EP0283011A2 — Process for producing olefin polymers and catalys…

Claim 1

Independent Claim 54 words

A solid catalyst component for α-olefin polymerization containing as catalyst components at least titanium, magnesium and chlorine which are impregnated into an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å.

Claim 2

Dependent Claim 54 words

A solid catalyst component for α-olefin polymerization containing as catalyst components at least titanium, magnesium and chlorine which are impregnated into an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å.

Claim 3

Dependent Claim 21 words

A solid catalyst component according to Claim 1, wherein the atomic ratio of titanium/magnesium and chlorine/magnesium are 0.01-0.8 and 1.8-10, respectively.

Claim 4

Dependent Claim 31 words

A solid catalyst component according to Claim 1, wherein the amount of the catalyst component impregnated into the organic porous polymer carrier is 1-70% by weight in the solid catalyst component.

Claim 5

Dependent Claim 31 words

A solid catalyst component according to Claim 1, wherein the organic porous polymer carrier is a porous polymer bead selected from the group consisting of polystyrenes, polyvinyl chlorides, polyolefins, and polyacrilonitriles.

Claim 6

Dependent Claim 145 words

A solid catalyst component according to Claim 1, which is a solid catalyst component containing a trivalent titanium compound obtained by reducing a titanium compound represented by the general formula Ti(OR¹) n X 4-n (wherein R¹ is a hydrocarbon group of 1 to 20 carbon atoms, X is a halogen atom; and n is a number satisfying 0 < n ≦ 4) with an organomagnesium compound in the presence of an organic porous polymer carrier having a mean particle diameter of 5 to 1000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å, or in the co-presence of said organic porous polymer carrier and an organo silicone compound having a Si-O bond to obtain a solid product, treating the solid product with an ester compound, and a mixture of an ether compound and titanium tetrachloride.

Claim 7

Dependent Claim 141 words

A solid catalyst component according to Claim 1, which is a solid catalyst component containing a trivalent titanium compound obtained by reducing a titanium compound represented by the general formula Ti(OR¹) n X 4-n (wherein R¹ is a hydrocarbon group of 1 to 20 carbon atoms, X is a halogen atom; and n is a number satisfying 0 < n ≦ 4) with an organomagnesium compound in the presence of an organic porous polymer carrier having a mean particle diameter of 5 to 1000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å, or in the co-presence of said organic porous polymer carrier and an organo silicone compound having a Si-O bond to obtain a solid product, treating the solid product with a mixture of an ether compound and titanium tetrachloride.

Claim 8

Dependent Claim 48 words

A solid catalyst component according to Claim 5 or 6, wherein the hydrocarbon group R¹ of the titanium compound represented by the general formula Ti(OR¹) n X 4-n is a alkyl groups having 2 to 18 carbon atoms or an aryl groups having 6 to 18 carbon atoms.

Claim 9

Dependent Claim 28 words

A solid catalyst component according to Claim 5 or 6, wherein the X of the titanium compound represented by the general formula Ti(OR¹) n X 4-n is chlorine.

Claim 10

Dependent Claim 35 words

A solid catalyst component according to Claim 5 or 6, wherein the n of the titanium compound represented by the general formula Ti(OR¹) n X 4-n is a number satisfying 2 ≦ n ≦ 4.

Claim 11

Dependent Claim 74 words

A solid catalyst component according to Claim 5 or 6, wherein the organomagnesium compound is a Grignard compound represented by the general formula RʹMgX (wherein Rʹ is a hydrocarbon group of 1 to 20 carbon atoms and X is a halogen atom), or a dialkyl magnesium compound or a diaryl magnesium compound both represented by the general formula RʺR‴Mg (wherein Rʺ and R‴ are each a hydrocarbon group having 1 to 20 carbon atoms).

Claim 12

Dependent Claim 19 words

A solid catalyst component according to Claim 5, wherein the ester compound is mono or polyvalent carboxylic acid ester.

Claim 13

Dependent Claim 18 words

A solid catalyst component according to Claim 5 or 6, wherein the ether compound is an dialkyl ether.

Claim 14

Dependent Claim 95 words

A solid catalyst component according to Claim 5 or 6, wherein the organosilicone compound having a Si-O bond is represented by the following general formula: Si(OR³) m R⁴ 4-m R⁵(R⁶₂SiO) p SiR⁷₃ or (R⁸₂SiO) q (wherein R³ is a hydrocarbon group having 1 to 20 carbon atoms; R⁴, R⁵, R⁶, R⁷ and R⁸ are each a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom; m is a number satisfying 0 < m ≦ 4; p is an integer of 1 to 1,000; and q is an integer of 2 to 1,000).

Claim 15

Dependent Claim 44 words

A solid catalyst component according to Claim 5 or 6, wherein the organosilicone compound having a Si-O bond is an alkoxysilane compound represented by the general formula Si(OR³) m R⁴ 4-m , in which m is a number satisfying 1 ≦ m ≦ 4.

Claim 16

Dependent Claim 42 words

A solid catalyst component according to Claim 5 or 6, wherein the organosilicone compound having a Si-O bond is used in an amount of 1 to 50 in terms of the atomic ratio of silicon atoms to titanium atoms in titanium compound.

Claim 17

Dependent Claim 41 words

A solid catalyst component according to Claim 5 or 6, wherein the organomagnesium compound is used in an amount of 0.1 to 10 in terms of the atomic ratio of the sum of titanium atoms and silicon atoms to magnesium atoms.

Claim 18

Dependent Claim 22 words

A solid catalyst component according to Claim 5 or 6, wherein the reduction is conducted at a temperature of -50° to 70°C.

Claim 19

Dependent Claim 32 words

A solid catalyst component according to Claim 5, wherein the ester compound is used in an amount of 0.1 to 50 moles per 1 mole of titanium atom in the solid product.

Claim 20

Dependent Claim 34 words

A solid catalyst component according to Claim 5 or 6, wherein the ether compound is used in an amount of 0.1 to 100 moles per 1 mole of titanium atom in the solid product.

Claim 21

Dependent Claim 47 words

A solid catalyst component according to Claim 5 or 6, wherein titanium tetrachloride is used in an amount of 2 to 2,000 moles per 1 mole of titanium atom in the solid product and in an amount of 1 to 100 moles per mole of ether compound.

Claim 22

Dependent Claim 28 words

A solid catalyst component according to Claim 5, wherein the solid product is treated with an ester compound in a diluent at a temperature of -50° to 150°C.

Claim 23

Dependent Claim 19 words

A solid catalyst component according to Claim 21, wherein the diluent is an aromatic hydrocarbon or a halogenated hydrocarbon.

Claim 24

Dependent Claim 36 words

A solid catalyst component according to Claim 5, wherein the ester-treated solid product is treated with a mixture of an ether compound and titanium tetrachloride in a slurry state using a solvent at 30° to 150°C.

Claim 25

Dependent Claim 23 words

A solid catalyst component according to Claim 23, wherein the solvent is an aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon or a halogenated hydrocarbon.

Claim 26

Dependent Claim 66 words

A catalyst system for α-olefin polymerization comprising at least (A) a solid catalyst component containing as catalyst components at least titanium, magnesium and chlorine which are impregnated into an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å, and (B) an organoaluminum compound.

Claim 27

Dependent Claim 66 words

A catalyst system for α-olefin polymerization comprising at least (A) a solid catalyst component containing as catalyst components at least titanium, magnesium and chlorine which are impregnated into an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å, and (B) an organoaluminum compound.

Claim 28

Dependent Claim 147 words

A catalyst system according to Claim 25, wherein the solid catalyst component is a solid catalyst component containing a trivalent titanium compound obtained by reducing a titanium compound represented by the general formula Ti(OR¹) n X 4-n (wherein R¹ hydrocarbon group of 1 to 20 carbon atoms, X is a halogen atom, and n is a number satisfying 0 < n ≦ 4) with an organo magnesium compound in the presence of an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å, or in the co-presence of said organic porous polymer carrier and an organo silicone compound having a Si-O bond to obtain a solid product, treating the solid product with an ester compound, and a mixture of an ether compound and titanium tetrachloride.

Claim 29

Dependent Claim 144 words

A catalyst system according to Claim 25, wherein the solid catalyst component is a solid catalyst component containing a trivalent titanium compound obtained by reducing a titanium compound represented by the general formula Ti(OR¹) n X 4-n R¹ is a hydrocarbon group of 1 to 20 carbon atoms, X is a halogen atom, and n is a number satisfying 0 < n ≦ 4) with an organo magnesium compound in the presence of an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å, or in the co-presence of said organic porous polymer carrier and an organo silicone compound having a Si-O bond to obtain a solid product, treating the solid product with a mixture of an ether compound and titanium tetrachloride.

Claim 30

Dependent Claim 82 words

A catalyst system for alpha-olefin polymerization according to Claim 25, wherein the organoaluminum compound (B) is a compound having at least one Al-C bond within the molecule and is represented by the general formula R⁹ γ AlY 3-γ or R¹⁰R¹¹Al-O-AlR¹²R¹³ (wherein R⁹, R¹⁰, R¹¹, R¹² and R¹³ are each a hydrocarbon group having 1 to 8 carbon atoms; Y is a halogen atom, a hydrogen atom or an alkoxy group; and γ is a number of satisfying 2 ≦ γ ≦ 3).

Claim 31

Dependent Claim 31 words

A catalyst system for alpha-olefin polymerization according to Claim 28, wherein the organoaluminum compound is a trialkylaluminum, a mixture of a trialkyl aluminum and a dialkylaluminum halide, or an alkyl alumoxane.

Claim 32

Dependent Claim 15 words

A catalyst system according to Claim 25, wherein an electron donor (C) is further added.

Claim 33

Dependent Claim 51 words

A catalyst system according to Claim 30, wherein the electron donor (C) is a compound selected from the group consisting of organo silicon compounds having a Si-OR² bond (R² represents a hydrocarbon residue having 1 to 20 carbon atoms) or a Si-N-C bond, aromatic carboxylic ester compounds and sterically hindered amines.

Claim 34

Dependent Claim 16 words

A catalyst system according to Claim 31, wherein the electron donor is an organo silicon compound.

Claim 35

Dependent Claim 50 words

A catalyst system according to Claim 32, wherein the organosilicon compound is an alkoxysilane compound represented by the general formula R¹⁴ t Si(OR²) 4-t (where R¹⁴ and R² each represents a hydrocarbon residue having 1 to 20 carbon atoms, and t represents a number satisfying 0 ≦ t ≦ 3).

Claim 36

Dependent Claim 33 words

A catalyst system according to Claim 30, wherein the electron donor is used in an amount of 0.01 to 5 moles per 1 mole of the aluminum atom in the organoaluminum compound (B).

Claim 37

Dependent Claim 87 words

A process for producing a granular thermoplastic elastomer and a granular elastomer which comprises polymerizing an α-olefin or copolymerizing α-olefins by the use of a catalyst system comprising at least a solid catalyst component (A) containing as catalyst components at least titanium, magnesium and chlorine which are impregnated into an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å and an organoaluminum compound (B).

Claim 38

Dependent Claim 87 words

A process for producing a granular thermoplastic elastomer and a granular elastomer which comprises polymerizing an α-olefin or copolymerizing α-olefins by the use of a catalyst system comprising at least a solid catalyst component (A) containing as catalyst components at least titanium, magnesium and chlorine which are impregnated into an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 µm and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 Å and an organoaluminum compound (B).

Claim 39

Dependent Claim 103 words

A process according to Claim 35, wherein the process comprises, in the first step, preparing an isotactic polypropylene by a polymerization reaction in liquefied propylene and/or in the gas phase, followed by, in the second step, preparing an ethylene-α-olefin random copolymer in the gas phase so that the ethylene content in the copolymer formed in the second step reaches 5 to 95% by weight and its intrinsic viscosity in tetralin at 135°C comes to 0.3 to 10 and the weight of the copolymer formed in the second step comes to 60 to 97% by weight based on the total weight of the polymers.

Claim 40

Dependent Claim 111 words

A process according to Claim 35, wherein the process comprises, in the first step, polymerizing ethylene in a slurry state in a propane solvent or a butane solvent or polymerizing ethylene in gas phase, followed by, in the second step, preparing an ethylene-α-olefin random copolymer by a polymerization reaction in the gas phase so that the ethylene content in the copolymer formed in the second step reaches 5 to 95% by weight and its intrinsic viscosity in tetralin at 135°C comes to 0.3 to 10 and the weight of the copolymer formed in the second step comes to 60 to 97% by weight based on the total weight of the polymers.

Claim 41

Dependent Claim 52 words

A process according to Claim 35, wherein the process comprises carrying out a random copolymerization of ethylene and α-olefin in the gas phase so that the ethylene content in the copolymer thus formed reaches 5 to 95% by weight and its intrinsic viscosity in tetralin at 135°C comes to 0.3 to 10.

Claim 42

Dependent Claim 16 words

A process according to Claim 35, wherein the catalyst system further contains an electron donor (C).

Claim 43

Dependent Claim 18 words

Granular thermoplastic elastomers and granular elastomers produced by the process according to any of Claims 35 to 39.

Process for producing olefin polymers and catalyst used therein

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