WO1999030822A1 - Catalyseurs d'amine de metal de transition du groupe 11 pour polymerisation olefinique - Google Patents

Catalyseurs d'amine de metal de transition du groupe 11 pour polymerisation olefinique Download PDF

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WO1999030822A1
WO1999030822A1 PCT/US1998/026657 US9826657W WO9930822A1 WO 1999030822 A1 WO1999030822 A1 WO 1999030822A1 US 9826657 W US9826657 W US 9826657W WO 9930822 A1 WO9930822 A1 WO 9930822A1
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group
alkyl
straight chain
cyclo
branched alkyl
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PCT/US1998/026657
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Robert T. Stibrany
Donald Norman Schulz
Smita Kacker
Abhimanyu Onkar Patil
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Exxon Research And Engineering Company
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Priority to EP98963937A priority Critical patent/EP1017491A1/fr
Priority to CA002285302A priority patent/CA2285302A1/fr
Priority to AU19160/99A priority patent/AU1916099A/en
Publication of WO1999030822A1 publication Critical patent/WO1999030822A1/fr

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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/08—Copper 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F4/54—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 other compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/17—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/18—Gold
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the invention is directed towards tetrahedral and psuedo-tetrahedral late transition metal polymerization catalyst complexes and their use in forming homopolymers from olefins or polar monomers and copolymers from olefins and polar monomers.
  • Polymers and copolymers may be formed from olefinic monomers by using transition metal metallocene catalyst technology.
  • This well-known technology uses catalysts containing early transition metal atoms such as Ti and Zr.
  • polyolefins formed by such metallocene catalysts posses enhanced properties over polyolefins produced by conventional Ziegler-Natta catalysts, further improvements in properties such as wettability and adhesiveness may be possible. It is believed that including polar monomers in an olefinic polymer or copolymer would improve wettability and adhesiveness in those materials. Unfortunately, polar monomers tend to poison early transition metal catalysts.
  • the invention is a catalyst system comprising: (a) a catalyst having the formula LM X ⁇ X 2 wherein Xi and X 2 are independently selected from the group consisting of halogens, hydride, triflate, acetate, triflouroacetate, tris perflourotetraphenyl borate, tetraflouro borate, Cl through C12 straight chain or branched alkyl or alkoxy, C3 through C12 cyclo alkyl or cyclo alkoxy, and aryl; M is selected from the group consisting of Cu, Ag, and Au; and L is a nitrogen-containing bidentate Iigand,
  • the invention is a substantially linear copolymer represented by the formula:
  • A is a segment derived from an acyclic aliphatic olefin of 2 to about 20 carbon atoms
  • R is H or CH 3 ;
  • X is -OR 1 or -COOR 1 ;
  • R 1 is an alkyl group of 1 to 24 carbon atoms; and Y is from about 0.02 to about 0.95
  • Figure 1 shows the structure of Cu(MeBBIOMe)Cl 2 .
  • Figure 2 shows the structure of Cu(tribut BBIM) Br 2 .
  • the catalyst of this invention is a complex having the formula LM X ⁇ X 2 , wherein L is a nitrogen-containing bidentate Iigand represented by the formula:
  • a and A are independently selected from the group consisting of
  • Rl is independently selected from the group consisting of hydrogen, Cl through C12 straight chain or branched alkyl, C3 through C12 cyclo alkyl, aryl, and trif-ouroethane;
  • R2 and R3 are independently selected from the group consisting of hydrogen, Cl through C12 straight chain or branched alkyl, C3 through C12 cyclo alkyl, Cl through C12 alkoxy, F, Cl, SO 3 , Cl through C12 perflouroalkyl, and N(CH 3 ) 2 ;
  • B is selected from the group consisting of non-substituted Cl through C12 straight chain or branched alkyl, C3 through C12 cyclo alkyl; methoxy; amino; halo; and Cl through C12 haloalkyl substituted straight chain or branched alkyl or cyclo alkyl of up to 12 carbon atoms or Cl - C40 aryl or alkylaryl groups.
  • Xi and X 2 are independently selected from the group consisting halogens, hydride, triflate, acetate, triflouroacetate, tris (perflourotetraphenyl) borate, and tetraflouro borate, Cl through C12 straight chain or branched alkyl or alkoxy, C3 through C12 cyclo alkyl or cyclo alkoxy, and aryl;
  • the metal M is selected from Cu, Ag, and Au. Among Cu, Ag, and Au, Cu is preferred; among Xi and X , halogens are preferred.
  • Suitable non-halide X ! and X 2 include triflate, triflouroacetate, tris perflourotetraphenyl borate, or tetraflouro borate.
  • the catalysts of the present invention are not poisoned by compounds containing hydrocarbyl polar functionalities when used in the formation of polymers and copolymers synthesized all or in part from olefinic monomers.
  • the catalysts of the present invention are useful in preparing polymers and copolymers formed from olefinic monomers, such as polyethylene; polymers and copolymers formed from monomers containing hydrocarbyl polar functionalities such as poly(methyl methacrylate); and copolymers derived from olefins and monomers containing hydrocabyl polar functionalities such as poly (ethylene-co-methyl methacrylate) .
  • a catalyst having the formula L M X ⁇ X 2 , wherein L, M, Xi, and X 2 are as previously defined is combined with an activating cocatalyst.
  • cocatalysts include aluminum compounds containing an Al-O bond such as the alkylalumoxanes such as methylalumoxane ("MAO") and isobutyl modified methylalumoxane; aluminum alkyls; aluminum halides; alkylaluminum halides; Lewis acids other than any of the foregoing list; and mixtures of the foregoing can also be used in conjunction with alkylating agents, such as methyl magnesium chloride and methyl lithium.
  • alkylalumoxanes such as methylalumoxane (“MAO") and isobutyl modified methylalumoxane
  • Alkyls aluminum halides
  • alkylaluminum halides Lewis acids other than any of the foregoing list
  • mixtures of the foregoing can also
  • Lewis acids examples include those compounds corresponding to the formula: R"" 3 B, wherein R"" independently each occurrence is selected from hydrogen, silyl, hydrocarbyl, halohydrocarbyl, alkoxide, aryloxide, amide or combinations thereof, said R"" having up to 30 nonhydrogen atoms. It is to be appreciated by those skilled in the art, that the above formula for the preferred Lewis acids represents an empirical formula, and that many Lewis acids exist as dimers or higher oligomers in solution or in the solid state. Other Lewis acids which are useful in the catalyst compositions of this invention will be apparent to those skilled in the art.
  • cocatalysts include salts of group 13 element complexes.
  • suitable cocatalysts and their use in organometallic polymerization are discussed in U. S. Patent No. 5,198,401 and PCT patent documents PCT/US97/10418 and PCT/US96/09764, all incorporated by reference herein.
  • Preferred activating cocatalysts include trimethylaluminum, triisobutylaluminum, methylalumoxane, ethylalumoxane, chlorodiethyaluminum, dichloroethylaluminum, triethylboron, trimethylboron, triphenylboron and halogenated, especially fluorinated, triphenyl boron compounds.
  • Most highly preferred activating cocatalysts include triethylaluminum, methylalumoxane, and fluoro-substituted triaryl borons such as tris(4- fluorophenyl)boron, tris(2,4-difluorophenylboron), tris(3,5- bis(trifluoromethylphenyl) boron, tris(pentafluorophenyl) boron, pentafluorophenyl- diphenyl boron, and bis(pentafluorophenyl) phenylboron.
  • fluoro-substituted triarylboranes may be readily synthesized according to techniques such as those disclosed in Marks, et al., J. Am. Chem. Soc, 113, 3623-3625 (1991).
  • the catalyst can be utilized by forming the metal complex LM X ⁇ X 2 and where required combining the activating cocatalyst with the same in a diluent.
  • the preparation may be conducted in the presence of one or more addition polymerizable monomers, if desired.
  • the catalysts are prepared at a temperature within the range from -100°C. to 300°C, preferably 0°C to 250°C, most preferably 0°C to 100°C.
  • Suitable solvents include liquid or supercritical gases such as CO 2 , straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, halogenated hydrocarbons such as chlorobenzene, and dichlorobenzene perfluorinated C 4 . 10 alkanes and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene and xylene.
  • liquid or supercritical gases such as CO 2 , straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3 -methyl- 1-pentene, 4- methyl-1-pentene, 1-octene, 1-decene, and 4-vinycylohexane, (including all isomers alone or in mixtures).
  • Other solvents include anisole, methylchloride, methylene chloride, 2-pyrrolidone and N-methylpyrrolidone.
  • Preferred solvents are aliphatic hydrocarbons and aromatic hydrocarbon, such as toluene.
  • the cocatalyst interacts with the catalyst to create a polymerization-active, metal site in combination with a suitable non-coordinating anion.
  • a suitable non-coordinating anion is a poor nucleophile, has a large size (about 4 Angstroms or more), a negative charge that is delocalized over the framework of the anion, and is not a strong reducing or oxidizing agent [S. H. Strauss, Chem. Rev. 93, 927 (1993)].
  • the anion When the anion is functioning as a suitable non-coordinating anion in the catalyst system, the anion does not transfer an anionic substituent or fragment thereof to any cationic species formed as the result of the reaction.
  • the equivalent ratio of metal complex to activating cocatalyst (where employed) is preferably in a range from 1:0.5 to 1:10 4 , more preferably from 1:0.75 to 1 : 10 3 .
  • the equivalent ratio of catalys polymerizable compound employed is from 10 "12 : to 10 _1 :1, more preferably
  • the catalysts of the present invention have a tetrahedral or psuedo- tetrahedral structure. It is believed that this structure is present when the catalyst is in the form of an isolated solid compound and when the catalyst is used in the presence of activating cocatalysts of this invention under homopolymerization or copolymerization conditions.
  • Figure 1 shows nitrogen atoms Nl and N3 together with metal atom Cul describe a tetrahedron with the metal atom at the apex and the nitrogen atoms occupying diagonally opposed positions on a base.
  • atoms Cll and C12 form a tetrahedron with Cul, the metal atom being at the apex and the chlorines occupying diagonally opposed basal positions.
  • Olefinic monomers useful in the forming homo and copolymers with the catalyst of the invention include, for example, ethylenically unsaturated monomers, nonconjugated dienes, and oligomers, and higher molecular weight, vinyl-terminated macromers. Examples include C 2 . 2 o olefins, vinylcyclohexane, tetrafluoroethylene, and mixtures thereof. Preferred monomers include the C 2 . ⁇ o ⁇ - olefins especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-l- pentene, and 1-octene or mixtures of the same.
  • Monomers having hydrocarbyl polar functionalities useful in forming homo and copolymers with the catalyst of the invention are vinyl ether and Ci to C 2 o alkyl vinyl ethers such as «-butyl vinyl ether, acrylates, such as Cl to C24, or alkyl acrylates such as t-butyl acrylate, and lauryl acrylate, as well as methacrylates such as methyl methacrylate.
  • the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from -100°C to 250°C preferably 0°C to 250°C, and pressures from atmospheric to 1000 atmospheres (100 Mpa).
  • Suitable polymerization conditions include those known to be useful for metallocene catalyst when activated by aluminum or boron-activated compounds. Suspension, solution, slurry, gas phase or other process condition may be employed if desired.
  • the catalyst may be supported and such supported catalyst may be employed in the polymerizations of this invention.
  • Preferred supports include alumina, silica, and polymeric supports.
  • the polymerization typically will be conducted in the presence of a solvent. Suitable solvents include those previously described as useful in the preparation of the catalyst. Indeed, the polymerization may be conducted in the same solvent used in preparing the catalyst. Optionally, of course, the catalyst may be separately prepared in one solvent and used in another.
  • the polymerization will be conducted for a time sufficient to form the polymer and the polymer is recovered by techniques well known in the art and illustrated in the examples hereinafter.
  • An important feature of the invention is the formation of substantially linear copolymers having the formula where A is a segment derived from an acyclic aliphatic olefin of 2 to about about 20 carbon atoms; R is H or CH 3 ; x is " OR 1 or " COOR 1 ; R 1 is an alkyl group of 1 to 24 carbon atoms and y is from about 0.02 to about 0.95 and preferrably y is from about 0.18 to about 0.85.
  • copolymers have polar functional monomer segments, — HDH 2 — CR- - which are substantially in the chain rather than at ends of branches.
  • -A- is a polymer segment derived from ethylene
  • the branch content of which is below about 20 branches/ 1000 carbon atoms, for example from about 0.5 to less than 20 branches.
  • a solution of ethanol and triethylorthoformate was prepared by refluxing 30 ml of 100% ethanol and 4 ml of triethylorthoformate.
  • a 245 mg (1.82 mmol) quantity of CuCl 2 (99.999% Aldrich) was dissolved in the ethanol/triethylorthoformate solution to form a yellow-green solution.
  • 584 mg (1.82 mmol) of solid MeBBIOMe an intensely yellow colored crystalline precipitate formed.
  • 3,3' (l-Ethylbenzimidazol-2yl) pentane copper (II) dichloride, Cu(tetEtBBIM)C ⁇ 2 was prepared by the Examples 1-3, using malonic acid and 1,2 phenylene diamine and ethyl iodide as the alkylating agent.
  • a suspension of 65 mg of [3,3'(1- ethylbenzimidazol-2yl)pentane]copper(II) dichloride, Cu(tetEtBBIM)Cl 2 was prepared in a solution consisting of 35 ml of methylene chloride and 0.5 ml of triethylorthoformate.
  • a solution of ethanol and triethylorthoformate was prepared by combining 35 mL of 100% ethanol and 4 mL of triethylorthoformate.
  • a 500 mg (2.93 mmol) quantity of CuCl -2H 2 O (Aldrich) was dissolved to form a green solution.
  • RT means ambient or room temperature, i.e. a temperature from about 20 °C to 26 °C.
  • a glass lined Parr reactor was loaded in an Ar glove box with 14.1 mg (0.024 mmol) of Cu (diEtBBIL)Cl 2 followed by 30 mL of toluene to give a pale yellow partially dissolved solution. Next 2.0 mL of 30% MAO was added to give a nearly colorless solution.
  • a high-pressure HASTELLOYTM reactor was loaded in an Ar glovebox with a slurry prepared by suspending 35 mg (0.077 mmol) of Cu(MeBBIOMe)Cl 2 in 4.0 mL of toluene followed by activation with 1.0 ml of 30% MAO (0.005 mol).
  • the reactor was pressurized with 5.6 g (0.20 mol) of ethylene and heated to 80.5 °C, resulting in a pressure of 5170 psig. The pressure dropped to 4390 psig over a 2.75 h period indicating an uptake of ethylene.
  • the polymerization was run using a slurry prepared by suspending 12.8 mg (0.022 mmol) of Cu(diEtBBIL)Cl 2 in 30 mL of toluene and 10 mL of 1,2-dichlorobenzene followed by activation with 2.5 ml of 30% MAO to give a yellow suspension.
  • the Parr reactor was pressurized with 500 psig of ethylene and heated to 80 °C and maintained at 80 °C for 1/2 h during which the pressure dropped from 730 psi to 580 psig.
  • the polymerization was run using a toluene slurry prepared by suspending 20.8 mg (0.029 mmol) of [3,3'(l-ethylbenzimidazol-2yl)pentane]copper(II) ditrifluoromethyl- sulfonate, Cu(tetEtBBIM)(trif) in 30 mL of toluene followed by activation with 2.0 mL of 30% MAO (0.01 mol) to give a yellow suspension.
  • the PARRTM reactor was pressurized with 300 psig of ethylene and heated to 90° C and further pressurized to 750 psig and maintained at 90 °C for 20 h during which the pressure dropped to 740 psi.
  • a high-pressure HASTELLOYTM reactor was loaded in an Ar glovebox with a slurry prepared by suspending 30.1 mg (0.066 mmol) of Cu(MeBBIOMe)Cl 2 in 2.0 mL of toluene followed by activation with 1.0 mL of 30% MAO (0.005 mol). This was followed by the addition of 0.67 g of 1-hexene.
  • a 20.1 mg (0.044 mmol) quantity of Cu(MeBBIOMe)Cl2 was added to a 100 mL round-bottomed flask in an Ar glovebox.
  • a 10 mL quantity of toluene was added to the flask, followed by 0.11 g of 30 wt. % MAO (0.57 mmol) resulting in an yellow slurry.
  • 7.45 g of t-butyl acrylate freshly distilled from CaCl2 and stabilized with 300 ppm of phenathiazine was added to the slurry.
  • the flask was covered with aluminum foil and the mixture was allowed to stir at room temperature for 18 hours in the dark.
  • a yellow suspension was prepared by adding 1.0 ml of 30% MAO to 25 ml of toluene containing 10.2 mg (0.022 mmol) of Cu(MeBBIOMe)Cl 2 . Then 5.0 mL «-butyl vinyl ether (44 mmol) was added to the suspension. The mixture was allowed to stir at RT for 20 h during which time the mixture became a viscous pale red-brown solution. The polymerization was quenched with methanol.
  • a Parr reactor was loaded with 33.5 mg (0.0679 mmol) of Cu (tet EtBBIM)Cl 2 followed by 35 mL of toluene, then by 2.0 mL of 30% MAO (.01 moles) in an argon dry box to give a yellow suspension.
  • the 6.0 mL (5.37g) (54 mmol) of t-butyl acrylate was added to give a yellow-green suspension.
  • the Parr was sealed and set up in a hood and pressurized with 750 psig of ethylene and polymerized at 90°C for 24 hours. The reaction mixture was cooled and quenched with MeOH.
  • a copolymer was prepared following the procedure of Examples 134 of PCT WO96/23010.
  • 1HNMR (CDC1 3 ): 2.2(t, -CH 2 CO 2 C(CH 3 ) 3 , ester ended branches), 1.6 (m, CH 2 CH 2 CO 2 C(CH 3 ) 3 , ester ended branches), 1.45 (s, -C(CH 3 ) 3 ), 0.95-1.45, (m, CH, and other CH 2 ). 0.75-0.95 (m, CH 3 , ends of hydrocarbon branches or ends of chains).
  • This spectrum shows that the esters are primarily located at the ends of hydrocarbon branches; integration gave 6.7 mole% t-butyl acrylate.
  • a Parr reactor was loaded with 26.1 mg (.055 mmol) or orange Cu (BBD ) Cl 2 , followed by 30 mL of toluene, and finally with 2.0 mL of 30% MAO (.010 mol). Then 4.0 mL (3.74g) (0.0374 mmol) of methyl methacrylate, containing 400 ppm of phenathiazine, was added.
  • the Parr reactor was sealed and set up in a hood and pressurized with 750 psig of ethylene and polymerized at 90°C for 19.5 hours. The reaction was quenched with MeOH. The polymer was collected by filtration to give 0.68 g of white polymer.
  • No backbone methine carbons were found by a DEPT (Distortionless Enhancement by Polarization Transfer) experiment, indicating no detectable backbone branch sites.
  • a Parr reactor was loaded with 33.3 mg (0.0673 mmol) of Cu (tetEtBBIM) Cl 2 and 30 mL of toluene, followed by the addition of 2.0 mL of 30% MAO (0.010 mol) to give a yellow suspension.
  • a 5 mL quantity (44 mmol) of n-butyl vinyl ether was added with no immediate color change.
  • the Parr reactor was sealed and taken to a hood containing the controllers for the reactor.
  • the reactor was pressurized with 750 psig of ethylene and the mixture was reacted at 60°C for 20 hours. The reaction was cooled, quenched and the product was isolated.
  • the polymer was soaked in MeOH/HCl to remove catalyst residues.
  • a polymerization tube was loaded with 17.9 mg (FW 744.5, 2.4 x 10 '5 mole) of Cu(diOctBBIL)Cl 2 catalyst, followed by 20.25 mL of toluene, and finally with 0.8 mL of 10% MAO (0.00138 mole). Then 3.0 g (FW 240.39, 0.0125 mole) of inhibitor free lauryl acrylate was added. The mixture was allowed to stir at room temperature for 24 hours. The yield was 47%, upon workup. 13 C NMR of the product showed characteristic polymer ester peak at 174.4 ppm as against to 166.1 peak for monomer ester.
  • a Parr reactor was loaded with 15.0 mg (FW 744.5, 2.01 x 10 "5 mole) of Cu(diOctBBIL)Cl 2 catalyst, followed by 30 mL of toluene, and finally with 2.4 mL of 10% MAO (0.00414 mole). Then 2.0 g (FW 240.39, 0.00832 mole) of inhibitor free lauryl acrylate was added.
  • the Parr reactor was sealed and set up in a hood and pressurized with 700 psig of ethylene and polymerized at 80°C for 48 hours. The polymer was collected by filtration to give 1.3g of product.

Abstract

L'invention porte sur une composition comprenant un catalyseur et un cocatalyseur d'activation. Le catalyseur a la formule LMX1X2 dans laquelle X1 et X2 représentent, indépendamment, halogénure, hydrure, triflate, acétate, trifluoroacétate, tris perfluorotétraphényl borate, tétrafluoroborate, alkyle à chaîne droite ou ramifiée ou alcoxy comprenant 1 à 12 atomes de carbone, cycloalkyle ou cycloalcoxy comprenant 3 à 12 atomes de carbone ou aryle. M représente Cu, Ag ou Au. L représente un ligand bidenté renfermant azote. L'azote en L est de préférence contenu dans des noyaux hétérocycliques à 5 ou 6 éléments dont deux sont liés à un groupe de pontage hydrocarbyle. Le cocatalyseur d'activation est en général un composé d'aluminium ou un acide de Lewis.
PCT/US1998/026657 1997-12-16 1998-12-16 Catalyseurs d'amine de metal de transition du groupe 11 pour polymerisation olefinique WO1999030822A1 (fr)

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EP98963937A EP1017491A1 (fr) 1997-12-16 1998-12-16 Catalyseurs d'amine de metal de transition du groupe 11 pour polymerisation olefinique
CA002285302A CA2285302A1 (fr) 1997-12-16 1998-12-16 Catalyseurs d'amine de metal de transition du groupe 11 pour polymerisation olefinique
AU19160/99A AU1916099A (en) 1997-12-16 1998-12-16 Group 11 transition metal amine catalysts for olefin polymerization

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WO2001092354A2 (fr) * 2000-05-31 2001-12-06 E. I. Du Pont De Nemours And Company Copolymeres d'ethylene et esters d'acrylate selectionnes
WO2002000666A1 (fr) 2000-06-23 2002-01-03 Exxonmobil Chemical Patents Inc. Activateurs de cocatalyste a substitution siloxy pour la polymerisation de l'olefine
WO2002016373A1 (fr) * 2000-08-18 2002-02-28 Exxonmobil Research And Engineering Company Complexes de metaux de transition tardifs, leur utilisation comme catalyseurs et polymeres obtenus a partir desdits complexes
EP1186619A2 (fr) * 2000-09-07 2002-03-13 Mitsui Chemicals, Inc. Copolymère d'oléfines contenant des groupes polaires, procédé pour sa préparation, composition thermoplastique de résine contenant le copolymère et son utilisation
US6476164B1 (en) 1999-10-22 2002-11-05 Exxonmobil Chemical Patents Inc. Carbenium cationic complexes suitable for polymerization catalysts
US6475946B1 (en) 1999-10-22 2002-11-05 Exxonmobil Chemical Patents Inc. Olefin polymerization catalysis with aryl substituted carbenium cationic complexes
US6486088B1 (en) 1998-10-23 2002-11-26 Exxonmobil Chemical Patents Inc. High activity carbenium-activated polymerization catalysts
WO2003000740A2 (fr) 2001-06-20 2003-01-03 Exxonmobil Chemical Patents Inc. Polyolefines formees au moyen d'un catalyseur, comprenant un anion non coordonnant, et articles renfermant ces polyolefines
US6506859B1 (en) 2000-08-18 2003-01-14 Exxonmobil Research And Engineering Company Polymerization using late transition metal catalyst complexes formed in situ
WO2003020778A1 (fr) * 2001-08-28 2003-03-13 Exxonmobil Research And Engineering Company Complexes catalyseurs de metaux de transition tardifs multidentes et procedes de polymerisation utilisant lesdits complexes
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US6689928B2 (en) 2000-04-04 2004-02-10 Exxonmobil Research And Engineering Company Transition metal complexes and oligomers therefrom
US6730757B2 (en) 2002-03-08 2004-05-04 Exxonmobil Research And Engineering Company Sulfur-containing and sulfur-nitrogen-containing catalysts for polymerization of olefins and polar monomers
WO2004046214A2 (fr) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Systeme catalyseur multiple pour la polymerisation d'olefines et polymeres ainsi produits
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WO2016098674A1 (fr) * 2014-12-15 2016-06-23 住友化学株式会社 Polymère
WO2017217417A1 (fr) * 2016-06-15 2017-12-21 住友化学株式会社 Stratifié, matériau de construction, bâtiment, et conteneur à isolation thermique
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US6562919B2 (en) 1998-10-23 2003-05-13 Exxonmobil Chemical Patents Inc. High activity carbenium-activated polymerization catalysts
US6806220B2 (en) 1998-10-23 2004-10-19 Exxonmobil Chemical Patents Inc. High activity carbenium-activated polymerization catalysts
US6838411B2 (en) 1999-10-22 2005-01-04 Exxonmobil Chemical Patents Inc. Olefin polymerization catalysis with aryl substituted carbenium cationic complexes
US6476164B1 (en) 1999-10-22 2002-11-05 Exxonmobil Chemical Patents Inc. Carbenium cationic complexes suitable for polymerization catalysts
US6475946B1 (en) 1999-10-22 2002-11-05 Exxonmobil Chemical Patents Inc. Olefin polymerization catalysis with aryl substituted carbenium cationic complexes
US6822057B2 (en) 1999-12-09 2004-11-23 Exxon Mobil Chemical Patents Inc. Olefin polymerization catalysts derived from Group-15 cationic compounds and processes using them
US7163993B2 (en) 1999-12-20 2007-01-16 Exxonmobil Chemical Patents Inc. Electrical devices from polymer resins prepared with ionic catalysts
US6562920B2 (en) 1999-12-20 2003-05-13 Exxonmobil Chemical Patents Inc. Processes for the preparation polyolefin resins using supported ionic catalysts
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US6689928B2 (en) 2000-04-04 2004-02-10 Exxonmobil Research And Engineering Company Transition metal complexes and oligomers therefrom
US6809209B2 (en) 2000-04-07 2004-10-26 Exxonmobil Chemical Patents Inc. Nitrogen-containing group-13 anionic compounds for olefin polymerization
WO2001092354A3 (fr) * 2000-05-31 2003-01-16 Du Pont Copolymeres d'ethylene et esters d'acrylate selectionnes
WO2001092354A2 (fr) * 2000-05-31 2001-12-06 E. I. Du Pont De Nemours And Company Copolymeres d'ethylene et esters d'acrylate selectionnes
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US7393907B2 (en) 2000-09-07 2008-07-01 Mitsui Chemicals, Inc. Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition containing the copolymer, and uses thereof
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US7094848B2 (en) 2003-05-13 2006-08-22 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system
US7285609B2 (en) 2003-05-13 2007-10-23 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system useful for polar monomers
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