JPS58120609A - High efficiency catalyst containing titanium and zirconium and olefin polymerization - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to polymerization processes using new and improved catalyst compositions useful for initiating and promoting the polymerization of a-olefins.

Polymerization of olefins such as ethylene, propylene and 1-butene in the presence of metal catalysts, particularly the reaction products of organometallic compounds and transition metal compounds, to produce relatively high molecular weight, substantially unbranched It is well known that polymers can be produced. Typically such polymerizations are carried out at relatively low temperatures and pressures.

Among the most widely used methods for producing linear olefin polymers is U.S. Pat. No. 8,118,115.
and 8.257,882 by Professor Karl Ziegler. In these methods, the catalyst used is based on Mendeleev's elemental cycle M
E.V.B.

It is obtained by mixing a compound of VIE and a group II transition metal with an organometallic compound. Generally, halides, oxyhalides and alkoxides of titanium, vanadium and zirconium are the most widely used transition metal compounds. Common examples of organometallic compounds are alkyls and haloalkyls of aluminum, alkyl aluminum halides, Grignard reagents, alkali metal aluminum halides, alkali borohydrides, metals, alkali metal hydrides, alkaline earth metal hydrides, etc. It is.

The polymerization is usually carried out in a reaction medium consisting of an inert organic liquid, for example an aliphatic hydrocarbon, and the catalysts mentioned above. 1
The eleven or more olefins may be contacted with the reaction medium in any suitable manner. A molecular weight regulator, usually hydrogen, is usually present in the reaction medium to suppress the formation of undesirably high molecular weight polymers.

Following polymerization, it is common to remove catalyst residues from the polymer by repeatedly treating the polymer with deactivating agents such as alcohols or other aqueous bases. Such catalyst deactivation and removal operations are expensive in terms of the time consumed and the equipment required to carry out such processes.

Moreover, most of the above-mentioned known catalysts work better in slurry form (i.e., when the polymer is not dissolved in the support) than in solution form (i.e., when the temperature is high enough to solubilize the incorporation into the support). It is efficient in producing polyolefins. The lower efficiency of such catalysts for solution polymerization is believed to be due to the general tendency of such catalysts to become rapidly exhausted or inactive due to the significantly higher temperatures commonly used in solution processes.

Additionally, processes involving copolymerization of ethylene with higher olefins exhibit significantly lower catalytic efficiencies than ethylene homopolymerization processes.

Recently, for example, US Pat. No. 8,892,159, US Pat.
and British time 1'l'1.805,610 and 1,868
, 487, disclosed a catalyst with relatively high efficiency. Although the increases in efficiency achieved by using these modern catalysts are significant, especially in copolymerization methods,
Even higher efficiency is desirable. These highly efficient catalysts generally produce polymers with relatively narrow molecular weight distribution. Therefore, in some applications such as injection molding, resulting in polymers and copolymers with relatively broad molecular weight distributions and solution polymerization temperatures above 140"C, polymers of desired purity can be obtained. It is desirable to have a high efficiency that is sufficient to obtain a high yield of olefin homopolymer or copolymer per unit of catalyst without requiring a separate treatment to remove the catalyst.

In one aspect, the present invention provides octavalent or tetravalent titanium compounds such as titanium trichloride or titanium tetraalkoxylate, zirconium compounds such as tri-butoxyzirconium chloride, and di-n-butoxymagnesium. Organic! Ziegler in the presence of a catalyst prepared by reacting a magnesium compound, a halogen source such as ethylaluminum dichloride and a halide source or an organoaluminium compound if the magnesium component does not contain sufficient aluminum. Under conditions specific to polymerization α
- It is a method of polymerizing olefins.

More particularly, the catalyst comprises: (A) an octavalent or tetravalent titanium compound or a mixture of such compounds; (B) a zirconium compound or a mixture of such compounds; (C) an organomagnesium compound; and CD) a halogen. It is a catalytic reaction product of a chemical source. Component (C) and (or) (Z))
does not contain a sufficient amount of aluminum compound, additional amounts of organoaluminum compound should be added. The magnesium component is (1) a complex of an organomagnesium compound and an organometallic compound that solubilizes the organomagnesium compound, or (2) a hydrocarbon-soluble organomagnesium compound. The halide source is a non-metal halide corresponding to the empirical formula R'X, where R' is hydrogen or an active monovalent deprivation machine residue and X is a halogen. Alternatively, the halide may have the empirical formula MR, -,
i is an organic residue, usually hydrocarbyl or hydrocarbyloxy, X is a halogen, V is a number corresponding to the valence of M, and α is a number from 1 to 1) It is a metal halide corresponding to The proportions of the aforementioned components of the catalytic reaction product are such that the molar ratio of the elements is as follows: Kg:Zr from about 1:1 to about 100
:1. Preferably from about 2.5:1 to about 50:11:
Most preferably from about 5:1 to about 25:1; Al:Zr from about 0.1:1 to about 100:1; preferably from about 0.6:1 to about 50:1: Most preferably from about 1:1 to about 25:1t: Zr:Ti from about 0.1:1 to about 50:1:
Preferably from about 0.5:1 to about 40=1: most preferably from about 1:l to about 20:l; the excess X:AL is from about 0.0005:1 to about 10
:1t; preferably from about 0.02:1 to about 2:1: most preferably from about 0.0111 to about 1.41.

The excess of X is an excess of halide over that theoretically required if the magnesium compound were to be converted to a dihalide.

Considering the decrease in activity of commonly used Ziegler catalysts in the copolymerization of a-olefins (especially at solution polymerization temperatures),
It is indeed surprising that the catalytic reaction product described above is a highly efficient catalyst capable of producing over 1 million parts by weight of olefin polymer or copolymer per part of transition metal under such polymerization conditions. That's true. Therefore, olefin polymers produced by this method generally contain less catalyst residue than polymers obtained in the presence of conventional catalysts, even after the conventionally obtained polymers are subjected to a catalyst removal treatment. Contains. Moreover, these catalytic reaction products have a relatively broad molecular weight distribution and, at relatively high amounts of zirconium, polymers result therefrom that have a lower melt index than corresponding catalysts without zirconium compounds.

The catalyst composition of the present invention is typically a dark brown slurry of very fine particles. The ygct present is a fine off-white precipitate containing a surface area of approximately 250 m''/l.

ZrcLm exhibits a wide range of particle sizes. If alcohol is present, the solid 11rcla will dissolve, possibly forming a compound of the general formula Zr(OR)zcly, where o<z<+ and 0<y<4. The exact structure of this Zr-Ti catalyst is unknown.

The invention is most advantageously carried out during the polymerization of alpha-olefins, generally in the presence of hydrogen as a molecular weight control agent, in a polymerization zone containing an inert diluent and the catalytic reaction product described above. tl! Advantageous for f is the copolymerization of ethylene and higher α-olefins using the catalytic reaction products of the invention. The process is most advantageously carried out in an inert atmosphere and relatively low pressure, although very high pressures are optional.

Olefins suitable for homopolymerization or copolymerization in the practice of this invention are generally #c aliphatic alpha-monoolefins or non-conjugated alpha-diolefins having from 2 to 18 carbon atoms. By way of example, the higher α-olefins include ethylene, phlopylene, phthene-1, pentene-1,
1,8-methylbutene-1,4-methylpentene-1,
Includes hexe/-11 octene-1, dodecene-1, octadecene-1% 1,4-hexadiene, and 1,7-octadiene.

The α-olefins may include other α-olefins and/or small amounts, i.e., up to about 25% by weight, based on the polymer, of styrene, α-methylstyrene, and similar ethylenes that do not destroy conventional Ziegler catalysts. It is understood that it may be copolymerized with other ethylenically unsaturated monomers, such as ethylenically unsaturated monomers. The biggest advantage is that aliphatic α-monoolefins,
50, especially based on ethylene and total monomers of ethylene;
In particular, from about 0.1 to about 40% by weight of propylene, butene-1, hexene-1, octene-1,4-methylpentene-1, l,4-hexadiene, l,7-octadiene or similar a - olefins or mixtures with non-conjugated α-diolefins.

As used herein, hydrocarbyl and hydrocarbyloxy are monovalent chlorinated water X residues. Preferably, hydrocarbyl is alkyl, cycloalkyl, aryl, aralkyl, alkenyl and similar hydrocarbon residues having from 1 to 20 carbon atoms, and from 1 to 10 carbon atoms.
Particularly preferred are alkyls having carbon atoms of . Similarly, preferably hydrocarbyloxy is 1 to 20
alkoxy, cycloalkoxy, aryloxy, aralkyloxy, alkenyloxy and similar oxyhydrocarbon radicals having from 1 to 10 carbon atoms, preference being given to alkoxy having from 1 to 10 carbon atoms.

Advantageously, the tetravalent titanium compound has the formula: T iXs (
OR) a-s (wherein X is halogen, especially chlorine or bromine, R is from 1 to 20, preferably from 1 to 10
is a hydrocarbyl group having up to 4 foot atoms and has an i-terminus of 0 to 4 vljIt). Such titanium compounds are preferably derived from tethanologenides in which one or more of the halogen atoms is replaced by an alkoxy or aryloxy group. Examples of such compounds are tetra-5-butoxytitanium,
Includes tetra(isopropoxy)titanium, di-butoxytitanium dichloride, monoethoxytitanium trichloride, and tetraphenoxytitanium.

Suitable octavalent titanium compounds include α- and γ-TiC and the empirical formula: TiZa (L) z , where Z is a halide and L is water or an organic electron donor,
Examples include octavalent titanium complexes, such as alcohols, ethers, ketones, amines, or olefins, where X is an integer from 1 to 6. Typically, the organic electron donor has 1 to 12 carbon atoms, and examples of suitable electron-donating compounds for use in donating electrons to the complex (%5hared) are fatty acids. family alcohols,
For example, isopropyl alcohol, ethanol, n-propyl alcohol, butanol and others with 1 to 12 carbon atoms: ethers with 1 to 20 carbon atoms: ketones; aldehydes; amines, niolefins, etc. It also includes water. In a preferred complex, Z is chloride or bromide, most preferably chloride, and L is an alcohol, especially isopropyl alcohol, s-7'' lobil alcohol, %-
such as phthalic alcohol and isobutyl alcohol,
It is an aliphatic alcohol having 2 to 8 carbon atoms and most preferably 8 to 6 carbon atoms. The exact structure of this complex is not known, but it has eight valence bonds for the halide ion and between 1 and 6, preferably 2 and 4, coordinate bonds for the electron donating compound. Believable.

In addition to .alpha.-TiC1, the .DELTA., .gamma. and .beta. crystalline forms of titanium trichloride are preferably used in the preparation of the complexes. Titanium tribromide, titanium trichloride, etc. are also suitable. Among the above, the γ- and α-forms of titanium trichloride are preferred.

These complexes and their method of preparation are described in more detail by Perkelbach in US Pat. No. 4,120,820.

A suitable zirconium compound has the formula: ZrX%(OR)
a-% (wherein each R is independently from 1 to 20, preferably (
is a hydrocarbyl group having from 1 to 10 carbon atoms, each X independently being a halogen atom, preferably chlorine or bromine, and the others having a valence from 0 to 4). It is something that you have.

Particularly suitable zirconium compounds are, for example, ZrCl
4, ZrEra, Zr((JsZ?s)+, Zr(On
Pr) 4, Zr(OEt)ICI,.

Zr(OEt)tBrt, Zr(OsPr), C1,
, Zr(OthPr)tBrt.

Zr(OiPr)2CL1, Zr(O4Pr), By
,,Zr(OsBs)1C5,Zr(OnB%)2B
rts includes mixtures thereof, etc. In the above formula, Et=ethyl, (Pde=inpropyl, %Pde=normal dipropyl and %Bs=normal butyl.

A zirconium compound represented by the empirical formula Zr(OE)zXWc in which O≦z(4) contains zirconium tetrahalide and
from up to about 20 carbon atoms, a suitable alcohol can be prepared in situ by addition to an aliphatic alcohol having from 1 to about 10 carbon atoms. The molar ratio of alcohol to zirconium halide is from about 0.01 to about 10, preferably from about 0.25 to about 4.

A suitable organomagnesium component has the empirical formula: MgR:・z
Mft'y (wherein R# is independently hydrocarbyl or hydrocarbyloxy, M is aluminum, zinc, boron, silicon, tin, phosphorous or mixtures thereof, and 2 is about 0 to 10; % is from about 0 to about 0.25, and 1 is a hydrocarbon soluble complex exemplified by the number corresponding to the valency of M. Polymerization temperatures above 180° C. The best catalytic effect
4, it is desirable to reduce the amount ta of aluminum in the complex as well as in the total catalyst. Therefore, for catalysts with Al:TiHl ratios of less than 120:1, Mfl:At atomic ratios of greater than 0.8:1, preferably from about 0.5:1 to lO:1 are preferred. It is desirable to have crabs.

Preferably the organomagnesium compound is a hydrocarbon soluble dihydrocarbylmagnesium such as magnesium dialkyl and magnesium diaryl. Examples of suitable magnesium dialkyls are in particular exo-butyl-sec-butylmagnesium, diisopropylmagnesium, di-9-hexylmagnesium, isopropyl-phthermacnesium, ethyl-hexylmagnesium, ethyl-hexylmagnesium, octylmagnesium and others in which each alkyl has from 1 to 20 carbon atoms. Examples of suitable magnesium diaryls include diphenylmagnesium, dibenzylmagnesium and ditolylmagnesium. Suitable organomagnesium compounds include alkoxylated and trioxylated alkyl and hyarylmagnesiums, and halogenated alkyl and arylmagnesiums, with halogen-free organomagnesium compounds being more preferred.

Suitable sources of halides include hydrogen halides, t-alkyl halides, allyl halides, benzyl halides, and other active hydrocarbyl halides, where hydrocarbyl is as previously defined herein. Active non-metal halides of the formulas hereinbefore described include active organic halides. Active organic halides are halogens having a mobile hydrogen that is at least as active as sec-butyl chloride, i.e. is lost towards other compounds, and preferably as active as t-butyl chloride. Hydrocarbyl. Besides organic dino-halides, organic dino-halides, trino-halides and other polyhalides which are active as defined hereinabove are also suitable for use herein. Examples of suitable active non-metal halides are hydrogen chloride, hydrogen bromide, t-chloride
Butyl, t-amyl bromide, allyl chloride, benzyl chloride,
Includes crotyl chloride, methylvinylcarvinyl chloride, α-phenylethyl JI, and diphenylbenzyl JE.

Suitable metal halogenides as hereinbefore described are:
These are organometallic halides and metal halides in which the metal is in group ■A or ■A of the Pendayev table. Suitable metal halides have the empirical formula AIEs-a'α, where R is independently a hydrocarbyl as hereinbefore defined such as alkyl, X is halogen, and α is It is an aluminum halide with a number from 1 to 8).

Most preferred are alkylaluminum halides such as ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, and diethylaluminum bromide, with ethylaluminum dichloride especially n. Alternatively, it is suitable to use metal halides such as aluminum trichloride or a combination of aluminum trichloride and an alkyl aluminum halide or a trialkyl aluminum compound.

The organic moiety of the organomagnesium compound, e.g. R'', and the organic moiety of the halide source, e.g. R and R'
is understood to be any other M moiety residue, as long as it does not contain functional groups which are suitably poisonous to conventional Ziegler catalysts. Preferably such organic moieties contain active hydrogen, i.e.
Contains nothing active enough to react with Zelewitenoff's reagent.

For ease of catalyst preparation, the catalyst is prepared by mixing the components of the catalyst in an inert liquid diluent in the following order: (1) halide source 0, (2) Fjr.
(4) Zirconium compound and (5) Organomagnesium component 0°. However, if the titanium and/or zirconium compound is overreduced (overreduced) by other catalyst components, It is understood that any suitable order of addition can be used, as long as the reduction is not achieved (as indicated by a severe decrease in catalyst efficiency or total inactivity of the catalyst).

These catalyst components are combined in OK sufficient proportions to yield the atomic ratios as shown.

If neither the organomagnesium compound nor the halide source contains aluminum, the total catalyst contains an alkyl aluminum compound, e.g.
It is necessary to include aluminum compounds such as fukylaluminium oxygenide or aluminum halides.

If a polymerization temperature lower than 180°C is used, Al
The atomic ratio of T2 is from about 0.1:1 to about 2000:
1, preferably from 1:1 to 200:1. However, when polymerization temperatures higher than 180° C. are used, the MW:A1 ratio is greater than 0.8:1, preferably from 0.5:1 to 10=1, and A
I:Ti ratio is less than 120:1, preferably 50:1
Aluminum compound*1* is used in a smaller proportion. The use of very low amounts of aluminum requires the use of high purity solvents or diluents, and the other components should be essentially free of impurities that would react with the aluminum alkyl. Otherwise, additional amounts of an organometallic compound, preferably an organoaluminum compound, as described above, must be used to react with such impurities.

Furthermore, the aluminum compound in the catalyst should be in the form of an alkyl aluminum halide substantially free of trialkylaluminum or halide alkylaluminum halides.

The preparation of the catalyst is preferably carried out in the presence of an inert diluent. The concentration of the catalyst components is preferably such that when the essential components of the catalytic reaction product are combined, the resulting slurry is from about 0.0006 to about 1.0 mole (mol/liter) K of magnesium. Inert organic diluents include liquefied ethane, propane, inobutane, %-butane, hexane, various hexane isomers, inoctane, 8 to 1%
Industrial solvents consisting of mixtures of paraffinic alkanes having up to 2 carbon atoms, saturated or aromatic hydrocarbons such as cyclohexane, methylcyclobencune, dimethylcyclohexane, dodecane, kerosene, nappe, etc.
% K, free of olefinic compounds and impurities), and especially those having a boiling point in the range from -50°C to 200°C. Suitable inert diluents also include benzene, toluene, ethylbenzene, cumene, and decalin.

The mixing of catalyst components to obtain the desired catalytic reaction product is
It is advantageously carried out under an inert atmosphere such as w1, argon or other inert gas at a temperature ranging from about -io o' to about 200°C, preferably from about 00 to about 100°C. The duration of mixing is not critical, as formation of the catalyst composition most often occurs within a minute or less. In preparing the catalytic reaction product, it is not necessary to separate the hydrocarbon-soluble from the hydrocarbon-insoluble components of the reaction product.

In the polymerization process using the catalytic reaction products described above, the polymerization is carried out by adding a catalytic amount of the catalyst composition g! This is done by adding Jt- or vice versa. The polymerization zone is heated at a temperature ranging from about 11" to 800°C, preferably at a solution polymerization temperature, such as from about 11" to 250°C, for a few seconds to several ratios, preferably 15
It is held for a residence time of seconds to 2 hours. It is generally desirable to carry out the polymerization in the absence of moisture and oxygen;
The catalytic amount of the catalytic reaction product is approximately o per liter of diluent.
, o o o i to about 0.1 mmol. The most favorable catalyst temperature is determined by the conditions such as temperature, pressure, solvent, and presence of catalyst poisons. However, the above range generally yields the highest catalyst yield in terms of weight of polymer per unit weight of titanium.

Generally, a carrier is used in the polymerization method, and it is
It may be an inert organic diluent or a solvent for excess monomer.

To realize the full benefits of the high efficiency catalyst of the present invention,
Care must be taken to avoid oversaturation of the solvent with the polymer. If such saturation occurs, the catalyst is depleted, and the full efficiency of the catalyst is not realized; for optimal effectiveness, K is the amount of polymer in the support that exceeds the total weight of the reaction mixture. It is preferred not to exceed about 50% by weight.

The polymerization pressure preferably used is relatively low, for example about 601 tons, 1000 psit; t C845-68
90kPa), special [100&I L700pajg (68
9 to 4820 kPa). However, polymerizations within the scope of this invention can occur at pressures from atmospheric to pressures determined by the capacity of the polymerization equipment. It is desirable to agitate the polymerization means to obtain better temperature control during the polymerization and to maintain a uniform polymerization mixture throughout the polymerization zone.

To optimize catalyst yield during the polymerization of ethylene, it is desirable to maintain an ethylene concentration in the solvent in the range of about 1 to about 10 wt.-1, most preferably about 1.2 to about 2 wt. suitable. To accomplish this, when feeding excess ethylene to the system, a portion of the ethylene can be degassed.

Hydrogen can be used in the practice of this invention to reduce the molecular weight of the resulting polymer. For purposes of this invention, it is advantageous for K to be used in concentrations ranging from about 0.001 to about 1 mole of hydrogen per mole of monomer. It has been found that larger amounts of hydrogen within this range generally result in lower molecular weight polymers. Hydrogen can be added to the polymerization vessel with the monomer stream or before, during, or after the addition of monomer to the polymerization vessel, but can be added separately to the vessel during or before the addition of the catalyst. .

The monomer or mixture of monomers may be agitated (a) in any conventional manner, preferably obtained by suitable stirring or other means.
The monomer is brought into contact with the catalytic reaction product by bringing the catalytic reaction product and the monomer together.

The agitation can be continuous during the polymerization or, in some cases, the polymerization mixture can be left unstirred while the polymerization occurs.

In the case of relatively fast reactions using relatively active catalysts, measures can be taken to remove the heat of reaction by refluxing the monomers and solvent (if either of the latter is present).

In either case, measures should be taken to dissipate the exotherm of polymerization. If desired, the monomers can be contacted with the catalytic reaction product in the vapor phase, in the presence or absence of liquid materials. Polymerization can be carried out batchwise, or by passing the reaction mixture through long reaction tubes in contact with a suitable coolant externally to maintain the desired reaction temperature, or in an equilibrium overflow reactor (aqsiLihriswithoverflow reactor).
It can be carried out continuously by passing the reaction mixture through a reactor (w reactor ) or a series thereof.

The polymer is easily recovered from the polymerization mixture by driving off unreacted monomer or solvent (if used). There is no need to further remove impurities. Thus,
A significant advantage of the present invention is that there is no catalyst residue removal step. However, in some cases it may be desirable to add small amounts of catalyst deactivators of the type commonly used to deactivate Nagler catalysts. The obtained polymer is
It has been found to not contain significant amounts of catalyst residues and to have a relatively broad molecular weight distribution.

The following examples are presented to illustrate the invention. All parts are by molar ratio and percentages are by weight. Melt index values I and 11° are ASTM D 12
88-70, the density value is determined by ASTM D1
248.

The following abbreviations are used in the examples.

BEM = s-7” thyl ethylmagnesium% B% = normal butyl DBM = s-butyl secondary-butylmagnesium DNHM
= Sea Calculation - Hexyl Magnesium EADC = Ethyl Aluminum Dichloride Et = = Ethyl M = Mole Ma = Minimethyl Pr Niingrovir tLP De = Orthopropyl Organometallic compounds and/or complexes are available from Texas Alkyrus Corporation, Lithium Corporation of - Commercially available from America and Schering AG Innstry Chemical Lean.

Examples 1-8 J4. ;1r(0悴Bs)3C1 manufacturing line Zde(0%B
s) 44.22F (0,011 mol) to 100.
01111K (116°
An isoparaffinic hydrocarbon fraction with a boiling point in the range of ˜184° C.) was added. Anhydrous electronic grade BCx was passed through the solution until a milky precipitate formed. Dry N in solution,
Excess HCt was removed from the contaminants by passing through.

B. Preparation of the Catalyst Composition The catalyst used was prepared by mixing in an inert atmosphere the following components in the order indicated: Isohar ■
E 96.97-sxlO, 95E
ADC1,,05m 0.011MZr(OsHs)scl t
sdo, osseM Ti(O4Pr)4 0.6
l11g, 5BAf DIVEM 1
．． 881L1100.01111 where X can be determined from the following table: e.g.
Earthquake-1dZde:11 ratio 1 0.28 1/8:12 0
．． 45 1/4:1 8 0.91 1/2:I A batch reactor containing C0 Polymerized Isopar ■E 21J Tutle was heated to 150° C. with stirring. The solvent vapor pressure is 21 Pa
A friend at 1g (145kPa). 19 pasg for this
(181&Pa) of hydrogen and 120 pg if (82?
&7'a) of ethylene was added to give 1609m411 (1
The total reactor pressure was 108 kPa). catalyst above a certain amount (
However, 7.5 d= o, o 015 mmol of Ti
)tl-injected into the reactor and raised the reactor pressure to 160 ml with ethylene.
pgs (1108&Pa) was kept constant. The total reaction time was 80 minutes. The catalytic efficiency can be found in Table 1 and the physical properties of the polymer can be found in Table 2.

The catalyst used was prepared under similar conditions as for the preparation of the catalysts in Examples 1-B. The following ingredients were mixed in the following order: Isopny ■ E 97.57
-3atO,95AI EADC1,Q5m Tt(O4Pr)a=Zr(OsBs),C1zdQ,
53Af DNHM L, 38'I
Lt100.0117 However, dew can be determined from the following table: Wheat z,
wit L (photograph white 1) Zr:Ti ratio 4
U, 8 0.025 0.100 4
:15 1.54 0.01g 0.1
00 8:16 8.88 0.006
0.100 16:IA*0.6 0.0
886 (LOO: 1* Comparative B0 polymerization The polymerization conditions were the same as Examples 1 to 8. The catalyst efficiency is shown in Table ■
The properties of the polymer are listed in Table 1.

Comparative Experiment B4 Preparation of Catalyst Composition The catalyst for this experiment was prepared under similar conditions as in Examples 1-8. The following ingredients were mixed in the following order: Imphal ■E 97.60111 g, g
5 EADC0.79m Zr (0*Bs)sCJ 0.141
110.40 5M l)BM
1.4 6 1ioo, am B9 Polymerization Polymerization conditions were the same as in Examples 1-8. 0.00
Addition of fromimole of Zr (catalyst 50d) resulted in no observable polymer.

Comparative Experiments C A Catalyst Preparation and Polymerization Comparative Experiments BK Comparative catalysts similar to those described were prepared and polymerizations were carried out as outlined in Examples 1-8.

Examples 7-8, t Zr(0*B attack scl's tribe Imphal■E 50.0xlKZrCla 1.L
? Add f.

Then add pure %C%OH1,87M1 under rapid stirring.

This results in a solution containing 0.1 n of Zr'ft.

Preparation of Catalyst Compositions The catalysts used in these experiments were prepared under similar conditions as in Examples 1-8. Mix the following ingredients in the following order: (7 bar ■E 97.68-a
cwll, 00M EADCO, 7am O, 025, M Ti(O4Pr)a Q, @Q
mO,lAf Zr(0*B*)scl (as produced in A above) [d O,62M BEM O,97i11
00-0117 However, 2 can be determined from the following table; It was the same as the case of ~8. The catalytic efficiency can be found in Table II and the polymer properties are listed in Table H.

The catalysts used were prepared under similar conditions as for the preparation of the catalysts in Examples 1-8. The following ingredients were mixed in the following order: Inhar E 97.68-
s-ylljl, oOEADCO, 75aj! 0.025Af T = (()jPr)4
0.6 11-1□, IM;1rcJ4 (Invar JE medium slurry) zlL7!0.8M %-
Butanol yiaJo, 62M BE
M 0.97m100.01u where 2 and V can be determined from the following table:
Example z, d y, yal Zr:Ti ratio Attack B@O
1l:Zr ratio 9 1.2 1.2 8:1
8: ID1.20 8:l
-B0 Polymerization Polymerization conditions were the same as in Examples 1-80. The catalyst efficiency can be found in Table 1K, and the polymer properties are listed in Table ■.

As can be seen in Table 1 for Examples 1 to 6 and Comparative Experiment A, increasing the level of zirconium compound in the catalyst while keeping other factors constant, the melt index of the catalyst without zirconium Case 16.
This decreases from 49710 minutes to 4.81/10 minutes for the catalyst containing 16 zirconium. This unexpectedly provides a way to control the molecular weight (melt index) of the polymer without adjusting the amount of conventional chain terminators (Hz).

Examples 7 and 8 again demonstrate this unexpected effect of reduced melt index when compared to Comparative Experiment C. Example 9 and comparative experiments also show a decrease in the melt index due to the presence of the zirconium compound due to the presence of phthyl alcohol.
Example 9 has a narrow molecular weight distribution, as shown by the s ratio.

Table ■ 1 16.89124407.590.96782 1
? , 81127.227.850.9678B 15
．． 09115.04 '1620.96714 8.9
868.517.670.96585 5J84471
8.810.96676 4.8086. Q88.11
90.9681A 16.87114.757.01
0.9668B" ----- CI8.629'All 7.180.9678?
1.8419.9610.850.96248 6.0
247.867.870.96499 2.4822.
168.940.9686D 2.1020.619
．． 810.9619 tatami No polymer was formed.

Procedural amendment (method) % formula % 1. Indication of the case Showa 1957 Patent No. 2340 2. Name of the invention 3. Relationship with the m-correct appetizer case Patent applicant name The Dow Chemical Company m1lli)
Please refer to the attached manual #tII building 6, contents of amendment

Claims (1)

[Claims] Ll (one or more polymerizations under conditions typical of Ziegler polymerization, in which the synthesis is carried out in the presence of a slurry catalyst containing titanium, zirconium, magnesium, halides and aluminum) In the method for polymerizing C-olefins, the catalyst comprises the following components: (A) an octavalent or tetravalent titanium compound; CE) a zirconium compound; (C) an organomagnesium compound selected from the following (1) an organic compound; a magnesium compound - or (2) a complex of an organomagnesium compound and an organometallic compound in an amount sufficient to solubilize the organomagnesium compound in a hydrocarbon solvent: ■) a halide source selected from (1) )
Active non-metal halides of the formula R'X (wherein R' is an organic radical such that the hydrogen or halogen atom
metal halide of y-a , halogen, ν is the number corresponding to the valence of M, and G is from 1 to V
); and the organomagnesium component (C)
and (or) of the halide source) when insufficient amounts of aluminum are obtained (A') of the formula AIB, IX
an aluminum compound of y#, where R and X are as defined above and V' and V'' each have a value from 0 to 8; be)
However, the proportions of these components are as follows: Mg:Zy is 1:1 to 100:It'', Al:ZrEi is 0.01:1 to 100:1, and Zr: Ti is 0.1:1 to 5o:1 in excess (DX', Al is 0.005:1 to 1o:1
is obtained by the reaction: and in the reaction, these components are in the following order: (α) (1) organomagnesium component (('l, (2)
(bXl) Contains aluminum: (bXl) halide component ■, (3) if required, aluminum component (E), and (4) titanium and zirconium components (A, B) in any order or as a mixture; the halide component (D), (2) the organomagnesium component (C), and then (3) the titanium and zirconium components (A, B) in any order or as a mixture; (2) titanium and zirconium components CA, B in any order or as a mixture, and then (3) organomagnesium component (C); A method characterized in that: 2. The titanium compound has the formula TiXn(OR)a-nk and the zirconium compound has the formula ZrXnC0R)an, where each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms. and each X is a halogen and 5 is 0 to 4), and the atomic ratio is Mf:Zr is 2.5:1 to 50:1 and Al
:Z is 0.5:1 to 50:1, Zr:Ti is 05:1 to 40:1, and excess X:Al is 0.5:1 to 50:1.
The method according to claim 1, wherein the ratio is between 0.002:1 and 2:1. 8. Valley X is halogen, and each RfJS independently C(=
C1o alkyl, and the atomic ratio is Mg:Zr from 5:1 to 25:1, Al:Zr from 1=1 to 25:1, and Zr:Ti from 1:1 to 20:1, with an excess 3. The method according to claim 2, wherein X:Al is 0.01:1 to 1.4:1. 4. The method according to claim 2, wherein the organomagnesium component is Cr-Ctodialkylmagnesium. 5. The method according to claim 2, wherein the organomagnesium component is a complex of dialkylmagnesium and trialkylaluminium having an atomic ratio of M(l to At) ranging from 0.5:1 to 10:1. 6. The tetravalent titanium compound is tetraisopropoxytitanium,
The method according to claim 4 or 5, which is tetraethoxytitanium, tetra-exo-butoxytitanium or tetramethoxytitanium. 7. Zirconium compound is Zr (OnBs)BCl,
Zr(OtsBu)4 or ZrX with a molar ratio of zirconium halide to alcohol from 0.25:1 to 4:1
7, wherein X is chlorine or bromine, and an aliphatic alcohol having from 1 to 8 carbon atoms. 8. Ethylene or ethylene and at least one other Cr
The method according to claim 4 or 5, wherein the mixture with -C2°α-olefin is polymerized. 9. The method according to claim 8, wherein a mixture of ethylene and at least 18i of 1-butene, 1-hexene and 1-octene is polymerized. Catalyst composition suitable for the polymerization of α-olefins under conditions characteristic of 1α Tiigler polymerization and prepared by the reaction of: (A) a titanium compound of the formula TiX% (OR) 4-% (wherein Each R is independently a hydrocarbyl group of CI-Cto; X is chlorine or bromine; Zirconium compounds (wherein each R is independently C1-c21.
CC) is an organomagnesium compound of the formula RxM, where each R" is independently an alkyl group of group) or a complex of the formula R; yg"REAL (where Mσ: Al
The atomic ratio of is from 0.5:1 to lO:1):
(D) a halide source selected from the following (13) an active nonmetal halide of the formula R'X, where R' is a hydrogen or halogen atom in which (2) Formula M
A metal halide of R, -,
R is an organic residue of 11i[5, usually hydrocarpyl or hydrocarbyloxy, X is halogen, 1
is a number corresponding to the valence of M, and G is a number from l to y); and the organomagnesium component (C
) and (or)...when insufficient amounts of aluminum are obtained by the halide source CD), the formula AIEy
lX, H, where R and X are as defined above and 1' and ν" are each 0
The ratio of these components is as follows: Mg:Zr has a valence of 81 and the total valence of V' plus V# is 8) l to 100:1 and Al:Z
r is 0.01:1 to 100:1 and Zr:
Ti is 0.1:1 to 50:1 with an excess of
:Al is from 0.005:1 to 10:1; and further these components are added in the following order: (cL)
(1) the organomagnesium component (C), (2) the halide component CD), (8) if required, the aluminum component ω and then (4) the titanium and zirconium components in any order or as a mixture. (A, B); (6) (1) When aluminum is contained, it is converted to halide component ω (2) Organomagnesium component (C)
, and l then (8) titanium and zirconium components (A, B) in any order or as a mixture: or (c) (1) halide component CD if it contains aluminum), (2 ) the titanium and zirconium components (A, B) in any order or as a mixture, and then (8) the organomagnesium component (C). LL titanium compound is tetra(C1-C4 alkoxy) titanium and the atomic ratio is Mg:Zr from 2.5:1 to 50:1 and AL
:Zr is 0-1:1 to 50:l and Zr:T
i is 0.5:1 to 40:l and X:A is in excess
t is 0.002:1 to 2:l.