EP0623149A4 - Polymerization of functionalized monomers with ziegler-natta catalysts. - Google Patents

Polymerization of functionalized monomers with ziegler-natta catalysts.

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Publication number
EP0623149A4
EP0623149A4 EP94902289A EP94902289A EP0623149A4 EP 0623149 A4 EP0623149 A4 EP 0623149A4 EP 94902289 A EP94902289 A EP 94902289A EP 94902289 A EP94902289 A EP 94902289A EP 0623149 A4 EP0623149 A4 EP 0623149A4
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European Patent Office
Prior art keywords
aryl
radicals
structural formula
alkyl radical
following structural
Prior art date
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Withdrawn
Application number
EP94902289A
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English (en)
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EP0623149A1 (fr
Inventor
Robert M Waymouth
Michael R Kesti
Geoffrey W Coates
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Leland Stanford Junior University
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Leland Stanford Junior University
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Publication of EP0623149A1 publication Critical patent/EP0623149A1/fr
Publication of EP0623149A4 publication Critical patent/EP0623149A4/en
Withdrawn legal-status Critical Current

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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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • 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
    • C08F10/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the invention ⁇ relates to functionalized polyolefins and particularly to methods of polymerizing alpha-olefins containing functional groups.
  • poly(alpha-olefins) has been an area of long-standing interest as it represents a useful method for modifying the chemical and physical properties of poly(alpha- olefins) .
  • Commercially useful improvements in the adhesive, thermal, rheological, morphological, and mechanical properties of the polymer can be achieved by introducing functionality onto the polymer.
  • polyolefin polymers containing functional groups show improved affinity for dyes and printing agents and are more compatible with polar polymers.
  • Post-polymerization functionalization techniques include free-radical grafting of unsaturated groups onto the polymer (Mukherjee et al., J. Macromol . Sci . Chem. , A19 (1983) , p. 1069) , polymer oxidation (Dasgupta, S., J. Appl . Polym. Sci . , 41 (1990), p. 233), anionic treatment of the polymer (Harada et al., Jpn Kokai Tokkyo Koho JP 62054713) , and high energy radiation of the polymer (Stamm et al., J. Appl . Polym. Sci . , 7 (1963), p. 753).
  • catalyst systems employing a cationic Group 4 metallocene and "compatible non-coordinating anions.”
  • New generation Ziegler-Natta type catalysts also includes catalysts based on Group 4 metallocenes and methylaluminoxane cocatalysts. These "new generation” catalysts are superior to the conventional catalysts for the polymerization of functionalized monomers and the copolymerization of functionalized monomers with alpha-olefins.
  • One aspect of the present invention is the choice of functional monomer to be polymerized with the new generation "cationic" metallocene catalysts.
  • These monomers include olefins containing functional groups such as ethers, silyl ethers, carbazoles, tertiary phosphines, and tertiary amines.
  • the formed polymers include homopolymers of functionalized monomers as well as copolymers of functionalized monomers with ethylene and alpha-olefins.
  • the formed polymers include both stereoregular (isotactic and syndiotactic) and stereorandom polymers.
  • the functionalized monomers include nonconjugated dienes and alpha-olefins with amine, phosphine, carbazole, and silylether groups.
  • Figures 1A and IB are C NMR spectra of syndiotactic poly(5-N,N-diisopropyl-l-pentene) and isotactic poly (5-N,N-diisopropyl-1-pentene) , respectively.
  • Figure 2 is a C NMR spectrum of l-hexene/5-
  • N,N-diisopropyl-l-pentene isotactic copolymer N,N-diisopropyl-l-pentene isotactic copolymer.
  • the present invention is based, in part, on the discovery that certain homogeneous Ziegler-Natta catalysts can be used for the polymerization of func ⁇ tionalized alpha-olefins. These catalysts do not require highly Lewis acidic aluminum cocatalysts, in contrast to conventional Ziegler-Natta catalysts.
  • the inventive catalysts comprise cationic Group 4 metallo- cenes in the presence of preferably a "compatible non- coordinating anions.”
  • compatible non- coordinating anions are those as described in EPA Nos. 277 003 and 277 004 filed January 27, 1988 by Turner et al. and EPA No. 427 697-A2 filed October 9, 1990 by Ewen et al.
  • a "compat ⁇ ible non-coordinating anion” means an anion which either does not coordinate with a cation or which is only weakly coordinated to said cation and thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • the recitation "compatible non-coordinating anion” specifically refers to an anion which when func ⁇ tioning as a stabilizing anion in the catalyst system of this invention does not transfer an anionic substituent or fragment thereof to said cation thereby forming a neutral four coordinate metallocene and a neutral boron by-product.
  • Compatible anions are those which are not degraded to neutrality when the initially formed complex decomposes.
  • inventive cationic metallocene catalysts are prepared by one of several known procedures as reported in EPA Nos. 277 003 and 277 004 filed January 27, 1988 by Turner et al.; EPA No. 427 697-A2 filed October 9, 1990 by Ewen et al.; Marks et al., J. Am. Chem. Soc. , 113 (1991), p. 3623; Chien et al., J. Am. Chem. Soc , 113 (1991), p. 8570; Bochman et al., Angew. Chem. Intl, Ed. Engl . , 7 (1990), p. 780; and Teuben et al., Organometallics , 11 (1992), p. 362 and references therein, all of which are incoporated herein.
  • the inventive Group 4 metallocenes may be represented by the following formula:
  • Suitable reagents used to generate the active "cationic" metallocene is preferably (but not limited to) one of the following four types: (1) a tertiary ammonium salt R 3 NH + A " , where A is a compatible non-coordinating anion (counterion) as defined by Turner (EPA Nos. 277 003 and 277 004) ; (2) Ox + A " where Ox + is a one electron oxidant and A " is a compatible non-coordinating anion (counter- ion) as defined by Turner (EPA Nos. 277 003 and 277
  • the monomers that can be polymerized with the catalyst system include alpha-olefins containing silyl or trityl ethers, trialkyl, dialkylaryl, diarylalkyl or triaryl amines, or trialkyl, dialkylaryl, diarylalkyl or triarylphosphines and alkylcarbazoles.
  • the metallocene component has the general formula (Ln)MX.X 2 , which is the same as the Group 4 metal compounds described above.
  • the aluminoxane component is either (i) a linear aluminoxane having the general formula Al 2 OR 4 (Al(R)-0) n or (ii) a cyclic aluminoxane having the general formula (Al(R)-0) n+2 , where n is a number from 4 to 20 and R is a methyl or ethyl radical.
  • the aluminoxane component is generally mixed with a metallocene component in a 100/1 to 10,000/1 molar ratio of aluminum to the Group 4 metal in suitable solvents such as toluene or heptane. It has been demonstrated that the aluminoxane catalysts can polymerize alpha-olefins containing silyether functional groups. (See Examples 12 and 16 herein.)
  • Analytical GPC data were obtained on Waters 10 A, 500 A, and Linear ultrastyra- gel columns employing a Waters 410 refractive index diffractometer with tetrahydrofuran as the mobil phase; molecular weights were calculated versus polystyrene standards.
  • DSC differential scanning calorimetry
  • TGA thermo gravimetric analysis
  • TMSO trimethylsiloxy
  • TBDMSO tert-butyldimethylsiloxy
  • 4-TMSO-l-pentene 4-TBDMSO-l- pentene, allyloxytrimethylsilane, allyloxy(tert-butyl- dimethylsilane)
  • 1,5-hexadiene-4-ol Wiley
  • 4-pentene-l-ol Wiley
  • allylalcohol Aldrich
  • the vial was placed in a toluene bath (20°C) and equipped with a thermometer and stir bar.
  • the reaction was initiated by adding 1.0 ml of a B(C 6 F 5 ) 3 /toluene solution (10.12 mg/ml, 0.020 mmol added). The solution slowly turned yellow (over 10 minutes) , then green-yellow at 25 minutes. Small aliquots (0.1 ml - 0.5 ml) were removed from the reaction mixture at reaction times of 0 minute and 30 minutes. Each aliquot was immediately quenched in a vial containing alumina and analyzed by GC. The reaction was quenched after 60 minutes via the addition of acetone which caused a color change from green to yellow. The following data was obtained:
  • the volatiles were removed in vacuo to leave a yellow oil.
  • EXAMPLE 2 A 50 ml schlenk tube was loaded with 12 mg (0.023) of B(C 6 F 5 ) 3 . An addition funnel was loaded with 842 mg (4.97 mmol) of 5-N,N-diisopropylamino-l-pentene, 17 g of C 2 Zr(CH 3 ) 2 and 3.9 ml of toluene and the addi ⁇ tion funnel attached to the 50 ml schlenk. The system was sealed, removed from the dry box, and cooled to -78°C in a dry ice/acetone bath. After approximately 10 minutes, the solution was added to the B(C 6 F 5 ) 3 .
  • the reaction vessel was moved to a dry ice/CCl 4 bath (-25°C) .
  • the solution slowly turned yellow after approximately 30 minutes.
  • the reaction was quenched with acetone after stirring at -25°C for 2 hours.
  • GC analysis of the quenched reaction mixture indicated 68% conversion.
  • the crude product was dissolved in hexanes, filtered through a plug of alumina and dried under vacuum to afford a light yellow wax.
  • Polymer characterization by NMR (CDC1 3 ) indicated a highly syndiotactic microstructure (Fig.
  • EXAMPLE 3 In a similar fashion as described in Example 1, 845 mg (1.1 ml, 4.99 mmol) of 5-N,N-diisopropylamino- 1-pentene, 2 ml of a EBTHIZr(CH 3 ) 2 /toluene solution (8 mg/ml, 0.041 mmol added) , 1.0 ml of a B(C 6 F 5 ) 3 /toluene solution (10.12 mg/ml, 0.020 mmol added) and 0.90 ml of toluene were reacted at 20°C. The solution turned light yellow over 10 minutes. GC analysis indicated 0% con- version.
  • EXAMPLE 6 In a similar fashion as described in Example 1, 16 g (0.042 mmol) of EBTHIZrMe 2 , 1.134 g (5.0 mmol) of 4-TBDMSO-l, 6-heptadiene, 1.0 ml of a B(C 6 F 5 ) 3 /toluene solution (10.6 mg/ml, 0.021 mmol added) and 2.6 ml of toluene were reacted at 22°C. Upon mixing, the solution turned yellow and a slight exotherm was detected (22- 26°C) . The reaction was monitored by GC and the following data was obtained:
  • Examples 1-7 are summarized in Table 1 and compared to 1-hexene.
  • Cp* pentamethylcyclopentadienyl
  • EBTHI ethylene-l,2-bis(n 5 -4,5,6,7-tetrahydro-l-indenyl)
  • TMS trimethylsilyl
  • TBDMS tert-butyldimethylsilyl.
  • N,N-diisopropylamino-l-pentene 210 mg (1.06 mmol) of triisobutylaluminum, 5.0 ml of toluene, 20 mg (0.053 mmol) of rac-EBIZrMe 2 , and 14 mg (0.027 mmol) of B(C 6 F 5 ) 3 were reacted at 20°C for 22 hours.
  • GC analysis indicated 48% conversion.
  • the polymer was isolated in the usual manner to obtain 1.59 g of a white, tacky powder which was analyzed by NMR (endgroup analysis indicated M n >25,000).
  • EXAMPLE 12 A 20 ml vial was loaded with a stir bar, 5 ml of toluene, 882 mg of 4-TMSO-l, 6-heptadiene, and 5 mg
  • EXAMPLE 15 A 20 ml vial was loaded with 5 ml of toluene, 6 mg of Cp 2 Zr(CH 3 ) 2 and 823 mg (3.39 mmol) of 11- trimethylsiloxy-1-undecene. A 13 mg (0.016 mmol) portion of [N,N-dimethylanilinium] [B(C 6 F 5 ) ] was added. Immediately, the solution turned yellow. The reaction was stirred for 30 min and then quenched with methanol; GC analysis indicated 54% conversion.
  • EXAMPLE 18 A 20 ml vial was loaded with 1.002 g (3.93 mmol) of 5-diphenylphosphino-l-pentene, 4 ml of toluene and 29 mg (0.074 mmol) of Cp 2 Zr(CH 3 ) 2 . A 20 mg portion of B(C 6 F 5 ) 3 was added. Immediately, the solution turned yellow. After 15 min, the solution turned orange. An aliquot was taken after 1.25 hours; GC analysis indicated 50% conversion. The reaction was quenched after 3 hours by exposing the solution to air; GC analysis indicated 88% conversion. The solvent was removed under vacuum to leave a viscous oil which was analyzed by H (endgroup analysis indicates M n — 2000) and 13 C NMR.
  • EXAMPLE 22 In the dry box, a 20 ml vial was loaded with 832 mg (4.91 mmol) of 5-N,N-diisopropylaminol-pentene, 429 mg (5.10 mmol) of 1-hexene, 3.25 ml of toluene, 68 mg of triisobutylaluminum and stirred for 30 minutes. rac-EBIZrMe 2 (6 mg, 0.016 mmol) and B(C 6 F 5 ) 3 (8 mg, 0.016 mmol) were added. The solution immediately turned dark brown and an exotherm was detected (20-28°C) .
  • the reaction was quenched after 65 minutes and worked up in the usual manner to obtain 584 mg (46%) of a colorless, sticky solid.
  • the C NMR spectrum is shown in Fig. 3.
  • the copolymer was treated with a methanol/ HCl solution for 20 minutes and then dried in vacuo. A glassy solid was obtained which was completely soluble in methanol and insoluble in hexanes which indicates that no homopolymer of 1-hexene is present.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Catalyseurs dérivés de la réaction de Cp*2ZrMe2 avec B(B6F5)3 ou [N,N-diméthylanilinium] [B(C6F5)4] (indiqué sous forme de [Cp*ZrMe]+X-, Cp* = pentaméthylcyclopentadiényle, X = B(C¿6?F5)4 ou CH3B(C6F5)3) sont actifs pour l'homopolymérisation de diènes et d'alpha-oléfines fonctionnalisées telles que 4-TMSO-1,6-heptadiène (TMSO = triméthylsiloxy), 5-TBDMSO-1-pentène (TBDMSO = tertbutyldiméthylsiloxy), 5-N,N-diisopropylamino-1-pentène, 5-diphénylphosphino-1-pentène et N-(1-pentène-4-yle)carbazole. D'autres catalyseurs organométalliques tels que [rac (EBTHI)ZrMe]?+X-¿ et [EBIZrMe¿2]?+X- (EBTHI = éthylène-1,2-bis(n5-4,5,6,7-tétrahydro-1-indényle, EBI = éthylène-1,2-bis(1-indényle)) sont des catalyesurs de polymérisation actifs pour la polymérisation d'oléfines fonctionnalisées, bien qu'ils soient plus facilement empoisonnés par les éthers de silyle; les catalyseurs [rac-(EBTHI)ZrMe]+X- polymérisent 4-TBDMSO-1,6-heptadiène et 5-N,N-diisopropylamino-1-pntène. Une série d'autres éthers de silyle ont été polymérisés. Des analyses 13C NMR préliminaires de polymères obtenus à partir des alpha-oléfines fonctionnalisées avec des catalyseurs [(EBTHI)ZrMe]+X- sont compatibles avec des microstructures hautement isotactiques. Des polymères surtout syndiotactiques sont produits à -25° en présence de catalyserus [Cp*¿2?ZrMe]?+X-¿, ce qui est compatible avec le contrôle de fin de chaîne. Le traitement d'éthers de polysilyle avec HCl permet d'obtenir de nouveaux polyalcools. L'ajout de HCl au poly(5-N,N-diisopropylamino-1-pentène) produit le polyélectrolyte correspondant. Les catalyseurs organométalliques/méthylaluminoxane sont actifs pour la polymérisation d'alpha-oléfines contenant des groupes éther de silyle.
EP94902289A 1992-11-25 1993-11-17 Polymerization of functionalized monomers with ziegler-natta catalysts. Withdrawn EP0623149A4 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US98169692A 1992-11-25 1992-11-25
US981696 1992-11-25
PCT/US1993/011186 WO1994012547A2 (fr) 1992-11-25 1993-11-17 Polymerisation de monomeres fonctionnalises a l'aide de catalyseurs de ziegler-natta

Publications (2)

Publication Number Publication Date
EP0623149A1 EP0623149A1 (fr) 1994-11-09
EP0623149A4 true EP0623149A4 (en) 1995-09-27

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EP94902289A Withdrawn EP0623149A4 (en) 1992-11-25 1993-11-17 Polymerization of functionalized monomers with ziegler-natta catalysts.

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EP (1) EP0623149A4 (fr)
JP (1) JPH07507095A (fr)
CA (1) CA2128691A1 (fr)
WO (1) WO1994012547A2 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE683118A (fr) * 1965-06-25 1966-12-27
US3476726A (en) * 1965-11-29 1969-11-04 Montedison Spa Homopolymers and copolymers of unsaturated tertiary amines,and process for producing the same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3357961A (en) * 1965-05-24 1967-12-12 Exxon Research Engineering Co Copolymers of ethylene and hexadiene 1, 5
DE3640948A1 (de) * 1986-11-29 1988-06-01 Hoechst Ag Verfahren zur herstellung eines 1-olefin-stereoblockpolymers
US4734472A (en) * 1986-12-24 1988-03-29 Exxon Research And Engineering Company Method for preparing functional alpha-olefin polymers and copolymers
US4794096A (en) * 1987-04-03 1988-12-27 Fina Technology, Inc. Hafnium metallocene catalyst for the polymerization of olefins
US4975403A (en) * 1987-09-11 1990-12-04 Fina Technology, Inc. Catalyst systems for producing polyolefins having a broad molecular weight distribution
US4892851A (en) * 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE683118A (fr) * 1965-06-25 1966-12-27
US3476726A (en) * 1965-11-29 1969-11-04 Montedison Spa Homopolymers and copolymers of unsaturated tertiary amines,and process for producing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
M.R.KESTI ET AL.: "Homogeneous Ziegler-Natta polymerisation of functionalized monomers catalyzed by cationic group IV metallocenes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 114, no. 24, 18 November 1992 (1992-11-18), WASHINGTON, DC US, pages 9679 - 9680 *
See also references of WO9412547A3 *

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Publication number Publication date
JPH07507095A (ja) 1995-08-03
WO1994012547A3 (fr) 1994-07-21
WO1994012547A2 (fr) 1994-06-09
CA2128691A1 (fr) 1994-06-09
EP0623149A1 (fr) 1994-11-09

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