WO1998046614A1 - Catalyseur et son utilisation pour la polymerisation - Google Patents

Catalyseur et son utilisation pour la polymerisation Download PDF

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Publication number
WO1998046614A1
WO1998046614A1 PCT/EP1998/002003 EP9802003W WO9846614A1 WO 1998046614 A1 WO1998046614 A1 WO 1998046614A1 EP 9802003 W EP9802003 W EP 9802003W WO 9846614 A1 WO9846614 A1 WO 9846614A1
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WO
WIPO (PCT)
Prior art keywords
compound
general formula
mmol
endo
group
Prior art date
Application number
PCT/EP1998/002003
Other languages
German (de)
English (en)
Inventor
Alexandra Jacobs
Walter Heitz
Beate Heinz
Original Assignee
Ticona Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE19716312A external-priority patent/DE19716312A1/de
Application filed by Ticona Gmbh filed Critical Ticona Gmbh
Priority to CA002286695A priority Critical patent/CA2286695A1/fr
Priority to EP98921435A priority patent/EP0973786A1/fr
Priority to JP54343798A priority patent/JP2001519821A/ja
Priority to AU74294/98A priority patent/AU7429498A/en
Publication of WO1998046614A1 publication Critical patent/WO1998046614A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring

Definitions

  • the present invention relates to a new catalyst and the use of the catalyst for the polymerization of functionalized and non-functionalized cycloolefins.
  • the vinyl polymerization of norbornene gives a polymer which is distinguished by a high glass transition temperature, a high density and a high refractive index, cf. Macromol. Chem. Phys 1886, 197, 3435-3453.
  • a polynorbornene substituted at the 2-position with an ester group such as the vinyl-polymerized 5-norbomene-2-carboxylic acid methyl ester, exhibits better solubility properties than the unsubstituted polynorbornene
  • n is a number> 1.
  • polynorbornene it is readily soluble in tetrahydrofuran, methyl acetate, acetone and other solvents.
  • the polymer of the methyl ester is amorphous, has a glass transition temperature that is above 250 ° C and has a higher density than polynorbornene.
  • Polymer-analogous implementations such as saponification and the production of blends are possible.
  • the ester can easily be prepared using the Diels-Alder reaction.
  • the polymerization is only possible with the palladium (II) nitrile catalysts used for the polymerization of norbornene possible very slowly.
  • the polymerization of various norbornene derivatives with Pd (II) chloro complexes has been described in US Pat. No. 3,330,815.
  • the object of the invention is to provide a new catalyst for the polymerization which has a higher reactivity and produces polymers with a higher molecular weight, and a process for the preparation of homopolymers and / or copolymers.
  • R 1 represents a mono- or polycyclic hydrocarbon
  • M 1 + is a transition metal from group VIIIb
  • X means at least one non- or weakly coordinating anion.
  • a preferred embodiment of the invention lies in the compound having the general formula (I),
  • R 1 is a mono- or polycyclic hydrocarbon with at least one unsaturated bond inside or outside the ring, M 1 + Rh, Ru, Pd, Co or Ni, X " BF 4 -, PF 6 -, SbF 6 -, AsF 6 -, CIO 4 -, BPh 4 -, whereby the phenyl groups by Fluorine or trifluoromethyl can be substituted, closo-boranes and carboranes and their halogenated derivatives or triflates means.
  • a particularly preferred embodiment of the invention lies in the compound having the general formula (I), where
  • R 1 is substituted or unsubstituted norbornene, cyclooctene, tricyclodecene or exo-methylenecyclohexene, M 1+ is Pd, X "is BF 4 -, PF 6 -, SbF 6 -, AsF 6 - or carboranes.
  • a very particularly preferred embodiment of the invention lies in the compound having the general formula (I), where R 1 is a compound having the general formula (II)
  • R 2 is a hydrogen atom, a C 1 -C 20 alkyl group, C 6 -C 20 aryl group, OR 3 -,
  • R 3 represents a hydrogen atom, a C 1 -C 20 alkyl group or C 6 -C 20 aryl group, a -CN , -SCN, -NR 3 2 , N 3 group or a halogen atom.
  • the compound having the general formula (I) is dissolved in at least one halogenated hydrocarbon, aliphatic or aromatic hydrocarbon, which may optionally contain a heteroatom such as halogen, oxygen or nitrogen.
  • the compound having the general formula (I) is preferably dissolved in methylene chloride, chloroform, nitromethane, dimethylformamide, N-methylpyrolidone, dimethylethylene urea, nitrobenzene, or chlorobenzene.
  • a compound having the general formula (I) and a cycloolefin which has at least one radical R 4 , the ratio of the compound having the general formula (I) to the cycloolefin being from 1: 1 to 1:10 and R 4 represents a COOR 3 , or -NC, COR 3 - group.
  • M 2+ is an alkali, alkaline earth metal, Ag, Tl or Cu.
  • a process for the preparation of the compound having the general formula (I) and a cycloolefin is provided, an amount from 1: 1 to 1:10, based on the compound having the general formula (I), and M 1+ R 1 Hal " with M 2+ X " is reacted in at least one solvent.
  • a process for the preparation of homopolymers and / or copolymers with at least one compound of the general formula (I) is provided as the catalyst system.
  • a method for producing a homo- and / or copolymer is provided by polymerization of 0.1 to 100% by weight, based on the total amount of monomers, of at least one polycyclic olefin of the formula III, IV, IV, V, VI , VII or VIII
  • the polycyclic olefins are preferably at least monosubstituted carboxylic acid and / or dicarboxylic acid derivatives and 0 to 99.9% by weight, based on the total amount of monomers, of at least one monocyclic olefin of the formula IX
  • R 13 , R 14 , R 15 and R 16 are the same or different and represent a hydrogen atom or a hydrocarbon radical, preferably a C 6 -C 10 aryl radical or a C -C ⁇ alkyl radical.
  • homo- and / or copolymers of norbomene carboxylic acid derivatives and norbomene dicarboxylic acid derivatives are obtained.
  • Homo- and / or copolymers of norbornene which is at least monosubstituted by carboxyl, ester, amide and nitrile groups or of norbornene carboxylic acid anhydride and imide are obtained.
  • Preferred examples of norbomene carboxylic acid and norbornene dicarboxylic acid derivatives are: bicyclo [2.2.1] hept-5-en-2-carboxylic acid methyl ester,
  • the derivatives can also be substituted in the 7-position.
  • the use of a compound with the general formula (i) is provided as a catalyst system for the production of homopolymers and / or copolymers.
  • the analysis would be carried out using the methods listed below.
  • the NMR spectra were recorded on a Bruker AC 300 spectrometer with a frequency of 300 MHz at 1 H-NMR and 75 MHz at 13 C-NMR.
  • the IR spectra were recorded on an FT-IR spectrometer 1600 from Perkin Elmer. Solids were measured as KBr compacts, liquids between two sodium chloride plates.
  • the GPC analyzes by means of gel permeation chromatography were carried out with a solution of 0.2 g polymer in 10 ml tetrahydrofuran on two 10 mm polymer mixed gel columns (600 * 8 mm) from PSS.
  • a differential refractometer and differential viscometer from Knauer served as the detector.
  • a Knauer pump was used. The inherent viscosities were determined at a temperature of 25 ° C for polymer solutions with 0.5 percent by weight in dichloromethane.
  • the GC analyzes were carried out on a Hewlett Packard 5890 gas chromatograph. The injector and detector were at a temperature of 300 ° C. The temperature program used was: Isotherm from 70 ° C for 4 minutes, then heat to 280 ° C at a rate of 15 ° C / min.
  • the capillary column HP-5 cross-linked with 5% Ph Me silicone) from Hewlett Packard with a film thickness of 25 mm, a length of 30 m and an inner diameter of 0.32 mm was used.
  • VZ viscosity number in cm 3 / g
  • the polymer was precipitated from methanol, filtered off, washed with methanol and dried at 100 ° C. for 8 hours. 1.82 g (71% of theory) of a white solid were obtained.
  • the filtrate was added to 0.80 ml (0.88 g, 5.8 mmol) of 5-norbornene-2-carboxylic acid methyl ester.
  • the polymerization solution was stirred for 5 days at room temperature.
  • the polymer was precipitated in methanol, filtered off, washed and dried at 100 ° C. for 8 hours. 0.84 g (96% of theory) of a white solid were obtained.
  • the polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 1.21 g (24% of the Theory) of a white solid.
  • the polymerization solution was stirred for half an hour at room temperature.
  • the polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 0.70 g (54% of theory) of a white solid were obtained.
  • the polymerization solution was stirred at a temperature of 40X for three hours.
  • the polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 194.8 mg (8.9% of theory) of a white solid were obtained.
  • the yellow polymerization solution was stirred at a temperature of 60% for half an hour.
  • the polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 251.6 mg (11.4% of theory) of a white solid were obtained.
  • the yellow polymerization solution was stirred for 5 days at room temperature. The solution turned green after 10 minutes. The polymer was precipitated in methanol filtered off, washed and dried at 100 ⁇ for 8 hours. 0.43 g (18.8% of theory) of a white solid were obtained.
  • the polymer was precipitated from methanol, filtered off and washed with methanol. The product was dried at 100X for 8 hours. 1.49 g (47% of theory) of the polymer were obtained.
  • the yellow catalyst solution was filtered through a Millipor filter and the filtrate was added to 3.34 g (22.0 mmol) of 5-norbornene-2-carboxylic acid ethyl ester in 3.6 ml of dichloromethane.
  • the yellow polymerization mixture was stirred at room temperature for 20 hours.
  • the Polymer was precipitated from methanol, filtered off, washed with methanol.
  • the product was dried at 100X for 8 hours. 0.47 g (14% of theory) of the polymer were obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un catalyseur et son utilisation pour la polymérisation. Ce catalyseur contient un composé de formule générale (I), dans laquelle R<1> représente un hydrocarbure monocyclique ou polycyclique, M<1+> représente un métal de transition du groupe VIIIb, X<-> représente au moins un anion sans activité de coordination ou présentant une faible activité de coordination.
PCT/EP1998/002003 1997-04-11 1998-04-07 Catalyseur et son utilisation pour la polymerisation WO1998046614A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002286695A CA2286695A1 (fr) 1997-04-11 1998-04-07 Catalyseur et son utilisation pour la polymerisation
EP98921435A EP0973786A1 (fr) 1997-04-11 1998-04-07 Catalyseur et son utilisation pour la polymerisation
JP54343798A JP2001519821A (ja) 1997-04-11 1998-04-07 触媒および重合のためのその触媒の使用
AU74294/98A AU7429498A (en) 1997-04-11 1998-04-07 Catalyst and use of catalysts in polymerisation

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19715104.3 1997-04-11
DE19715104 1997-04-11
DE19716312.2 1997-04-18
DE19716312A DE19716312A1 (de) 1997-04-11 1997-04-18 Katalysator und Verwendung des Katalysators für die Polymerisation

Publications (1)

Publication Number Publication Date
WO1998046614A1 true WO1998046614A1 (fr) 1998-10-22

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Application Number Title Priority Date Filing Date
PCT/EP1998/002003 WO1998046614A1 (fr) 1997-04-11 1998-04-07 Catalyseur et son utilisation pour la polymerisation

Country Status (5)

Country Link
EP (1) EP0973786A1 (fr)
JP (1) JP2001519821A (fr)
AU (1) AU7429498A (fr)
CA (1) CA2286695A1 (fr)
WO (1) WO1998046614A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2177598A1 (fr) * 2008-10-14 2010-04-21 INTERNATIONAL FLAVORS &amp; FRAGRANCES INC. Isomères de l'acide bicyclo[2.2.1]hept-5-ène-2-carboxylique, ester éthylique et leur utilisation dans des compositions de parfums

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7989571B2 (en) 2002-07-10 2011-08-02 Lg Chem, Ltd. Method for producing norbornene monomer composition, norbornene polymer prepared therefrom, optical film comprising the norbornene polymer, and method for producing the norbornene polymer
DE60311103T2 (de) * 2002-07-10 2007-10-25 Lg Chem, Ltd. Auf norbornenester basierendes polymerisat und verfahren zu seiner herstellung
US7312285B2 (en) 2002-07-10 2007-12-25 Lg Chem, Ltd. Method for preparing norbornene based addition polymer containing ester or acetyl functional group
KR100561068B1 (ko) 2002-07-10 2006-03-15 주식회사 엘지화학 노보넨-에스테르계 부가중합체 및 이의 제조방법
KR101046430B1 (ko) * 2008-09-11 2011-07-05 삼성전기주식회사 저유전율 및 저손실 특성을 가진 노르보넨계 중합체, 이를이용한 절연재, 인쇄회로기판 및 기능성 소자

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4447066A1 (de) * 1994-12-29 1996-07-04 Hoechst Ag Heterocyclische Carbene enthaltende Metallkomplexverbindungen
US5569730A (en) * 1993-11-16 1996-10-29 The B. F. Goodrich Company Addition polymers derived from norbornene-functional monomers and process therefor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5569730A (en) * 1993-11-16 1996-10-29 The B. F. Goodrich Company Addition polymers derived from norbornene-functional monomers and process therefor
DE4447066A1 (de) * 1994-12-29 1996-07-04 Hoechst Ag Heterocyclische Carbene enthaltende Metallkomplexverbindungen

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ACTA POLYM. (1997), 48(9), 385-391 CODEN: ACPODY;ISSN: 0323-7648, 1997 *
CHEMICAL ABSTRACTS, vol. 127, no. 22, 1 December 1997, Columbus, Ohio, US; abstract no. 307733, HEINZ, B. S. ET AL: "Poly(norbornene carboxylic acid ester). Synthesis and properties" XP002075149 *
CHEMICAL ABSTRACTS, vol. 129, Columbus, Ohio, US; abstract no. 68084, HEINZ, BEATE S. ET AL: "Pd(II)-catalyzed vinylic polymerization of norbornene and copolymerization with norbornene carboxylic acid esters" XP002075150 *
MACROMOL. RAPID COMMUN. (1998), 19(5), 251-256 CODEN: MRCOE3;ISSN: 1022-1336, 1998 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2177598A1 (fr) * 2008-10-14 2010-04-21 INTERNATIONAL FLAVORS &amp; FRAGRANCES INC. Isomères de l'acide bicyclo[2.2.1]hept-5-ène-2-carboxylique, ester éthylique et leur utilisation dans des compositions de parfums

Also Published As

Publication number Publication date
JP2001519821A (ja) 2001-10-23
AU7429498A (en) 1998-11-11
CA2286695A1 (fr) 1998-10-22
EP0973786A1 (fr) 2000-01-26

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