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US4157435A
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Process for preparing highly stereoregular polyolefins and catalyst used therefor
Assignee: Mitsui Chemicals Inc
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Filing: 1976-08-02
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Granted: 1979-06-05
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Expires: 1996-08-02
Abstract
Abstract A process for preparing highly stereoregular polyolefins in the presence of a catalyst comprising (A) a titanium-containing solid catalyst component composed of an organic complex derived from (I) A MAGNESIUM HALIDE (II) AN ORGANOPOLYSILOXANE SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULA Q(Q2SiO)nSiQ3, (Q2SiO)n and X(Q2SiO)nSiQ2X, (iii) an organic carboxylic acid ester, and (IV) A TITANIUM COMPOUND OF THE FORMULA Ti(OR)lX4-l, and (B) an organoaluminum catalyst component of the formula R'mAl(OR')3-m, SAID ORGANIC COMPLEX BEING DERIVED BY BRINGING THE COMPONENT (I) INTO CONTACT WITH A COMBINATION OF THE COMPONENTS (II) AND (III) OR A COMBINATION OF THE COMPONENTS (II), (III) AND (IV) UNDER MECHANICAL PULVERISATION CONDITIONS AND THEN TREATING THE RESULTING PULVERIZED COMPOSITION WITH THE COMPONENT (IV) IN THE ABSENCE OF MECHANICAL PULVERIZATION.
Inventors
- 👤 Akinori Toyota
- 👤 Norio Kashiwa
- 👤 Syuji Minami
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 15:20
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/02; C08F4/022; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/904; Y10S526/906
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
325 words
A process for preparing highly stereoregular polyolefins, which comprises polymerizing or copolymerizing α-olefins having at least 3 carbon atoms in the presence of a catalyst, said catalyst comprising (A) a titanium-containing solid catalyst component composed of an organic complex derived from (i) a magnesium dihalide, (ii) an organo polysiloxane selected from at least one of the group consisting of: compounds of the formula Q(Q.sub.2 SiO).sub.n SiQ.sub.3 wherein Q's are identical or different, and represent a moiety selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl, with the proviso that all Q moieties are not hydrogen at the same time, and n is an integer of 1 to 1000; compounds of the formula (Q.sub.2 SiO).sub.n wherein Q is the same as defined above, and n is an integer of 2 to 1000; and compounds of the formula X(Q.sub.2 SiO).sub.n SiQ.sub.2 X wherein Q is the same as defined above, n is an integer of 1 to 1000, and X is halogen, (iii) an organic carboxylic acid ester, and (iv) a titanium compound of the formula Ti(OR).sub.l X.sub.4-l wherein R is a moiety selected from the group consisting of alkyl groups and a phenyl group optionally substituted with an alkyl group with 1 to 4 carbon atoms, X is a halogen, and l is 0 or an integer of 1 to 4, and (B) at least one organoaluminum catalyst component of the formula R'.sub.m Al(OR').sub.3-m wherein R' moieties are identical or different, and represent alkyl, and m is a positive number of 1.5 to 3, said organic complex being derived by bringing the component (i) into contact with a combination of the components (ii) and (iii) in a molar ratio (i)/(ii)/(iii) of 1/1000-0.01/10-0.005 or a combination of the components (ii), (iii) and (iv) in a molar ratio (i)/(ii)/(iii)/(iv) of 1/1000-0.01/10-0.005/100-0.001 under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 2
Dependent Claim
325 words
A process for preparing highly stereoregular polyolefins, which comprises polymerizing or copolymerizing α-olefins having at least 3 carbon atoms in the presence of a catalyst, said catalyst comprising (A) a titanium-containing solid catalyst component composed of an organic complex derived from (i) a magnesium dihalide, (ii) an organo polysiloxane selected from at least one of the group consisting of: compounds of the formula Q(Q.sub.2 SiO).sub.n SiQ.sub.3 wherein Q's are identical or different, and represent a moiety selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl, with the proviso that all Q moieties are not hydrogen at the same time, and n is an integer of 1 to 1000; compounds of the formula (Q.sub.2 SiO).sub.n wherein Q is the same as defined above, and n is an integer of 2 to 1000; and compounds of the formula X(Q.sub.2 SiO).sub.n SiQ.sub.2 X wherein Q is the same as defined above, n is an integer of 1 to 1000, and X is halogen, (iii) an organic carboxylic acid ester, and (iv) a titanium compound of the formula Ti(OR).sub.l X.sub.4-l wherein R is a moiety selected from the group consisting of alkyl groups and a phenyl group optionally substituted with an alkyl group with 1 to 4 carbon atoms, X is a halogen, and l is 0 or an integer of 1 to 4, and (B) at least one organoaluminum catalyst component of the formula R'.sub.m Al(OR').sub.3-m wherein R' moieties are identical or different, and represent alkyl, and m is a positive number of 1.5 to 3, said organic complex being derived by bringing the component (i) into contact with a combination of the components (ii) and (iii) in a molar ratio (i)/(ii)/(iii) of 1/1000-0.01/10-0.005 or a combination of the components (ii), (iii) and (iv) in a molar ratio (i)/(ii)/(iii)/(iv) of 1/1000-0.01/10-0.005/100-0.001 under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 3
Dependent Claim
24 words
The process of claim 1 wherein said magnesium compound (i) is selected from the group consisting of magnesium chloride, magnesium bromide and magnesium iodide.
Claim 4
Dependent Claim
111 words
The process of claim 1 wherein said silicon component (ii) is selected from at least one of compounds of the formula Q(Q 2 SiO) n SiQ 3 wherein Q moieties are the same or different and each selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl and C 6 -C 8 aryl; compounds of the formula (Q 2 SiO) n wherein Q is the same as defined above and n is an integer of 2 to 1000; and compounds of the formula X(Q 2 SiO) n SiQ 2 X wherein Q and n are the same as defined above, and X is halogen.
Claim 5
Dependent Claim
169 words
The process of claim 1 wherein said organic carboxylic acid ester (iii) is an organic carboxylic acid ester selected from the group consisting of esters formed between C 1 -C 8 saturated or unsaturated aliphatic carboxylic acids optionally substituted by halogens and alcohols selected from the group consisting of C 1 -C 8 saturated or unsaturated aliphatic primary alcohols, C 3 -C 8 saturated or unsaturated alicyclic alcohols and C 1 -C 4 saturated or unsaturated aliphatic primary alcohols substituted by C 6 -C 8 aromatic moieties or halogen; esters formed between C 7 -C 12 aromatic monocarboxylic acids and alcohols selected from the group consisting of C 1 -C 8 saturated or unsaturated aliphatic primary alcohols, C 3 -C 8 saturated or unsaturated alicyclic alcohols and C 1 -C 4 saturated or unsaturated aliphatic primary alcohols substituted by C 6 -C 8 aromatic moieties or halogen; and alicyclic carboxylic acid esters selected from the group consisting of methyl cyclopentanecarboxylate, methyl hexahydrobenzoate, ethyl hexahydrobenzoate, methyl hexahydrotoluate and ethyl hexahydrotoluate.
Claim 6
Dependent Claim
65 words
The process of claim 1 wherein the amount of said catalyst is such that the proportion of said titanium-containing solid catalyst component (A) is 0.0001 to 1.0 m-mol/liter, calculated as titanium atom, based on the volume of the liquid phase of the polymerization system, and the proportion of said organoaluminum catalyst component (B) is 1/1 to 100/1 in terms of the aluminum atom/titanium atom ratio.
Claim 7
Dependent Claim
169 words
The process of claim 1 wherein said organic carboxylic acid ester (iii) is an organic carboxylic acid ester selected from the group consisting of esters formed between C 1 -C 4 saturated or unsaturated aliphatic carboxylic acids optionally substituted by halogens and alcohols selected from the group consisting of C 1 -C 4 saturated or unsaturated aliphatic primary alcohols, C 5 -C 6 saturated or unsaturated alicyclic alcohols and C 1 -C 4 saturated or unsaturated aliphatic primary alcohols substituted by C 6 -C 8 aromatic moieties or halogen; esters formed between C 7 -C 10 aromatic monocarboxylic acids and alcohols selected from the group consisting of C 1 -C 4 saturated or unsaturated aliphatic primary alcohols, C 5 -C 6 saturated or unsaturated alicyclic alcohols and C 1 -C 4 saturated or unsaturated aliphatic primary alcohols substituted by C 6 -C 8 aromatic moieties or halogens; and alicyclic carboxylic acid esters selected from the group consisting of methyl cyclopentanecarboxylate, methyl hexahydrobenzoate, ethyl hexahydrobenzoate, methyl hexahydrotoluate and ethyl hexahydrotoluate.
Claim 8
Dependent Claim
15 words
The process of claim 3 wherein said silicon component (ii) is a linear alkyl polysiloxane.
Claim 9
Dependent Claim
39 words
The process of claim 7 wherein the linear alkyl polysiloxane is selected from at least one of the group consisting of methyl polysiloxane and ethyl polysiloxane, each having a viscosity of not more than 200 centipoises at 25° C.
Claim 10
Dependent Claim
26 words
The process of claim 6 wherein the organic carboxylic acid ester (iii) is a C 1 -C 4 primary alkyl ester of an aromatic carboxylic acid.
Claim 11
Dependent Claim
20 words
The process of claim 9 wherein the ester is selected from the group consisting of methyl benzoate and ethyl benzoate.
Claim 12
Dependent Claim
14 words
The process of claim 1 wherein the titanium compound (iv) is a titanium tetrahalide.
Claim 13
Dependent Claim
12 words
The process of claim 11 wherein the titanium tetrahalide is titanium tetrachloride.
Claim 14
Dependent Claim
17 words
The process of claim 1 wherein R' is a C 1 -C 4 straight-chain or branched-chain alkyl.
Claim 15
Dependent Claim
18 words
The process of claim 13 wherein the organoaluminum catalyst component is triethyl aluminum, tributyl aluminum, or their combination.
Claim 16
Dependent Claim
56 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with components (ii), (iii) and (iv) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 17
Dependent Claim
55 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with components (ii) and (iii) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 18
Dependent Claim
69 words
The process of claim 1 wherein said titanium-containing solid catalust component composed of an organic complex is derived by bringing the component (i) into contact with components (ii) and (iii) under mechanical pulverization conditions, then contacting the resulting pulverized product with the component (iv) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 19
Dependent Claim
67 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with component (iii) under mechanical pulverization conditions, then contacting the resulting pulverized product with the component (ii) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 20
Dependent Claim
82 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with component (iii) under mechanical pulverization conditions, then contacting the resulting pulverized product with the component (ii) under mechanical pulverization conditions, and further contacting the resulting pulverized product with the component (iv) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 21
Dependent Claim
67 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with component (ii) under mechanical pulverization conditions, then contacting the resulting pulverized product with the component (iii) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 22
Dependent Claim
82 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with component (ii) under mechanical pulverization conditions, then contacting the resulting pulverized product with the component (iii) under mechanical pulverization conditions, and further contacting the resulting pulverized product with the component (iv) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 23
Dependent Claim
62 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with component (ii) and an adduct of component (iv) and component (iii) under mechanical pulverization conditions, and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 24
Dependent Claim
72 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with component (ii) under mechanical pulverization conditions, then contacting the resulting pulverized product with an adduct of component (iv) and component (iii) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 25
Dependent Claim
64 words
The process of claim 1 wherein said titanium-) containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with components (ii), (iii) and an adduct of component (iv) and component (iii) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 26
Dependent Claim
63 words
The process of claim 1 wherein said titanium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with components (ii), (iv) and an adduct of component (iv) and component (iii) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 27
Dependent Claim
64 words
The process of claim 1 wherein said titamium-containing solid catalyst component composed of an organic complex is derived by bringing the component (i) into contact with components (ii), (iii), (iv) and an adduct of component (iv) and component (iii) under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 28
Dependent Claim
315 words
A catalyst for polymerization or copolymerization of α-olefins having at least 3 carbon atoms consisting essentially of (A) a titanium-containing solid catalyst component composed of an organic complex derived from (i) a magnesium dihalide (ii) an organo polysiloxane selected from at least one of the group consisting of: compounds of the formula Q(Q.sub.2 SiO).sub.n SiQ.sub.3 wherein Q's are identical or different, and represent a moiety selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl, with the proviso that all Q moieties are not hydrogen at the same time, and n is an integer of 1 to 1000; compounds of the formula (Q.sub.2 SiO).sub.n wherein Q is the same as defined above, and n is an integer of 2 to 1000; and compounds of the formula X(Q.sub.2 SiO).sub.n SiQ.sub.2 X wherein Q is the same as defined above, n is an integer of 1 to 1000, and X is a halogen, (iii) an organic carboxylic acid ester, and (iv) a titanium compound of the formula Ti(OR).sub.l X.sub.4-l wherein R is a moiety selected from the group consisting of alkyl groups and a phenyl group optionally substituted by an alkyl group with 1 to 4 carbon atoms, X is a halogen, and l is 0 or an integer of 1 to 4, and (B) at least one organoaluminum catalyst component of the formula R'.sub.m Al(OR').sub.3-m wherein R' moieties are identical or different, and represent alkyl, and m is a positive number of 1.5 to 3, said organic complex being derived by bringing the component (i) into contact with a combination of the components (ii) and (iii) in a molar ratio (i)/(ii)/(iii) of 1/1000-0.01/10-0.005 or a combination of the components (ii), (iii) and (iv) in a molar ratio (i)/(ii)/(iii)/(iv) of 1/1000-0.01/10-0.005/100-0.01 under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
Claim 29
Dependent Claim
315 words
A catalyst for polymerization or copolymerization of α-olefins having at least 3 carbon atoms consisting essentially of (A) a titanium-containing solid catalyst component composed of an organic complex derived from (i) a magnesium dihalide (ii) an organo polysiloxane selected from at least one of the group consisting of: compounds of the formula Q(Q.sub.2 SiO).sub.n SiQ.sub.3 wherein Q's are identical or different, and represent a moiety selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl, with the proviso that all Q moieties are not hydrogen at the same time, and n is an integer of 1 to 1000; compounds of the formula (Q.sub.2 SiO).sub.n wherein Q is the same as defined above, and n is an integer of 2 to 1000; and compounds of the formula X(Q.sub.2 SiO).sub.n SiQ.sub.2 X wherein Q is the same as defined above, n is an integer of 1 to 1000, and X is a halogen, (iii) an organic carboxylic acid ester, and (iv) a titanium compound of the formula Ti(OR).sub.l X.sub.4-l wherein R is a moiety selected from the group consisting of alkyl groups and a phenyl group optionally substituted by an alkyl group with 1 to 4 carbon atoms, X is a halogen, and l is 0 or an integer of 1 to 4, and (B) at least one organoaluminum catalyst component of the formula R'.sub.m Al(OR').sub.3-m wherein R' moieties are identical or different, and represent alkyl, and m is a positive number of 1.5 to 3, said organic complex being derived by bringing the component (i) into contact with a combination of the components (ii) and (iii) in a molar ratio (i)/(ii)/(iii) of 1/1000-0.01/10-0.005 or a combination of the components (ii), (iii) and (iv) in a molar ratio (i)/(ii)/(iii)/(iv) of 1/1000-0.01/10-0.005/100-0.01 under mechanical pulverization conditions and then, as an additional step, treating the resulting pulverized composition with the component (iv) in the absence of mechanical pulverization.
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| 3.5 Years (Year 4) | 1982-06-04 | 1982-12-04 | 1983-06-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-06-04 | 1986-12-04 | 1987-06-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-06-04 | 1990-12-04 | 1991-06-05 | $7700.00 | Window Closed / Lapsed |