogenated norbornadienes as well Norbornadienes with fully halogenated alkyl groups.
Der Katalysator wird in der Regel in Mengen eingesetzt, so daß das molare Verhältnis von Cycloolefin zu Nickel im Bereich von 100 bis 100.000 liegt. The catalyst is generally used in amounts so that the molar ratio of cycloolefin to nickel in the range of 100 to 100,000.
Die Polymerisation wird in der Regel bei Temperaturen im Bereich von 0 bis 100°C und Drücken im Bereich von 1 bar bis 10 bar durchgeführt. The polymerization is usually at temperatures in the range from 0 to 100 ° C and pressures in the range from 1 bar to 10 bar carried out.
Die Polymerisation kann mit einem polaren Kettenabbruchmittel oder einem vinylischen Monomer beendet werden. The polymerization can be carried out using a polar chain terminator or a vinyl monomer.
Durch die Beendigung der Polymerisation mit einem Alkohol, wie Methanol oder Ethanol, Wasser oder organischen oder anorganischen Säuren können Polycycloolefine mit einer Glasübergangstemperatur von 100°C oder höher, insbesondere von 200°C oder höher bei einem gewichtsmittleren Molekulargewicht MW im Bereich von 50.000 bis 2.000.000, insbesondere im Bereich von 500.000 bis 1.000.000 und einer Uneinheitlichkeit MW/Mn von 2,0 insbesondere 1,5 oder darunter erhalten werden. By terminating the polymerization with an alcohol such as methanol or ethanol, water or organic or inorganic acids, polycycloolefins with a glass transition temperature of 100 ° C or higher, in particular of 200 ° C or higher with a weight average molecular weight M W in the range from 50,000 to 2,000,000, in particular in the range from 500,000 to 1,000,000 and a non-uniformity M W / M n of 2.0, in particular 1.5 or below, are obtained.
Durch Zugabe eines vinylischen Monomeren, beispielsweise Styrol kann ein funktionalisiertes Polynorbornen erhalten werden. Das Molekulargewicht kann durch die Zeit, nach der Styrol zugegeben wird, kontrolliert werden. By adding a vinyl monomer, for example styrene a functionalized polynorbornene can be obtained. The Molecular weight can vary by the time after which styrene is added will be controlled.
Die erfindungsgemäßen Pfropfcopolymeren zeichnen sich durch gute mechanische Eigenschaften aus und sind selbst bei hohen Molekulargewichten der Pfropfgrundlage noch löslich. The graft copolymers according to the invention are notable for good ones mechanical properties and are even at high Molecular weights of the graft base are still soluble.
[NiBr(NPMe3)]4 wurde wie in Krieger et al., Z. anorg. allg. Chem. 1998, 624 Seite 781 beschrieben, hergestellt. [NiBr (NPMe 3 )] 4 was as described in Krieger et al., Z. anorg. allg. Chem. 1998, 624 page 781.
Der Anteil Polynorbornen (PN) im Pfropfcopolymeren wurde durch OS-Abbau des Pfropfcopolymeren bestimmt. The proportion of polynorbornene (PN) in the graft copolymer was determined by OS degradation of the graft copolymer determined.
Die mechanischen Eigenschaften der Pfropfcopolymeren wurden an Filmen (3,7 mm × 38 mm, aus Lösung bei 25°C) und einer Verstreckungsgeschwindigkeit von 50 mm/min ermittelt. The mechanical properties of the graft copolymers were: Film (3.7 mm × 38 mm, from solution at 25 ° C) and one Drawing speed of 50 mm / min determined.
Unter Inertgasatmosphäre wurden in einem 1 L Zweihalsrundkolben mit Rückflusskühler 3 g Polybutadien (M = 54.1 g/mol pro Repetiereinheit, 55 mmol C=C-Doppelbindungen M = 400 000 und 30 mg Ionol in 300 ml Toluol unter Rühren bei 25°C gelöst. Zu der viskosen Lösung wurden anschließend 3 mol p-Toluylsulfonylhydrazid M = 186,23 g/mol) pro mol zu hydrierender C=C-Doppelbindung hinzugegeben und unter Rückfluß erhitzt. Nach 6-7 h wurde das Reaktionsgemisch auf RT abgekühlt und in Methanol ausgefällt. das Polymer wurde abfiltriert, zweimal mit heißem Wasser gewaschen und aus heißem Cyclohexan erneut in Methanol ausgefällt. Das Produkt wurde 2 Tage bei 45-50°C im Vakuumtrockenschrank getrocknet. Under an inert gas atmosphere in a 1 L two-necked round bottom flask with reflux condenser 3 g polybutadiene (M = 54.1 g / mol per Repeating unit, 55 mmol C = C double bonds M = 400,000 and 30 mg Ionol dissolved in 300 ml of toluene with stirring at 25 ° C. To the viscous solution were then 3 mol p-tolylsulfonylhydrazide M = 186.23 g / mol) per mol of C = C double bond to be hydrogenated added and heated under reflux. After 6-7 h it was Cooled reaction mixture to RT and precipitated in methanol. the polymer was filtered off, washed twice with hot water and out hot cyclohexane precipitated again in methanol. The product was dried for 2 days at 45-50 ° C in a vacuum drying cabinet.
In einem 100 ml Stickstoffrundkolben wurde die in Tabelle 1
angegebene Menge des teilhydrierten Polybutadiens bei 70°C in 12 mL
Toluol gelöst. Der viskosen Lösung wurden 3 mL Norbornen (20 mmol,
1.88 g, 80 Gew.-% in Toluol) und 1 mL Katalysatorlösung
(0.5 mg/ml [NiBr(NPMe3)]4 in Toluol, 2 µmol Ni), zugesetzt. Die
Polymerisation wurde durch Zugabe von 1 mL der
Cokatalysatorlösung (5 mg/mL B (C6F5)3 in Toluol, 10 µmol B(C6F3)3) gestartet.
Nachdem 30 min bei 70°C gerührt worden war, wurde das
Reaktionsgemisch in 200 mL angesäuertes Methanol (Methano/HClconc = 200/1)
eingegossen und mehrere Stunden stehengelassen. Das Polymer wurde
abfiltriert, sorgfältig mit Methanol gewaschen und 4 Tage bei 60°C
im Membranpumpenvakuum getrocknet.
Reaktionsbedingungen: n(Ni) = 2 µmol, n(Ni) : n(Norbornen) =
1 : 10000, n(Ni) : n(B) = 1 : 5, Vges. = 25 mL Lösungsmittel: Toluol,
Reaktionszeit: 30 min, Reaktionstemperatur: 70°C.
The quantity of partially hydrogenated polybutadiene given in Table 1 was dissolved in 12 ml of toluene at 70 ° C. in a 100 ml round-bottomed flask. 3 mL norbornene (20 mmol, 1.88 g, 80% by weight in toluene) and 1 mL catalyst solution (0.5 mg / ml [NiBr (NPMe 3 )] 4 in toluene, 2 µmol Ni) were added to the viscous solution. The polymerization was started by adding 1 ml of the cocatalyst solution (5 mg / ml B (C 6 F 5 ) 3 in toluene, 10 μmol B (C 6 F 3 ) 3 ). After stirring at 70 ° C. for 30 min, the reaction mixture was poured into 200 ml of acidified methanol (methano / HCl conc = 200/1) and left to stand for several hours. The polymer was filtered off, washed thoroughly with methanol and dried for 4 days at 60 ° C. in a membrane pump vacuum.
Reaction conditions: n (Ni) = 2 µmol, n (Ni): n (norbornene) = 1: 10000, n (Ni): n (B) = 1: 5, V tot. = 25 mL solvent: toluene, reaction time: 30 min, reaction temperature: 70 ° C.
Claims (13)
X ein kovalent gebundener oder schwach koordinierender Ligand R unabhängig voneinander ein C1-C20-Alkyl,
C6-C20-Aralkyl oder ein C1-C20-Alkyl-phospha-cyclopentanyl bedeuten und
X is a covalently bound or weakly coordinating ligand R independently of one another is a C 1 -C 20 alkyl,
C 6 -C 20 aralkyl or a C 1 -C 20 alkyl-phospha-cyclopentanyl mean and
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| DE2002119991 DE10219991A1 (en) | 2002-05-03 | 2002-05-03 | Polycycloolefin/graft copolymer with partially hydrogenated polydiene as graft base has high molecular weight, narrow molecular weight distribution, good solubility, and good mechanical properties |
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| DE2002119991 DE10219991A1 (en) | 2002-05-03 | 2002-05-03 | Polycycloolefin/graft copolymer with partially hydrogenated polydiene as graft base has high molecular weight, narrow molecular weight distribution, good solubility, and good mechanical properties |
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