US4387198A — Process for producing α-olefin polymers

Claim 1

Independent Claim 433 words

A process for producing propylene polymers which comprises: (1) milling (A-1) a trivalent metal halide selected from the group consisting of aluminum trichloride (anhydrous), ferric chloride (anhydrous) and aluminum tribromide (anhydrous), together with (A-2) a divalent metal compound selected from the group consisting of Mg(OH) 2 , Ca(OH) 2 , Zn(OH) 2 , Mn(OH) 2 , MgO, CaO, ZnO, MnO, MgAl 2 O 4 , Mg 2 SiO 4 , Mg 6 MnO 8 , MgCO 3 , MnCO 3 , MgCO 3 .CaCO 3 , SnCl 2 .2H 2 O, MgCl 2 .nH 2 O (n=1˜6), NiCl 2 .6H 2 O, MnCl 2 .4H 2 O KMgCl 3 .6H 2 O, MgCl 2 .nMg(OH) 2 .mH 2 O (n=1˜3, m=1˜6), 3MgO.2SiO 2 .2H 2 O, 3MgCO 3 .Mg(OH) 2 .3H 2 O and Mg 6 Al 2 (OH) 14 CO 3 .4H 2 O, in a proportion of 0.1 to 20 mols of (A-2) to one mol of (A-1), and (2) reacting the resulting mixture of (A-1) with (A-2) at a temperature of room temperature (20° C.) to 500° C., to obtain a solid product (I); (3) reacting with this solid product (I), (OMg) an organomagnesium compound expressed by the general formula (MgR 2 ) a .(R'MgX) b (wherein R and R' each represent an alkyl group of 1 to 20 carbon atoms or an alkyl-substituted or non-substituted phenyl group of 1 to 10 carbon atoms; X represents Cl, Br or I; and a and b each represent a number of 0 to 1, the total of a and b being 1), (ED) an electron donor selected from the group consisting of alcohols, ethers, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, ureas, thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, thioethers, thioalcohols and polysiloxanes, and (EA) an electron acceptor selected from the group consisting of AlCl 3 (anhydrous), SiCl 4 , SnCl 2 , SnCl 4 , TiCl 4 , ZrCl 4 , PCl 3 , PCl 5 , VCl 4 , SbCl 5 , SCl 2 , MnCl 2 , FeCl 2 and NiCl 2 , at a reaction temperature of 0° to 500° C., preferably 20° to 200° C., (OMg), (ED) and (EA) being respectively reacted one to 10 times, TiCl 4 being employed as said electron acceptor at least once, and (OMg), (ED) and (EA) being respectively employed in an amount of 5 to 50 parts by weight each time, based on 100 parts by weight of said solid product (I), to obtain a solid product (II); (4) combining with one part by weight of this solid product (II),

Claim 2

Dependent Claim 433 words

A process for producing propylene polymers which comprises: (1) milling (A-1) a trivalent metal halide selected from the group consisting of aluminum trichloride (anhydrous), ferric chloride (anhydrous) and aluminum tribromide (anhydrous), together with (A-2) a divalent metal compound selected from the group consisting of Mg(OH) 2 , Ca(OH) 2 , Zn(OH) 2 , Mn(OH) 2 , MgO, CaO, ZnO, MnO, MgAl 2 O 4 , Mg 2 SiO 4 , Mg 6 MnO 8 , MgCO 3 , MnCO 3 , MgCO 3 .CaCO 3 , SnCl 2 .2H 2 O, MgCl 2 .nH 2 O (n=1˜6), NiCl 2 .6H 2 O, MnCl 2 .4H 2 O KMgCl 3 .6H 2 O, MgCl 2 .nMg(OH) 2 .mH 2 O (n=1˜3, m=1˜6), 3MgO.2SiO 2 .2H 2 O, 3MgCO 3 .Mg(OH) 2 .3H 2 O and Mg 6 Al 2 (OH) 14 CO 3 .4H 2 O, in a proportion of 0.1 to 20 mols of (A-2) to one mol of (A-1), and (2) reacting the resulting mixture of (A-1) with (A-2) at a temperature of room temperature (20° C.) to 500° C., to obtain a solid product (I); (3) reacting with this solid product (I), (OMg) an organomagnesium compound expressed by the general formula (MgR 2 ) a .(R'MgX) b (wherein R and R' each represent an alkyl group of 1 to 20 carbon atoms or an alkyl-substituted or non-substituted phenyl group of 1 to 10 carbon atoms; X represents Cl, Br or I; and a and b each represent a number of 0 to 1, the total of a and b being 1), (ED) an electron donor selected from the group consisting of alcohols, ethers, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, ureas, thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, thioethers, thioalcohols and polysiloxanes, and (EA) an electron acceptor selected from the group consisting of AlCl 3 (anhydrous), SiCl 4 , SnCl 2 , SnCl 4 , TiCl 4 , ZrCl 4 , PCl 3 , PCl 5 , VCl 4 , SbCl 5 , SCl 2 , MnCl 2 , FeCl 2 and NiCl 2 , at a reaction temperature of 0° to 500° C., preferably 20° to 200° C., (OMg), (ED) and (EA) being respectively reacted one to 10 times, TiCl 4 being employed as said electron acceptor at least once, and (OMg), (ED) and (EA) being respectively employed in an amount of 5 to 50 parts by weight each time, based on 100 parts by weight of said solid product (I), to obtain a solid product (II); (4) combining with one part by weight of this solid product (II),

Claim 3

Dependent Claim 125 words

1 to 500 parts by weight of (OAl) an organoaluminum compound, and 0.05 to 20 parts by weight of (ED) an electron donor, and at the time of this combination, subjecting (a) a combination of the solid product (II) with (OAl) or (b) a combination of the solid product (II), (OAl) and (ED) to polymerization treatment with 0.01 to 500 parts by weight based on one part of the solid product (II), of (α-0) an α-olefin, at a temperature of 0° to 100° C. for one minute to 20 hours, and when said combination (a) is subjected to polymerization treatment, further adding (ED), to obtain a preactivated catalyst; and (5) polymerization propylene or propylene and at least one α-olefin in the presence of this catalyst.

Claim 4

Dependent Claim 125 words

1 to 500 parts by weight of (OAl) an organoaluminum compound, and 0.05 to 20 parts by weight of (ED) an electron donor, and at the time of this combination, subjecting (a) a combination of the solid product (II) with (OAl) or (b) a combination of the solid product (II), (OAl) and (ED) to polymerization treatment with 0.01 to 500 parts by weight based on one part of the solid product (II), of (α-0) an α-olefin, at a temperature of 0° to 100° C. for one minute to 20 hours, and when said combination (a) is subjected to polymerization treatment, further adding (ED), to obtain a preactivated catalyst; and (5) polymerization propylene or propylene and at least one α-olefin in the presence of this catalyst.

Claim 5

Dependent Claim 80 words

A process according to claim 1 wherein R i MgX (wherein R i represents an alkyl group of 1 to 10 carbon atoms and X represents Cl, Br or I), C 6 H 5 MgX (wherein X is same as defined above), CH 3 (C 6 H 4 )MgX (wherein X is same as defined above) or Mg(R i ') 2 (wherein R i ' represents an alkyl group of 1 to 8 carbon atoms) is employed as said (OMg).

Claim 6

Dependent Claim 27 words

A process according to claim 1 wherein said reaction for obtaining the solid product (II) is carried out in suspension manner for one minute to 10 hours.

Claim 7

Dependent Claim 30 words

A process according to claim 1 wherein said reaction for obtaining the solid product (II) is carried out in milling manner with a ball mill for 5 to 200 hours.

Claim 8

Dependent Claim 31 words

A process according to claim 1 wherein said reaction for obtaining the solid product (II) is carried out in milling manner with a vibration mill for 10 minutes to 50 hours.

Claim 9

Dependent Claim 15 words

A process according to claim 1 wherein TiCl 4 alone is employed as said (EA).

Claim 10

Dependent Claim 25 words

A process according to claim 1 wherein TiCl 4 is employed only once as said (EA) when said (EA) is employed one to 10 times.

Claim 11

Dependent Claim 27 words

A process according to claim 7 wherein at least one member selected from said group consisting of (EA) is employed as (EA) other than TiCl 4 .

Claim 12

Dependent Claim 40 words

A process according to claim 1 wherein a reaction product obtained by reacting said (OMg) with said (ED) at 20° to 200° C. for one minute to 10 hours is employed in place of employing said (OMg) and said (ED).

Claim 13

Dependent Claim 207 words

A process according to claim 1 wherein at least one member selected from the group consisting of (CH 3 ) 3 Al, (C 2 H 5 ) 3 Al, (n-C 3 H 7 ) 3 Al, (n-C 4 H 9 ) 3 Al, (i-C 4 H 9 ) 3 Al, (n-C 6 H 13 ) 3 Al, (i-C 6 H 13 ) 3 Al, [CH 2 CH(CH 3 )(CH 2 ) 2 CH 3 ] 3 Al, (n-C 8 H 17 ) 3 Al, (n-C 10 H 21 ) 3 Al, (C 2 H 5 ) 2 AlCl, (n-C 3 H 7 ) 2 AlCl, (i-C 4 H 9 ) 2 AlCl, (C 2 H 5 ) 2 AlF, (C 2 H 5 ) 2 AlBr, (C 2 H 5 ) 2 AlI, (C 2 H 5 )AlCl 2 , (i-C 4 H 9 )AlCl 2 , (C 2 H 5 ) 2 AlH, (CH 3 ) 1 .5 AlCl 1 .5, (C 2 H 5 ) 1 .5 AlCl 1 .5, (C 2 H 5 O)Al(C 2 H 5 ) 2 and (C 2 H 5 O) 2 Al(C 2 H 5 ) is employed as said (OAl) to be combined with the solid product (II).

Claim 14

Dependent Claim 41 words

A process according to claim 1 wherein at least one member selected from the group consisting of ethylene, propylene, butene-1, hexene-1, heptene-1, octene-1, decene-1, 4-methyl-pentene-1, 2-methyl-pentene-1, 3-methyl-butene-1 and styrene is employed as said (α-O) to be employed for said polymerization treatment.

Claim 15

Dependent Claim 35 words

A process according to claim 1 wherein said polymerization treatment with said (α-O) is carried out in the presence of 0 to 5000 g of α-olefin polymer particles per g of the solid product (II).

Claim 16

Dependent Claim 25 words

A process according to claim 1 wherein said polymerization of propylene or propylene and at least one α-olefin is carried out by gas phase polymerization.

Claim 17

Dependent Claim 29 words

A process according to claim 12 wherein said polymerization of propylene or propylene and at least one α-olefin is carried out by slurry polymerization followed by gas phase polymerization.

Claim 18

Dependent Claim 29 words

A process according to claim 12 wherein said polymerization of propylene or propylene and at least one α-olefin is carried out by bulk polymerization followed by gas phase polymerization.

Claim 19

Dependent Claim 18 words

A process according to claim 1 wherein said polymerization treatment is carried out in the coexistence of hydrogen.

Claim 20

Dependent Claim 26 words

A process according to claim 1 wherein said polymerization of propylene or propylene and at least one α-olefin is carried out in the coexistence of hydrogen.

Claim 21

Dependent Claim 40 words

A process according to claim 1 wherein a reaction product obtained by reacting said (ED) with said (EA) at 20° to 200° C. for one minute to 10 hours is employed in place of employing said (ED) and said (EA).

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1986-06-06	1986-12-06	1987-06-07	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1990-06-06	1990-12-06	1991-06-07	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1994-06-06	1994-12-06	1995-06-07	$7700.00	Window Closed / Lapsed

Process for producing α-olefin polymers

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