JPS63202604A - Polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain a polymer with high stereoregularity by polymerization of an alpha-olefin in the presence of a catalyst prepared by prepolymerization of the alpha-olefin in the presence of a catalyst formed from a highly active Ti solid catalyst component, organometallic compound catalytic component and organic halogen compound catalytic component. CONSTITUTION:The objective polymer can be obtained by polymerization of an alpha-olefin in the presence of a catalyst prepared by prepolymerization of the alpha-olefin in the presence of a catalyst formed from (AS) a highly active Ti solid catalyst component with Mg, Ti and halogen as the essential components (e.g. as the essential components, a Mg compound such as dimethylmagnesium or MgCl2, a Ti compound such as TiCl4 and a halogen atom such as chlorine), (B) an organometallic compound catalytic component with the metal being group I, II or III metal of the periodic table [e.g., triethylaluminum, LiAl(C2 H5)4], and (C) an organic halogen compound catalytic component (e.g., methyl chloride, hexyl bromide).

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION J The present invention relates to a method for polymerizing α-olefin, and particularly to a polyα-olefin having excellent stereoregularity. More specifically, in a method of polymerizing α-olefin using a highly active α-olefin prepolymerization catalyst with excellent stereoregularity, even higher activation can be achieved without reducing stereoregularity. Regarding the method. E. Prior Art] Methods for producing crystalline polyolefins by polymerizing α-olefins such as propylene and 1-butene in the presence of stereoregular catalysts have been proposed in many prior art and are well known. Among these polymerization methods, formation from (axis) a highly active titanium solid catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, (b) an organometallic compound catalyst component, and (c) an electron donor catalyst component Methods for obtaining highly stereoregular polymers with high catalytic activity by polymerizing α-shaped fins in the presence of a catalyst have also been proposed in many previous technologies. It has been adopted on an industrial scale as an excellent polymerization method that does not require the removal of catalysts and amorphous polymers from the polymerized polymer, and there is a strong demand for streamlined technology, and a polymerization technology with even higher activation is required. There is. On the other hand, Junto Motode has already published in Japanese Patent Publication No. 57-31726 a titanium catalyst component obtained by treating a magnesium halogen compound/titanium halogen compound composite with an organic acid ester and a titanium compound, and a titanium catalyst component obtained from the periodic table.
proposed a method for polymerizing α-olefins in the presence of organometallic compounds of Group 3 or Group 3 metals, and published Japanese Patent Publication No. 56-454.
Publication No. 03 describes a solid catalyst component (^) obtained by reacting a titanium compound with an organometallic compound belonging to Groups 1 to 3 of the Periodic Table in the presence of a magnesium halogen compound φ titanium halogen compound complex; A method is proposed in which olefins are polymerized in the presence of a catalyst consisting of an organometallic compound component (B) of metals from Groups 1 to 3 of the Periodic Table. However, all of these methods have low polymerization activity and stereoregularity (there is a need for a polymerization method that is even better in these performances. [Problems to be Solved by the Invention] The present inventors have - Recognizing that the technology in the field of polymerization of fins is in the above-mentioned situation, this has been proposed in the past (
a) Highly active titanium solid catalyst component containing magnesium, titanium, halogen and electron donor as essential components, ω) Yes 8
! In a method of polymerizing an α-olefin in the presence of a catalyst formed from a metal compound catalyst component and (c) an electron donor catalyst component, further achieving high activation of the catalyst without reducing stereoregularity. As a result of intensive studies on possible methods, we found that at least (^) a highly active titanium solid catalyst component, (B) an organometallic compound catalyst component, and (C)
) It has been discovered that the above object can be achieved by polymerizing α-olefin in the presence of a catalyst obtained by prepolymerizing α-olefin in the presence of a catalyst formed from an organic halogen compound catalyst component, and the present invention invention has been achieved. [Means for Solving the Problems] According to the present invention, at least (^) a highly active titanium solid catalyst component containing magnesium, titanium, and halogen as essential components, (B) periodic table Organo* group compound catalyst component of Group 1 to Group 3 metals,
and (C) prepolymerizing α-olefin in the presence of a catalyst formed from an organic halogen compound catalyst component, and in the presence of the resulting α-olefin pre-am synthesis catalyst,
A method for polymerizing α-olefin is provided, which comprises polymerizing α-olefin. Hereinafter, the present invention will be explained in detail. In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymers but also copolymers. . The titanium catalyst component (A) used in the present invention is a highly active catalyst component that contains magnesium, titanium, and halogen as essential components, and contains a specific electron donor described later as an optional component. This titanium catalyst component (A) has a specific surface area of approximately: (m2/g or more), which is preferable, compared to commercially available magnesium halides. about 40 to about 1000 m2/g, more preferably about 80 to about 800 va2/g,
A hexane wash at room temperature does not substantially change its composition. In the titanium catalyst component (A), the electron donor/titanium (atomic ratio) is about 5 to about 200, particularly about 5 to about 100, and the electron donor/titanium (
molar ratio) is approximately 0. Preferably, the component (A) has a magnesium/titanium (atomic ratio) of about 2 to about 1001, particularly about 4 to about 50. It may contain other electron donors, metals, elements, functional groups, etc. It may also contain organic or inorganic diluents, such as silicon compounds, aluminum, polyolefins, etc. Such titanium catalyst components (A) is obtained, for example, by mutual contact of a magnesium compound (or magnesium metal), optionally an electron donor and a titanium compound;
Optionally, other reactants such as silicon, phosphorus,
Compounds such as aluminum can be used. As a method for producing such titanium catalyst component (A),
For example, JP 50-108385, JP 50-126
No. 590, No. 51-20297, No. 51-2818'
No. 1, No. 51-64586, No. 51-92885,
No. 51-136625, No. 51-87489, No. 5
No. 2-100596, No. 52-147688, No. 52
-104593, 5:3-2580, 53-
No. 40093, No. 53-43094, No. 55-1: No. 5102, No. 56-135103, No. 56-811
No. 56-11908, No. 56-18606, No. 5B-83006, No. 58-138705, No. 58
-138706, 58-138707, 58-
No. 138708, No. 58-138709, No. 58-1
No. 38710, No. 58-138715, No. 60-23
No. 404, No. 61-21109, No. 61-37802
No. 61-37803, No. 55-152710, and the like. Several examples of methods for producing these titanium catalyst components (A) will be briefly described below. (1) Grinding a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence or absence of an electron donor, a grinding aid, or the like or without grinding the electron donor and/or an organoaluminum compound. pretreatment with reaction aids such as or halogen-containing silicon compounds,
Alternatively, the solid obtained without pretreatment is reacted with a titanium compound that forms a liquid phase under the reaction conditions. (2) A solid titanium complex is precipitated by reacting a magnesium compound having no 31-element ability with a liquid titanium compound in the presence or absence of an electron donor. (3) React the material obtained in (2) with a titanium compound. (4) React the material obtained in (1) or (2) with an electron donor and a titanium compound. φ) A magnesium compound or a complex compound of a magnesium compound and an electron donor is ground in the presence or absence of an electron donor, a grinding aid, etc., and in the presence of a titanium compound. The solid obtained with or without pretreatment with a reaction aid such as an aluminum compound or a halogen-containing silicon compound is treated with a halogen or a halogen compound or an aromatic hydrocarbon. (6) Treating the compound obtained in (1) to (4) above with a halogen, a halogen compound, or an aromatic hydrocarbon. Among these preparation methods, those manufactured by Will, using liquid titanium halide, or those using a halogenated hydrocarbon after or during use of a titanium compound are preferred. Examples of electron donors that can be a component of the highly active titanium catalyst component (A) of the present invention include alcohols, heptenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, and acid amides. , oxygen-containing electron donors such as acid anhydrides, ammonia, amines, nitriles,
Examples include nitrogen-containing electron donors such as incyanate, and more specifically, methanol, ethanol,
Alcohols with 1 to 18 carbon atoms such as propatool, pentanol, hexanol, octatool, 2-ethylhexanol, dodecamer, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbennor alcohol; phenol , cresol, xylenol, ethylphenol, propylphenol, cumyl phenol, /nylphenol, naphthol, and other phenols having 6 to 25 carbon atoms; acetone, methyl ethyl ketone, methyl isobutyl ketone , acetophenone, benzophenone and other ketones having 3 to 15 carbon atoms; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde,
Aldehydes having 2 to 15 carbon atoms such as naphthaldehyde; methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, pro1, j
,! ++ 6- +LII-enemy-11J j
-11-, two saliva; Ethyl acid, 1,2-
Ethyl cyclohexanecarboxylate, di2-ethylhexyl 1,2-cyclohexanedicarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benol benzoate, toluyl methyl acid,
Ethyl toluate, amyl toluyl, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, trimethyl heptalate, noethyl heptalate,
An organic compound having 2 to 30 carbon atoms containing an ester described below that is preferably contained in a titanium catalyst acid lanthanum, such as butyl heptatarate, dioctyl heptatalate, γ-bunarolactone, δ-valerolactone, coumarin, hetatalide, ethylene carbonate, etc. Acid esters: Inorganic acid esters such as ethyl silicate, butyl silicate, vinyltriethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane; acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride, heptal Acid halides having 2 to 15 carbon atoms such as acid trichloride; methyl ether, ethyl ether, isopropyl ether, methyl ether,
Ethers having 2 to 20 carbon atoms, such as amyl ether, tetrahydro-7rane, anisole, and 7-22 ether; Acid amides, such as acetic acid amide, benzoic acid 7-mide, and toluic acid amide; Benzoic anhydride, 7-talic anhydride Acid anhydrides such as methylamine, ethylamine, noethylamine, tributylamine, piperidine, tribenzylamine, aniline, bilinone, picoline, tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile, tolnitrile; etc. can be mentioned. Two or more types of these electron donors can be used. The electron donor desirably contained in the titanium catalyst component is an ester, and more preferably an electron donor of the general formula % (where R+ is a substituted or unsubstituted hydrocarbon group, R2, R
5, R8 is hydrogen or a substituted or unsubstituted hydrocarbon group, RJ
, R4 are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. Further, R3 and R4 may be connected to each other. The hydrocarbon group substituted for R'-R' above includes a heteroatom such as N, O, S, etc., for example, C-
0-C%C0OR, C00H, OH, So, H, -C-
It has a group such as N-C-1N H2. )c
Examples include those having a skeleton that is A-shaped. Particularly preferred among these are nocarboxylic acid noesters in which at least one of R'%R2 is an alkyl group having 2 or more carbon atoms. Specific examples of preferable polyvalent carbonyl esters include diethyl succinate, butyl succinate, noethyl methylsuccinate, noisobutyl α-methylglutarate, butylmethyl malonate, noethyl malonate, diethyl ethylmalonate, and noethyl isopropylmalonate. , butyl diethyl malonate, phenyl diethyl malonate, diethyl malonate, allyl diethyl malonate, noisobutyl diethyl malonate, noflumalbutyl diethyl malonate, dimethyl maleate, monooctyl maleate, dioctyl maleate, butyl maleate , dibutyl butyl maleate, diethyl butyl maleate,
Aliphatic polycarboxylic acid esters such as diisopropyl β-methylglutarate, noallyl ethylsuccinate, no-2-ethylhexyl 7malate, diethyl itaconate, dibutyl itaconate, dioctyl citraconate, dimethyl citraconate, 1,2-cyclohexanecarboxylic acid Noethyl, diisobutyl 1,2-cyclohexanecarboxylate,
Alicyclic polycarboxylic acid esters such as dienal tetrahydro-7talate, diethyl nazic acid, monoethyl heptalamate, dimethyl heptalarate, methylethyl heptalarate, mo/isobutyl heptalarate, mono-normal butyl heptalarate, 7
Diethyl tallate, ethyl isobutyl 7-talate, ethyl n-butyl 7-talate, 11-propyl 7-talate, 7
Diisopropyl tallate, di-n-butyl heptalate, diisobutyl heptalate, non-n-hebutyl heptalate, di-2-ethylhexyl heptalate, di-n-octyl heptalate, dineobentyl heptalate, heptalamate Zodecyl, benzylbutylphenyl heptatalate, diethyl naphthalenenocarboxylate, dibutyl naphthalenenocarboxylate, triethyl trimellitate,
Examples include aromatic polycarbonate esters such as butyl trimellitate, and heterocyclic polycarboxylic acid esters such as 3,4-7 randicarboxylic acid. Specific examples of preferable polyhydric hydroxy compound esters include 1,2-7cetoxybenzene, 1
-Methyl-2,3-noacetoxybenzene, 2,3-diacetquinaphthalene, ethyleneglyfur nobivalate, butanool biparate, and the like. Examples of esters of hydroxy-substituted carboxylic acids include benzoylethyl salicylate, acenalisobutyl salicylate, acetylmenarsalinalate, and the like. Other examples of polyvalent carboxylic acid esters that can be supported in the titanium catalyst component include adipine diethyl,
7 Neusoptyl divicate, diisopropyl sebacate,
n-butyl sebacate, di-n-octyl sebacate,
Mention may be made of esters of long chain dicarboxylic acids such as 2-ethylhexyl sebacate. Among these polyfunctional esters, those having the skeleton of the above-mentioned general formula are preferred, and esters of 7-talic acid, maleic acid, substituted malonic acid, etc. and alcohols having 2 or more carbon atoms are more preferred. Particularly preferred is a diester of 7-talic acid and an alcohol having 2 [h] carbon atoms. Other electron donor components that can be supported on the titanium catalyst component include RCOOR' (RSE (,' is a hydrocarbyl group that may have a substituent, and at least one of them is a branched chain (tilt cyclic) ) or a ring-containing chain group).For example, as R and/or R', (CH3)2CH-
, C 2 H s CH (CH,)-, (C
H3)2CHCH,-, (CH.)3C-, C2HSC
It may be a group such as H H 3 CH2=C-. ■(or +('
If either one of them is a group as described above, the other may be a group as described above, or another group, such as IJP, 1
r〕11Ja Busy going to and from lectures

[Specifically,
trimethylacetic acid, trimethylacetic acid, α-methylbutyric acid, β-
Examples include various monoesters such as methylbutyric acid, methacrylic acid, and benzoyl acetic acid, and various monocarboxylic acids of alcohols such as isopropyl alcohol, isobutyl alcohol, and tert'7'alcohol. Donate electrons. Nisder carbonate can also be selected as a body. Specifically, examples include noethyl carbonate, ethylene carbonate, diisopropyl carbonate, phenylethyl carbonate, and no7dyl carbonate. When supporting these electron donors, it is not necessarily necessary to use them as starting materials, but compounds that can be converted into these in the process of preparing the titanium catalyst component are used and converted into these compounds at the step of producing the titanium catalyst. It's okay. Although other electron donors may coexist in the titanium catalyst component, their coexistence in too large a quantity will have an adverse effect, so they should be kept to a small amount. Come to Book 9 Moe. 4N:P! (A) Gou Sendan-nee is l"
The magnesium compound used in the preparation of M4 is a magnesium compound with or without reducing ability. Examples of the former include magnesium compounds having magnesium-carbon bonds or magnesium-hydrogen bonds, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, butylmagnesium, noamylmagnesium, nohexylmagnesium, butylmagnesium, ethylmagnesium chloride, and propylmagnesium. Examples include magnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, and butylmagnesium hydride. These magnesium compounds can be used, for example, in the form of a complex compound with organoaluminium, etc., and may be in a liquid or solid state.On the other hand, as a magnesium compound without reducing ability, magnesium chloride is used. , magnesium halides such as magnesium bromide, magnesium iodide, magnesium fluoride; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, impropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; phenoxymagnesium chloride, Allyloxymagnesium halides such as methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, ptoxymagnesicum, n-octoxymagnesium, 2-ethylhexoxymagnesium; phenoxymagnesium, dimethyl 7 Examples include aryaxymagnesium such as /xymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate. Also,
These magnesium compounds without reducing ability may be those derived from the above-mentioned magnesium compounds having reducing ability, or those derived during the preparation of the catalyst component. For example, magnesium compounds with reducing ability and polysiloxane compounds, Examples include a method of converting it into a magnesium compound without reducing ability by contacting it with a compound such as a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, or an alcohol. Also,
The magnesium compound may be a complex compound with other metals, a composite compound, or a mixture with other metal compounds.
Furthermore, a mixture of 2M or more of these compounds may be used. Among these, preferred magnesium compounds are those without reducing ability, and particularly preferred are halogen-containing magnesium compounds, particularly magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride. In the present invention, there are various titanium compounds used for preparing the solid titanium catalyst component (A), but usually Ti(
OR) gX, (R is a hydrocarbon group, X is halodane, O
A tetravalent titanium compound represented by ≦“≦4” is preferable.More specifically, T iC1,, TiBr, , 'l'
i1. Tetrahalogenated titanium such as Ti(OCH,
)CI,,Ti(OC2HS)C11,Ti(On-
C,H,)Ch,T i(OCzHs)B l”3,T
Trihalogenated alkoxy titanium such as i(O1soC<Ha)Brz; Ti(OCHs), zc 12,
T i(OC2H5)2C12,'l'1(On C
= H*) t e l □, Ti(OCd(s)2
Dihalogenated alkoxy titanium such as 8r2; T i (
OCH1) sc l, T i (OC2H5)3Cl, T
i(On C4HI)3CI, 1” 1(OCzHs
) monohalogenated trialkoxytitanium such as zBr;
T i (OCH3) 4, "l'! (OC28S) 4,
Examples include tetraalkoxytitanium such as 'l' + (On -C4Hs)4. Preferred among these are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be used after being diluted with a hydrocarbon or halogenated hydrocarbon. Titanium catalyst components (A> made by 7R, titanium compound, magnesium compound, and electron donor to be supported, as well as electron donors that may be used as necessary, such as alcohol, 7-ethyl, moacarboxylic acid) The amount of ester, silicon compound, aluminum compound, etc. to be used varies depending on the preparation method and cannot be absolutely specified, but for example, the amount of electron donor to be supported per 1 mol of magnesium compound is 0.05 to 5 mol, and the titanium compound is 0.05 to 5 mol.
The ratio can be approximately 0.00 mol. Examples of the halogen atom constituting the titanium catalyst component include fluorine, chlorine, central atom, iodine, and mixtures thereof, with chlorine being particularly preferred. When the titanium solid catalyst component (A) contains an electron donor in the method of the present invention, a polymer having particularly excellent stereoregularity can be obtained by the polymerization method of the present invention. In the present invention, the titanium solid catalyst component (A
) and an organometallic compound catalyst component of a metal from Group 1 to Group 3 of the periodic table, such as an organic aluminum compound catalyst component (
Polymerization or copolymerization of olefins using a combination catalyst of components B) and (C) described later. CB) may be (i) an organoaluminum compound having a small number (both one A1-carbon bond in the molecule), such as the general formula % (where R1 and R2 are carbon atoms, usually 1 to 15
, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, ■ is Oku-≦3, n is 0≦n<3, p is 0≦1summer<3, q is the number of 0≦q: (and m + n + p + An organoaluminum compound represented by the general formula % (where M' is Li%Na5K and R1 is the same as Aft), a group 1 metal represented by the general formula %, and aluminum and Examples include complex alkylated products of, (to) dialkyl compounds of Group 2 metals represented by the general formula % (where R1 and R2 are the same as above, and M2 is Mg, Zn, and Cd). Examples of the organoaluminum compounds belonging to (i) above include the following. General formula % formula %) (Here, R1 and (7R" are the same as above, - is preferably a number of 1.5≦-3), General formula R'AIX3-m (Here, R1 is the same as above. X is halogen, - is preferably 0 < ta < 3), general formula R' A
I Hs-m (where R1 is the same as above, a+ is preferably 2≦[1
<3), general formula R'mA I(OR")nX q (where R1 and R2 are the same as above, X is /N rodene, 0<
m≦3.0≦n<3.0≦q<3, and a++n+q=3
) can be given as an example. Among the aluminum compounds belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tribunal aluminum, trialkyl aluminum such as triisoprenyl aluminum, dialkyl aluminum alkoxide such as diptylaluminium butoxide, and ethyl aluminum sesquiethoxy In addition to alkylaluminum sesquialkoxides such as butylaluminum sesquibutoxide, l(l A1(OR
2). , butylaluminum chloride;
Dialkyl aluminum halogenides such as diethylaluminium bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, alkyl aluminum sesquihalodenides such as ethyl aluminum sesquipromide, ethyl aluminum dichloride, probyl aluminum dichloride, butyl Partially halogenated alkylaluminiums such as alkylaluminum dihalodenides such as aluminum nobromides, sialyl hydrides such as diethylaluminum hydride, butylaluminum hydride, alkylaluminum rhamnohydrides such as probylaluminum ramushihydride, etc. Partially hydrogenated alkyl aluminum, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, partially flukoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxybromide. As a compound belonging to direct distribution Gi), LiΔI (C2H
5) 4, L i A l (C, H+ s ) 4, etc., and examples of compounds belonging to the above (g) include diethylzinc and noethylmagnesium. Alkylmagnesium halides such as ethylmagnesium chloride can also be used. Among these, it is preferable to use trialkylaluminum, alkyl aluminum halide, a mixture thereof, etc. Examples include organic halogen compounds consisting of a hydrogen group and a halogen group such as chlorine, bromine, iodine, and halogen groups.More specifically, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, and bromide. Ethyl, ethyl iodide, propyl heptadide, isopropyl heptadide, n7'ropyl chloride, isopropyl chloride, n-propyl bromide, isopropyl bromide, isopropyl iodide, n-butyl chloride, 5ec-butyl chloride, isobutyl chloride , tert-butyl chloride, te bromide
rt-butyl, tert-butyl iodide, rho 7 mil chloride, active 7 mil chloride, isoamyl chloride, tert- chloride
7mil, neopentyl chloride, isoamyl bromide, te bromide
Alkyl halides such as rt-7 mil, rhohexyl chloride, hexyl bromide, hebutyl chloride, octyl chloride, decyl chloride, vinyl chloride, vinyl bromide, vinyl iodide,
Unsaturated monohalogen derivatives such as 1-propenyl chloride, isopropenyl chloride, isopropenyl bromide, methylene chloride, methylene bromide, methylene iodide, ethylidene chloride,
Ethylene chloride, propylidene dichloride, propylene dichloride, impropylidene dichloride, isopropylidene dibromide,
Saturated nohalogen derivatives such as 1,2-dichlorobutane, 1,3-dichlorobutane, pentamethylene dichloride, hexamethylene dichloride, unsaturated nohalogen derivatives such as vinylidene dichloride, 1,2-dichloroethylene, other chloroform, trichloropropane , Illized carbon and other multi-halogen derivatives. Among these organic halogen compounds, chlorides are preferred, and chlorides containing branched hydrocarbon groups are particularly preferred. In the present invention, (A) a highly active titanium-hedral catalyst component containing magnesium, titanium, and halogen as essential components; (B) an organometallic compound catalyst component belonging to Groups 1 to 3 of the periodic table;
In addition to (C') an organic halogen compound catalyst component, (D) a catalyst component consisting of an organic silicon compound or highly sterically hindered amines can optionally be used. Among the [D] catalyst components used in the present invention, the organic silicon compound is generally 5i-0-C or 9i-N
-C, 觑 TF奥 1-例文进联 7-9 Reran, aryloxysilane, and the like. For example, C1 formula RnS i(OR')
4-n (wherein, 0≦n≦3, R is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group, etc., or a halogen, R1 is a hydrocarbon group, For example, a silicon compound represented by an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxyfurkyl group, etc. (however, n R1 (4-n) OR1 groups may be the same or different) is used. can be given. Other examples include siloxanes having an OR1 group, silyl esters of carboxylic acids, and the like. Other examples include compounds in which two or more silicon atoms are bonded to each other via oxygen or nitrogen atoms. The above organosilicon compounds can be used by reacting a compound without Si OC bond with a compound having 0-C bond in advance or by reacting them in the polymerization field to convert them into a compound having 5i-QC bond. good. Examples of this include combinations of halogen-containing silane compounds or silicon hydrides that do not have Si-0-C bonds, and alkoxy group-containing aluminum compounds, alkoxy group-containing magnesium compounds, other metal alflates, alcohols, formic acid esters, ethylene oxides, etc. Examples include combination use. The organosilicon compound may also contain other metals (eg, aluminum, tin, etc.). More specifically, trimethylmethoxysilane, trimethylethoxysilane, nomethyldimethoxysilane, dimethyljethoxysilane, isobrobyldimethoxysilane, L-butylmethylnomethoxysilane, t-butylmethylethoxysilane, t-amylmethyl Noethoxysilane, nophenyldimethoxysilane, phenylmethylrenomethoxysilane, diphenyljethoxysilane, bis0
-Tolylnomethoxysilane, bis-tolyldimethoxysilane, bis p-)lylnomethoxysilane, bis p-tolyldethoxysilane, bisethylphenyldimethoxysilane, cyclohexylnomethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldimethoxy Silane, ethyltriethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltriaryxoxysilane, ■-pyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ -chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
t-Butyltriethoxysilane, n-butyltriethoxysilane, 1so-1 tiltriethoxysilane, phenyltrimethoxysilane, γ-7 mi/pyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane , vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane,
2-Norbornanetriethoxysilane, 2-Flubornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethyl7ethoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxy Silane, dimethyltetraethoxydisiloxane, etc. (naethyltriethoxysilane, n-propyltriethoxysilane, butyltriethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane,
Vinyltributoxysilane, nophenylcimethoxysilane, phenylmethyldimethoxysilane, bis p-)lylzomethoxysilane, p-tolylmethyldimethoxysilane, cyclohexyltomethoxysilane, cyclohexylmethyldimethoxysilane, 2-/nepornantriethoxy Silane, 2-flubornanemethyldimethoxysilane, diphenyljethoxysilane, ethyl silicate and the like are preferred. In addition, the amines with large steric hindrance include 2.2,
6,6-tetramethylpiverinone, 212°5,5-tetramethylpyrrolinone, or the like are preferred. Component (D) can also be used in the form of an adduct with other compounds. In the polymerization method of the present invention, when the catalyst component (D) is used, a polymer particularly excellent in stereoregularity can be obtained with higher commercial activity from an α-olefin having 3 or more carbon atoms such as propylene. The catalyst used in the olefin polymerization method of the present invention is an α-
This is an α-olefin prepolymerization catalyst obtained by prepolymerizing olefin. In the method of the present invention, α-
The following method can be exemplified as a method for forming the olefin prepolymerization catalyst. [11 Forming a catalyst in advance by contacting component (A), component (B), component (C), and optionally component (D) in an inert medium, and then contacting the catalyst with α-olefin. α-olefin reserve? R Now a method of forming a catalyst. (1)) A method of forming an α-olefin prepolymerization catalyst by contacting the components in the presence of an α-olefin, optionally in an inert medium or in an α-olefin medium. [31 After forming a catalyst in advance by contacting (A>component, (B) component, (C) component, and optionally (D) component), optionally in an inert medium or with an α-olefin A method of forming an α-olefin pre-4s polymerization catalyst by contacting with α-olefin in a medium. In the method of the present invention, component (A), component (B),
When the catalyst is formed by contacting component (C) and optionally component (D) in the absence of α-olefin, the temperature during the contacting process is usually -50 to 100°C;
The temperature is preferably -20 to 30°C, and the time required for the contact treatment is usually 1 minute to 10 hours, preferably 5 minutes to 2 hours. The contacting process is optionally carried out in the absence of the α-olefin component, in an inert medium, and when contacted in an inert medium, the catalyst is formed in suspension. When the catalyst is formed in a suspension, the catalyst suspension can be used as is for the prepolymerization of a-trimmed fins, or the catalyst formed from the suspension can be used as is. can also be separated and used for prepolymerization of α-onfin. In addition, in the method of the present invention, as described above, component (A), component (B), component (C) and optionally component (D) are mixed in an inert medium as necessary in the presence of α-olefin. by contacting in a medium or alpha-olefin medium,
Formation of the catalyst and formation of the α-olefin prepolymerization catalyst can be performed simultaneously or sequentially. In the method of the present invention, each of the components (A), (B), (C) and optionally (D) in the formation of the catalyst or the a-fin pre-polymerization catalyst (11) The ratio is as follows: The ratio of metal atoms M of component (B) to 1 gram atom of titanium of component (A) is usually in the range of 1 to 100 gram atoms, preferably 2 to 30 gram atoms. , the ratio in terms of halogen atoms X of component (C) to 1 gram atom of titanium of component (A) is usually 0.1 to 10 gram atoms, preferably 0.3
The ratio of (D) r#, to 1 gram atom of titanium of component (A) is usually in the range of 0.3 to 30 mol, preferably 0.7 to 5 mol. It is. In the method of the present invention, the prepolymerization is carried out at a concentration of 0.5 to 500 Fl per gram of the commercially active titanium solid catalyst component (A).
, preferably 1 to 100 g, more preferably 2 to 10 g, of α-olefin. The α-olefins used in the prepolymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, Examples include 1-dodecene and 1-tetradecene, but propylene is preferred. The prepolymerization temperature is -20°C to 70°C, preferably -11°C.
The temperature range is from 0°C to 60°C, more preferably from 0°C to 50°C. The time required for prepolymerization is usually 0.5 to 20 hours, preferably 1 to 10 hours. The prepolymerization can be carried out either batchwise or continuously, and can be carried out at normal pressure or under pressure. In the prepolymerization, a molecular weight agent such as hydrogen may be present, but the intrinsic viscosity [1] measured in decalin at at least 135°C is 0.2 dl/g or more, preferably 0.5 to 20 dl/g. It is preferable to keep the amount to a level that allows the production of a prepolymer. Prepolymerization is carried out without a solvent or in an inert medium. P
Prepolymerization in an inert hydrocarbon medium is preferred from the viewpoint of productivity. Examples of the inert hydrocarbon medium used in the prepolymerization include the above-mentioned solvents. The concentration of the solid catalyst in the prepolymerization reaction system in prepolymerization is usually 1 as the concentration of transition metal atoms in the solid catalyst.
0-6 to 1 gram atom/2, preferably 10″″4
and 10-2 gram atoms/2. In the method of the invention, the formation of said catalyst or said α-
Inert media that may be used in the formation of olefin prepolymerization catalysts include aliphatic hydrocarbons such as ethane, propane, butane, pentane, methylbenzene, hexane, heptane, octane, decane, butane, kerosene, gas oil, etc. Examples include alicyclic hydrocarbons such as , cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene, and an inert medium consisting of a mixture of two or more of these may be used. You can also do it. Similarly, as the α-olefin medium, the α-olefin exemplified as the α-onfin for prepolymerization can be similarly exemplified. In the α-olefin polymerization method of the present invention, the α-olefin prepolymerization catalyst is formed in the form of an R suspension by the above prepolymerization. The suspension can be used as such, or the catalyst produced from the suspension can be used after being separated. The α-olefin prepolymerization catalyst obtained by the above-mentioned pre-11 polymerization exhibits excellent polymerization activity in the polymerization of α-olefin. The olefins used for polymerization in the method of the present invention include ethylene, propylene, 1-butene, 4-methyl-1
-pentene, 1-octene, etc., and these can be subjected not only to homopolymerization but also to random copolymerization or block copolymerization. In copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can be selected as copolymerization components. Among these olefins, homopolymerization of propylene, 1-butene, or 4-notyl-1-pentene, or a mixture of these olefins and other olefins, with propylene or 1-butene as the main component (for example, 50 mol % or more, preferably 70 mol % or more), it is preferable to apply the method of the present invention to the polymerization or copolymerization of mixed olefins. In the process of the invention, the polymerization of the olefin is carried out in the gas phase or in the liquid phase, for example in the form of a slurry. In slurry polymerization, an inert hydrocarbon may be used as a solvent,
The olefin itself can also be used as a solvent. In the method of the present invention, the polymerization of α-olefin is carried out by the above α-olefin.
- In the zero polymerization reaction carried out in the presence of an olefin prepolymerization catalyst, it is possible to use only the above α-olefin prepolymerization catalyst, or in addition to the above α-olefin prepolymerization catalyst, component (B), (C) Component and (
D) It can be carried out by adding any one, two or three components of m. In the method of the present invention, the proportion of each catalyst component present in the polymerization reaction system is about o, o o i to about 0.5 milligram atom/l in terms of T1 atom for the catalyst component (A), particularly About 0.005 to about 0.5 mm! 7 gram atom/1, and for the catalyst component (B), the * Preferably, the catalyst component (D) contains about 0.1 to about 500 mol, preferably about 0.5 mol, of the catalyst component (D) per gram atom of titanium in the catalyst component (A). The range is from 100 moles to 100 moles. In the polymerization reaction, when performing polymerization by adding the catalyst component (B) in addition to the above α-olefin prepolymerization catalyst,
! The ratio of component (B) is about 1 to about 2000 gram atoms of gold and about 500 gram atoms. Similarly, in addition to the above α-olefin prepolymerization catalyst, the catalyst component (
When conducting polymerization by adding D), the proportion of component (D) added is about 0 to 1000 mol, preferably about 0 to about 100 mol, per 1 gram atom of titanium in the catalyst component (A). is within the range of The olefin polymerization temperature is preferably from about 20 to about 200
C., more preferably about 50 to about 180.degree. C., and the pressure is preferably from normal pressure to about 100 kg/cm2. Polymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, it is also possible to carry out the polymerization in 28 different stages under different reaction conditions. [Effects of the Invention] In the present invention, especially when applied to the stereoregular polymerization of α-olefin having 3 or more carbon atoms, a polymer having a stereoregularity index can be produced with high catalytic efficiency. Furthermore, in relation to the high activity, the polymer yield per unit solid catalyst component is superior to that of conventional proposals at the level of obtaining polymers with the same stereoregularity index. It is possible to reduce the catalyst residue, especially the halogen content, and it is possible to omit the catalyst removal operation, as well as to significantly suppress the tendency of molds to rust during molding. (Example) Next, it will be explained in more detail with reference to Examples. Example 1 [Preparation of solid 'ri catalyst component [Al] 7.14 g (75 mmol) of anhydrous magnesium chloride,
Decane: (8a+1 2-ethylhexyl alcohol 35.1 mj2 (225 mmol) at 130℃
After the time heating reaction was completed and a homogeneous solution was obtained, 1.7 g (11.3 mmol) of 7-talic anhydride was added to this solution.
Stirring and mixing are further performed at 130° C. for 1 hour to dissolve heptallic anhydride in the homogeneous t8 solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped over 1 hour into 200 mj2 (1.8 mol) of titanium tetrachloride maintained at -20°C. After charging, the temperature of this mixed solution was raised to 110°C over 4 hours, and when it reached 110°C, diisobutyl 7 thale) 5.03ml (18
, 75 mn+ol) and then kept at the same temperature for 2 hours with stirring. After the completion of the 2-hour reaction, the solid part was collected by hot filtration, and this solid part was 275 talf) T i
After chlorination with Cl 4 nitrite, the reaction was heated again at 110° C. for 2 hours. After the reaction is completed, the solid portion is again collected by hot filtration and thoroughly washed with decane and hexane at 110° C. until no free titanium compound is detected in the washing liquid. The catalyst component [Ai] is stored as a hexane slurry in the solid Ti synthesized by the above production method, and the concentration of the catalyst slurry is also measured at the same time. A part of this was dried to obtain a solid 'l'1 catalyst component [Al composition was titanium 2
゜4% by weight, chlorine 56% by weight, magnesium 19% by weight
The content of diisobutyl phthalate was 13.6% by weight. 1'f''i Catalyst component [Pretreatment of Al] In a 4001 4001 stirrer-equipped four-necked glass reactor, purified hexane 100 (up to) 1, triethylaluminum 1.0 mmol, and cyphenyl methoxysilane 2 were added under a nitrogen atmosphere. mmol, tert
After adding 0.5 mmol of butyl chloride and 2.0 grams of the above solid Ti catalyst component [Al], propylene was fed to the reactor at a rate of 3.2 Nl/Hr for 1 hour at a temperature of 20°C. When the supply of propylene is finished, the inside of the reactor is purged with nitrogen, and after performing a washing operation consisting of removing the supernatant liquid and adding purified hexane twice, resuspend in purified hexane and transfer the entire amount to the catalyst bottle. did. At this time, the total capacity was also measured, and the catalyst slurry concentration was also measured. 1 Polymerization] 750 ml of purified hexane in an autoclave with an internal volume of 21
0.75 Io101 of triethylaluminum, 0.075 mmol of nophenylnomethoxysilane, and the pretreated product of the catalyst component LAI were added at 60°C in a propylene atmosphere to 0°0075 mmIJ mole (the catalyst component) in terms of titanium atoms. [equivalent to 22.8 milligrams in terms of Al] was added. After introducing 200ml of hydrogen,
The temperature was raised to 70°C, and propylene polymerization was carried out for 2 hours. The pressure during polymerization was maintained at 7 kg/c and 2 G. After the polymerization was completed, the slurry containing the produced polymer was filtered and separated into a white powdery polymer and a liquid phase. After drying, the am of the white powdery polymer was 334.5 g, the extraction residue with boiling n-hebutane was 98.9536, the Ml was 2.7, and its apparent density was 0.44 g/+nl. Ta. On the other hand, 1.3 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. The activity was therefore 14.00 g pp/g-catalyst, and the fI for the total polymer was 98.5%. Comparative Example 1 The same pretreatment operation as in Example 1 was carried out except that 1 mmol of titanium tetrachloride was not added during the pretreatment of the Ti catalyst component tA]. Further, polymerization was carried out in the same manner as in Example 1, and the results of zero polymerization are shown in Table 1. Examples 2 to 5 Preliminary contact was carried out in the same manner as in Example 1, except that the amount of t-butyl chloride added and the solvent used during preliminary contact were changed as shown in Table 1, and propylene was polymerized. . The results are shown in Table 1. Example 6 The same method as in Example 1 was used except that the propylene supply rate and time during the preliminary contact were changed to 8 Nl/Hr and 4 hours, respectively, without conducting the preliminary Ia contact, and without polymerizing propylene. I did it. The results are shown in Table 1. Example 7 [Preparation of solid Ti catalyst component IAI] A high-speed stirring device (manufactured by Tokushu Kika Kogyo) with an internal volume of 21 was heated to sufficient N.
After 2 substitutions, M! lI kerosene 700 Shin 1, commercially available MgC
10 g of l□, 24.2 g of ethanol, and 3 g of Emazol 320 (trade name, manufactured by Kako Atlas Co., Ltd., sorbitan distearate)) were added, and the system was heated with stirring, and heated to 120° C. and 301 IPPJl at 800 rpm: Stirred. Under continuous stirring, using a Teflon tube with an inner diameter of 51111, the liquid was transferred to a 2121 round flask (equipped with a stirrer) filled with refined kerosene 11 previously cooled to -10°C. The generated solid is tPl! 1 and washed thoroughly with hexane to obtain a carrier. After suspending 7.5 g of the carrier in 1501 titanium tetrachloride at room temperature, 331 syn-n-octyl cyclohexanedicarboxylate was added, and after stirring and mixing at 120°C for 1.5 hours,
After removing the supernatant liquid by decantation, the solid portion was again suspended in 150+II titanium tetrachloride, and again suspended in 130+II titanium tetrachloride.
Stirring and mixing was performed for 1 hour at ℃. A reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component [AI]. The components were 2.6% by weight of titanium, 60% by weight of chlorine, and 19% by weight of magnesium in terms of atoms. [1'i catalyst component [AI pretreatment 1 In the pretreatment of Example 1, the Ti catalyst component used was carried out except that AI was replaced from the Ti catalyst component of Example 1 to the above '1' i catalyst component. Pretreatment and propylene polymerization were carried out in the same manner as in Example 1. The results are shown in Table 2. Comparative Example 2 A pretreatment was carried out in the same manner as in Example 7, except that 1 mmole of titanium tetrachloride was not added during the pretreatment of 1゛i catalyst component [AI]. Further, polymerization was carried out in the same manner as in Example 7. The polymerization results are shown in Table 2. Example 8 [Solid Ti catalyst component [Preparation of AI] 6 g of Mg*X in the form of 7 lakes and 100 l of n-hexane were added to a 400 ml flask and washed at 68°C for 1 hour.
Dry with nitrogen. Next, 1 g of ethyl silicate cord solution 0.1
1 in n-hexane and 1 in 50 mBull
A solution consisting of 25 g was added over a period of 1 hour to bring the temperature of the M mixture to 70°C and 61 L! 50℃ after completion of 6 reactions kept in darkness
It was washed six times using n-hexane. After suspending 7 g of the solid obtained in this way in 100 ml of T1Cl, 5.5 mmol of diisobutyl 7-talate was added and the reaction was carried out at 120°C for 1 hour. 1001 of T i Cl 4 was added at 120°C, 1
A time reaction was performed. After the reaction was completed, the solid Ti catalyst component [AI] was prepared by thoroughly washing with hexane. The Ti catalyst component [2.8% by weight of AI or titanium,
The contents were 60% by weight of chlorine, 19% by weight of magnesium, and 11.3% by weight of diisobutyl heptatarate. [Ti catalyst component [AI pretreatment J] Same method as Example 1 except that in the pretreatment of Example 1, the Ti catalyst component I used was changed from the Ti catalyst component of Example 1 to the above Ti catalyst component. Comparative Example 3 In Example 8, the same catalyst components as in Example 8 were used except that 1 mmol of titanium tetrachloride was not added during pretreatment of AI Pretreatment was carried out in a similar manner. Further, polymerization was carried out in the same manner as in Example 8. The polymerization results are shown in Table 2. Examples 9 to 12 In Example 7, the Ti catalyst component [cyclohexanedicarvone 11 used in 1nil production of AI! ) n-octyl was replaced with the electron donor shown in Table 3, and the cyphenylsimethoxysiphne used in the pretreatment of the riTi catalyst component I and the polymerization of propylene was replaced with the electron donor shown in Table 3. The same method as in Example 7 was carried out except that the 'l' i catalyst component [AI was
After pretreatment of I, propylene was polymerized. The results are shown in Table 3. Comparative Examples 4 to 7 Example 9 except that in Examples 9 to 12, Ti catalyst component [TiC1, was not added during pretreatment of AI]
Propylene was polymerized by pretreatment in the same manner as in steps 1-12. The results are shown in Table 3. Examples i 3 to 15 In Example 1, Ti catalyst component [0.5 mmol of tert-butyl chloride added before pretreatment of AJ was added in Table 4
The pretreatment was carried out in the same manner as in Example 1, except that , and propylene was polymerized in the same manner as in Example 1. The results are shown in Table 4.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing one example of a catalyst preparation method in the α-olefin polymerization method of the present invention. 1 other person

Claims (1)

[Claims] (1) At least (A) a highly active titanium solid catalyst component containing magnesium, titanium and halogen as essential components, (B) periodic table 1
An α-olefin prepolymerization catalyst obtained by prepolymerizing an α-olefin in the presence of a catalyst formed from an organometallic compound catalyst component of a Group to Group 3 metal, and (C) an organic halogen compound catalyst component. A method for polymerizing α-olefin, which comprises polymerizing α-olefin in the presence of.