JPS5981309A - Olefin polymerization catalyst - 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 The present invention relates to a catalyst having a motor for producing olefin polymers while controlling molecular weight distribution. More particularly,
The present invention relates to a process for the preparation of such a catalyst by using a magnesium porous or magnesium siloxide support, the molecular weight distribution of which is altered by the addition of an alkyl aluminum chloride compound.

A number of catalysts using organomagnesium complexes to produce zz2 IJ olefin complexes are known.

However, these catalysts generally have relatively low catalytic efficiencies at pressures due to the production of polymers with high bulk densities.

Increasing catalyst efficiency generally produces polymers with lower bulk densities. These catalysts generally require complex preparation techniques. In addition, these catalysts do not offer the flexibility to change the molecular weight distribution of the 11 complex to suit a particular application.

It is known in the art that polyolefin polymers, such as polyethylene and copolymers of polyethylene and other monomers, are useful in a variety of applications. Methods for manufacturing products from these polymers include film blow molding, injection molding, blow molding, and the like.

However, the molecular distribution of a polymer is important in determining whether the polymer is suitable for these various uses. For example, in injection molding using polyolefin polymers, a narrow molecular weight distribution is preferred in order to obtain the best product compared to blow molding techniques where a broad molecular weight distribution is preferred.

A magnesium catalyst known in the prior art is disclosed in US Pat. No. 4.027.089. Table 5 of this reference shows that approximately so
A catalyst efficiency of o, o o Oy has been reported.

The examples show that catalysts prepared with C1/Afg atomic ratios of 5 to 10 yield polyethylene with a narrow molecular distribution.

U.S. Pat. No. 3,907,759 describes a method for making a catalyst in which magnesium siloxide is reacted with a titanium compound, provided that the titanium compound is required to contain a halogen. U.S. Pat. No. 4,218,339 describes a polymerization catalyst prepared by reacting the reaction product of an alkylmagnesium chloride and a polymethylhydridosilomylene with tetra-n-butyl titanate and silicon tetrafluoride. There is. The highest catalytic activity in this reference is shown in practical example 20. Although the reference describes the divine halogenating agents that are useful, it does not include the use of aluminum compounds named chlorine.

U.S. Time i ('144,039,472, No. 4,105
, 846 JI-J, No. 4.199.476, and No. 412 Q, 699 all describe catalysts prepared from magnesium alkoxide, titanium alkoxide and ethylaluminum chloride. Belgian Percentage No. 19,609 describes a similar catalyst except that the magnesium alkoxide is produced in situ from magnesium metal and alcohol (-1 catalyst efficiency (as shown in Example 16)) with titanium 1.g. European Patent Application No. 38,565 is similar to U.S. Pat. No. 4,218 except that an electron donor compound is included in the preparation of the catalyst.
, No. 339] describes a similar catalyst.

US Pat. No. 4,115,3194F reacts a halogenated magnesium compound with a titanium compound to obtain a reaction product and then uses a silicon compound after or during the halogenation of the magnesium compound. Column 4, lines 23 to 30 describe that the atomic ratio of transition metal/Mct is in the range of 0.02 to 20 and the ratio of halogen/transition metal is in the range of 0.5 to 100 [2]. The resulting C1/Mg atomic ratio is 0
．． 01-200 (1). Ethylene homopolymers produced using these catalysts are described as having narrow molecular weight distributions.

U.S. Patent Nos. 4,330,646 and 4330.647
No. 4.330.651 and No. 4.335.229
The issue describes all polymerization catalysts in which the molar ratio of alkoxy+siloxy to magnesium alkoxide is smaller than zo. U.S. Pat. No. 4,374,755 teaches magnesium isosiloxide compounds and methods of making the same. This patent also describes compounds that are useful starting materials for producing active catalysts for the polymerization of olefins. However, this reference does not disclose highly efficient catalysts or catalysts that can modify the molecular weight distribution.

It would therefore be a great advantage to the art to provide a method for producing catalysts with high efficiency and with variable molecular weight distribution.

It is therefore an object of the present invention to provide a catalyst with high efficiency for the polymerization of olefins and a process for the production of such a catalyst. Other objectives will be apparent to those skilled in the art from the following description.

This time, we have developed a highly efficient catalyst that can change the molecular weight distribution of the obtained polymer or copolymer.
~20 alkyl groups, cycloalkyl groups, alkaryl groups, aralkyl groups, aryl groups or alkoxy groups, each of which may be further substituted with halogen;
It has been discovered that it can be prepared from a magnesium-containing support where n is greater than 0 and V is equal to or greater than 810.05. When using these carriers, the value of n refers to the average of these foci in all carriers, such that the value of n can vary from molecule to molecule, while the average value of be. Preferably (-<, n is about 0.05 to about 50
It is. These polymeric support materials are contacted with non-halide transition metal alkoxides and finally halogenated to produce polymerization catalysts.

More specifically, the catalyst of the present invention comprises: 1) a hydropolysiloxane of the general formula 0%) of the general formula RMgR or Rldg
React with OR's sololol magnesium or alkylmagnesium alkoxide to at least 1.0 sin1
2) contacting the reaction product with at least one non-ride transition metal alkoxide having at least one of the general formula % (); 3) React the mixture of (1) and (2) with 7. a rogensing agent to obtain a polymerization catalyst in which the ratio of rogens to magnesium is at least ZO, provided that each R is independently hydrogen or has a carbon number of 1 -20 alkyl group, carbon number 6-20(7)71J-l group, aralkyl group or alkaryl group, and (a) and (b) are O
more dog-like, provided that the sum of a) and (b) does not exceed 3, m is 1 or more than 2, q is 0 to 1, and r
is 2 to 4, and 2q+γ is very similar to the valence of M, and Z
+ZI is equal to the valence of M, and p is greater than 1,
It can be manufactured by M is generally any transition metal that forms a polymerization catalyst, preferably titanium,
79 nanonium, chromium, turconium, or a mixture thereof.

Instead of the hydropolysiloxane, yft'su[oxy(silylene) ester] of the general formula R200 1II II +SL-0 -C-R, -C-0+UR1 can be used instead of the hydropolysiloxane. Can be used. However, in the above formula, R, SR2, R, and R,
id independently represents hydrogen, halogen, alkyl and alkoxy groups having 1 to 30 carbon atoms, aryl having 6 to 300 carbon atoms, aryloxy, cycloalkyl and cycloalkoxy groups, and R6 is a monoalkyl group having 1 to 30 carbon atoms, carbon Number 6-3
0 cycloalkyl group, alkaryl group, aralkyl group, aryol group or bicycloalkyl group, and n
is thicker than 2.

The reaction product of the silicon compound and the methylkylmagnesium and/or i-alkylmagnesium alkoxide can be combined with the halogenating agent and the transition metal alkoxide in any order. However, for slurry polymerization, the reaction product is first combined with the transition metal alkoxide,
It is then suitable to combine it with a halosaponizing agent. For solution polymerization, the order of halogenating agent then transition metal alkoxide or any suitable order of addition in the case of a slurry is preferred.

The molar ratio of silicon to magnesium is such that substantially all of the magnesium alkyl is converted to magnesium siloxide. This molar ratio of silicon to magnesium is at least 2 when starting with methylkylmagnesium.
:l, and may be higher than that. The molar ratio of silicon to magnesium must be at least 1:1 when starting with an alkylmagnesium alkoxide.
V, but it may be higher than that.

Molten G! In the gold thread, the molar ratio of magnesium to titanium should be in the range of about 4:1 to about 2oo:i, with the most preferred range being about lO:1 to about 100:1. Although catalyst efficiency increases as the molar ratio of magnesium to titanium increases, it has also been discovered that the catalyst residual color associated with magnesium increases with this increase in catalyst efficiency. The most significant of these residues are chloride ions. Therefore, the same person in the art believes that excessive amounts of chlorine can cause corrosive polyethylene f: For polyethylene without flaking, i.e., colorless, a low amount of titanium is required, so chlorine in the resulting polyethylene is You will find that the ratio of magnesium to titanium must be chosen so that a compromise can be made between the amount of titanium and the amount of titanium.

Suitable hydropolysiloxanes used in the preparation of the catalysts of the present invention have (a) values of 0.1 to 2 and (b) values of 1.2 or 3.
has a value. provided that the sum of a) and (b) does not exceed 3. Representative, but non-limiting, examples of hydropolysilostelezanes useful in the practice of this invention include polymethylhydrosiloxane IPMIIS), polyethylhydrosiloxane Siloxane, polymethylhydro-methylsiloxane copolymer, polymethylhydro-methyloctylsiloxane copolymer, polyethoxyhydrosiloxane, tetramethylsosiloxane, SOFES Nilsonroxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, These are polyphenylhydrosiloxane, polyeicronhydrosiloxane, polychlorophenylhydrosiloxane, and mixtures thereof.

Representative, but non-limiting examples of methylkylmacnesium compounds useful in preparing the catalysts of the present invention include subbutylmagnesium, n-butyl-86C-butylmagnesium, butylethylmagnesium, butyloctylmagnesium. , soeikonlumagnesium, soe n-hexylmagnesium・O, (12) trimethylaluminum, soeikonlumagnesium・0.1 triethylaluminum, These are butylmagnesium/2-triisobutylaluminum, butyloctylmagnenium/2-triisobutylaluminum, luminum, butylethylmagnesium-lithylaluminum, and mixtures thereof.

Representative, but non-limiting, examples of alkylmagnesium alkoxides are butylmagnesium butoxide and butylmagnesium propoxylate. These substances can be added separately or prepared in situ, such as by reaction of 1 mole of alcohol with 1 mole of noalkylmagnenium.

Representative, but non-limiting examples of transition metal alcoholic compounds useful in the preparation of the present invention include tetraisopropyl titanate, tetra-n-butyl titanate, tetrabis(2-ethylhexyl) titanate, and tetrabis(2-ethylhexyl)titanate. −
n-butyl/gunadate, tetra-n-propyl zirconate and tetra-n-butyl solconate, isopropyl titanate decamer, i.e. iso-C,II,
O [IT i (0-in-C, H712-0:
+, o Itsu C3.117, butyl (triisoglot d4
c) Titanium, tetraeicosyl titanate and mixtures thereof.

Halogenating agents useful in the practice of this invention generally do not include transition metal halides. This is because the use of such halogenating agents adds additional reduced or unreduced transition metal halides into the catalyst. However, such halogenating agents can also be used to alter the efficiency of the catalyst if desired. The halogenating agent can be either a liquid or a gaseous substance that can form a solution with the useful hydrocarbon. Representative, but non-limiting, examples of halogenating agents useful in the present invention include methylaluminum lachloride, methylaluminum sesquichloride,
Isobutylaluminum dichloride, isobutylaluminum sesquichloride, ethylaluminum sochloride, soethylaluminum chloride, ethylaluminum sesquichloride, 5nC14, 5iC14,
HCl1H5iC13, aluminum chloride, ethylboron dichloride, boron chloride, diethylboron chloride, HCCl, , Pct, , POCI
, acetyl chloride, thionyl chloride, dihualinghuang, methyltrichlorosilane, somethylsochlorosilane, TiC'14, CCl4, tert-butylchloride, α-chlortoluev and VCl4. Among these, alkyl aluminum cess-v chloride,
Preference is given to methylkylaluminum chloride and alkylaluminum isochloride, and those in which the alkyl group is methyl, ethyl or isobutyl.

This time, it was discovered that when comparing Haloken and magnesium, the molecular weight distribution changes in slurry polymerization regardless of the solubility of the carrier. For example, changing the chlorine to magnesium ratio from 4.1 to 8:1 will broaden the molecular weight distribution of the polymer. Suitably, the ratio of halogen, preferably chlorine, to manesium is from about 3=1 to about 16:1.

As the halogenating agent for the transition metal halide, non-transition metal halides are not suitable for the purpose of the present invention.

It is likely that the transition metal halide is given an excessive amount of transition metal to the reaction, so that the transition metal is not completely reduced, thus reducing the catalyst activity. However, these jackets may also be used with the present invention. The most preferred halogenating agents are chlorinating agents, among which soethylaluminum chloride, ethylaluminum isochloride, ethylaluminum sesquichloride, and their methyl and isobutyl congeners are preferred.

In order to widen the molecular weight distribution of the produced polymer, the atomic ratio of ct7mg produced by the transition metal halide is 0.5.
The chloride in the final catalyst obtained must be obtained from aluminum or boron compounds or mixtures thereof, and the chloride is added in the final chloride step. That is, as described herein, the final CL/M
At least 80% of the total chloride of Q is obtained from aluminum or boron sources, or mixtures thereof. Preferably, more (90% or more) of the total chloride is derived from aluminum or boron.

The molecular weight distribution of slurry offshore systems, whether soluble or insoluble, can be varied by changing the C't/Mg atomic ratio in the Mg support-based catalyst. This effect is observed only when excess chloride is added using aluminum-containing compounds or boron-containing compounds. This is because common types of solid compounds perform similar functions and behave similarly. This effect is not seen under solution polymerization conditions.

When a silicon compound such as silicon tetrachloride is used as a halosaponification agent, a polymer with a narrow molecular weight distribution is produced even if the atomic ratio of C1/Mg is small. /.Replacing the halogenating agent with a tin halide, such as tin tetrachloride, produces a polymer with a substantially less broad molecular weight distribution at high ct7mg atomic ratios.

Magnesium siloxide compounds can be solubilized in hydrocarbons by addition of trialkylaluminium compounds. The trialkylaluminum compound can be added either before or after carrying out the reaction to produce the magnesium siloxide compound.

4! ``Combinability is achieved by adding not more than 1 mole of trialkylaluminum compound to the magnesium siloxide adduct; however, when n is much larger than 1, at least 2 moles of trialkylaluminum are required. Solubilization of the carrier is suitable for more precisely controlling the particle size distribution of the resin produced by slurry polymerization.

One trialkylaluminium compound useful in the practice of this invention is of the formula AIIR"), where R2 represents an alkyl group having 1 to 20 carbon atoms or hydrogen, and at least 2
R2 is preferably alkyl.

Representative, but non-limiting examples of aluminum alkyls useful in the practice of this invention are triethylaluminum, tributylaluminum, triisobutylaluminum, soethylaluminum, diethylaluminum hydride, isoprenylaluminum, and trimethylaluminum.

When using an alkyl aluminum solubilizer, n may be equal to 0. When n is equal to Oe, the magnesium compound is similar to that of US Pat. No. 4.374.755. However, the material of the present invention, unlike U.S. Pat. No. 4,374,755, which uses titanium halides,
Contacted with titanium tetraalkoxide and then chlorinated. The presence of aluminum alkyl provides a soluble catalyst for halogenation, while the use of titanium alkoxide and hyhalokene supplements provides high activity.

When producing a magnesium compound with n = 0, the formula t
A siloxane of <A, 5i (OHI<) can be used. Here, R3 is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, an aryol group, or an alkoxy group having 6 to 20 carbon atoms. and S is 1.2 or 3. Contacting the siloxane with methylkylmagnesium or alkylmagnesium alkoxy to dissolve the saturated aliphatic hydrocarbon 1) inert to the hydrocarbon as defined by L The reaction product Maki 1 is produced. In particular, the solubility is at least 0.01 Jf a in hexane at 25°C.
Defined as capable of forming a solution of This reaction product m is subsequently contacted with an aluminum alkyl of formula At(R2)3 to render it soluble in the hydrocarbon.

Next, this solubilized reaction product is brought into contact with an alkyl alkoxide fragment as described above, and is rogogenated to produce a 1-polymer catalyst.

Representative, but non-limiting examples of these organosiloxanes used with aluminum alkyls include:
Trimethylhydroxysilane, triethylhydroxysilane, triphenylhydroxysilane, diethyldihydropanedisilane, soisoprobylsohydroxysilane, triethyldihydroxysilane, socyclohexylsohydroxysilane, diphenylsohydroxysilane, butyltrihydroxysilane and phenyltrihydroxysilane It is hydroxysilane.

A high cocatalyst to catalyst ratio is suitable for trapping all impurities. However, increasing the height is detrimental to efficiency as the cocatalyst tends to reduce titanium too much and tends to reduce the activity of the catalyst.

This reduction in activity is particularly true in the case of solution polymerizations carried out at high reaction temperatures. Cocatalysts are also known to solubilize magnesium compounds at high temperatures, resulting in 17 that under solution conditions the catalyst support is eroded and dissolved by high aluminum concentrations. Therefore, in solution offshore, a low cocatalyst to catalyst ratio (preferably aluminum to titanium ratio) is often best. Therefore, under slurry polymerization conditions, the ratio of aluminum to titanium should be high. However, under solution conditions, the reaction can be reduced to about 220
It has been discovered that when operating at temperatures at or below the aluminum to titanium ratio should be increased in parallel with the slurry conditions. 1 ~ Kashi solution reaction at about 220℃
In the above case, the ratio of aluminum to titanium is low to reduce vulgarization of the magnesium compound and to obtain erosion of the catalyst support.The preferred cocatalyst to catalyst ratio is therefore about 1 in molar ratio.
00 to about 2000. These ratios range from about ioo to 2000 under slurry polymerization conditions.

For molten polymerization conditions, a suitable cocatalyst to catalyst ratio ranges from about lθ to about 2000 molar ratios.

Representative, but non-limiting examples of aluminum alkyls useful in the practice of this invention include aluminum triethyl, aluminum tributyl, triisobutylaluminum, soethylaluminum chloride, imprenylaluminum, trimethylaluminum, trimethylaluminium as a cocatalyst. These are aluminum chloride, trioctylaluminum, soethylaluminum ethoxide, tridecylaluminum, trioctylaluminum, trihexylaluminum, and hissoethylaluminum glopoxide.

In preparing the catalysts of this invention, preferred embodiments include polysiloxanes, such as polymethylhydridosiloxane, containing about 40%
The process involves reacting silicon, magnesium and fluminiram in an atomic ratio of about 2.1:1.0:0.1 with a methyldolmagnesium/aluminium alkyl solution at a temperature of ~90°C.

The resulting reaction product is mixed with a tetraalkyl titanate and then reacted with a halogenating agent such as ethylaluminum isochloride. The resulting catalyst is in slurry form. This can be used subsequently without any washing or decant steps. A suitable magnesium to titanium atomic ratio is from about 1 to about 200, preferably from about 5 to 100.

For use in the catalyst-slurry and solution systems of the present invention,
The molar ratio of silicon to magnesium is such that substantially all of the magnesium alkyl is converted to magnesium siloxide. It must be noted that an excess of some silicon compounds, such as polymeric hydridosiloxanes, is not critical, except in the cost of the catalyst, and in fact has advantages, such as in the bulk density of the slurry powder. The atomic ratio of silicon to magnesium must be at least 2:1 but can be very high. The excess silicon can be free silicon polymer or magnesium-bound polymeric siloxide as described herein. Furthermore, the catalyst efficiency in slurry polymerization is influenced by the atomic ratio of Si7Kg. A suitable atomic ratio for optimum catalytic efficiency is at least 2.0/i,o (Si/Ma
1 to about 4.0/1.0 (Si/MQ).

Lower atomic ratios are fatal to catalyst efficiency, and higher atomic ratios do not show any improvement.

One of several alternative methods can be used in making the catalyst of the invention. The catalyst preparation can be heated after addition of the halogen ions.

The temperature is about 50 to about 150°C, and one hour is about 10 minutes to several hours. The catalyst is heated for a sufficient period of time, but this will vary widely as some halogen sources react only slowly.

Thus heating improves this reaction as does increasing contact time.

An alternative method of catalyst production requires decanting the catalyst slurry to remove the halides that dissolve in the hydrogen ash. However, this method does not offer any advantages over the preferred method unless a large excess of halogen source is added. A large excess of halogen in the catalyst can increase the chlorine or halogen content of the polyethylene, making it corrosive. In other production methods, the Ti present does not chlorinate a significant proportion of MgO-5i bonds to xg-ct bonds and C
11 MQ high enough to maintain Mg ratio below 4
Titanium halide (preferably chloride) is used in the /Ti molar ratio. Therefore, if you want to widen the molecular weight distribution,
Only small amounts of transition metal group halides can be used as the halogen source.

In solution polymerization systems, the catalyst is useful at temperatures ranging from about 120°C to about 300°C. Under slurry heavy content conditions,
The catalysts are useful at conditions known to those skilled in the art, typically from about 40 to about 90°C and pressures up to about 40,000 p 8 i g or more. It is known to use hydrogen to control the molecule t in either system. These catalysts can be used in place of conventional catalysts without modifying the process equipment.

The catalyst of the present invention will normally be effective when a 10'' parameter at residence is observed. In slurry polymerized yarns, the residence time should be in the range of about 10 to about 10 hours, usually about 1 to 5 hours; -For liquid solution systems, the residence time should be about 1 hour.
It should be from 20 to about 1 hour, usually from 40 to about 1 hour.

These differences in residence times are due to the rate of polymerization and thermal deactivation of the catalyst in solution systems. Although the temperature of slurry polymerization does not give a low polymerization rate, the catalyst remains active for a long period of time, and thus increased residence time can be used to achieve good catalyst utilization. Solution polymerization, on the other hand, has a high polymerization rate, but the catalyst is thermally inactivated and thus the catalyst activity decreases rapidly with time (7, usually becoming relatively insufficient after 11 polymerizations). .

The present invention is;! Polymerization can be carried out either in a 14-continuous manner or in a batch manner, with a continuous 11-continuous polymerization being preferred.

Similarly, the reactor used may be a %f' type reactor or a stirred tank type reactor as commonly used, but any reactor which allows good contact between the ethylene and the catalyst can be used.

Molecular weight control can be achieved by using hydrogen as is known in the art. Furthermore, the control of molecular weight is
For combinations of hydrogen or temperature in both the slurry and the solution, dissolution can be effected by reactor temperature in the case of polymerization. Generally, higher temperatures cause a decrease in molecular weight. This tendency is more pronounced in soluble vI1 than in slurry polymerization systems. It is noticeable in the polymerization system.

In slurry polymerization reactions, the catalyst is typically heated at 40 to about 90°C and about 4000°C under conditions known to those skilled in the art.
The total reactor pressure in psi and conditions including the use of hydrogen to control the molecular weight.

These catalysts can generally be used in place of conventional catalysts without modification.

The catalyst of the present invention provides narrow and broad molecular weight distributions in the resulting polymers. The molecular weight distribution in the sura IJ4 combined system, whether soluble or insoluble, is
It can be changed by changing the atomic ratio of MQ. This effect is observed only when adding 51i1J of chlorine, using aluminum-containing compounds or boron-containing compounds. This is because both types of compounds exhibit the same function and behave similarly.

Moreover, this effect is not observed under solution polymerization conditions.

For example, changing the halogen to magnesium ratio, as represented by (chlorine), from 4:1 to 8:1 broadens the molecular weight distribution of the polymer. Preferably, the ratio of halogen, preferably chlorine, to magnesium ranges from about 3:1 to about 16:1. It has now been discovered that catalytic activity tends to decrease as the chlorine to magnesium ratio increases. However, in order to widen the molecular weight distribution, molar ratios of 6:l to 12:1 are most significant, and even about 8=1
It has also been found that the molar ratio of halogen to magnesium is the most suitable.

Although the ratio of chlorine to magnesium affects the molecular 41 distribution in slurry systems, it was surprisingly discovered that in the case of solution polymerization systems, the molecular weight distribution is not affected, but rather the catalytic activity is changed. This surprising contrast of effects in the solution and slurry IJ-38 systems cannot be explained, but it clearly exists.

Slurry polymerization catalysts having C1711g molar ratios of 6:1 or higher provide 12-lyethylene catalysts with reduced catalytic efficiency. Unexpectedly, Si/Mg in the catalyst
It has been discovered that increasing the molar ratio improves catalyst efficiency. Si/Mg atomic ratio from total Zl to 2. ．． Catalysts prepared with increasing Si/Mg molar ratios of 8=1 produced polyethylene with a broad molecular weight distribution with increased catalytic efficiency in slurry polymerization. Increasing the atomic ratio increases the catalyst efficiency by about 3 times.

When performing slurry polymerization, the ratio of magnesium to titanium should be in the range of about 1:1 to about 50:1, with a preferred range of about 5=1 to about 25:1. It should be noted that in the slurry 1 combination system, as the molar ratio of magnesium to titanium increases, the bulk density of the 11 combination decreases while the catalytic efficiency increases. It will therefore be clear to those skilled in the art that a balance must be struck between catalyst efficiency and the decreasing density of the polymer.

The following examples further illustrate the invention. In the example,
All parts and percentages are by weight unless otherwise noted. The examples illustrate the invention but are not intended to cover it.

In the following examples, subbutylmagnesium is used as Lith
ium Corporation of Ameri
It was obtained as a heptane solution from cα. Polymethyl hydridosio-Q San (PMH5l is pgtarchS1
/stems, Inc0. Triethylaluminum chloride il 7' e zαs Alk
yls.

It was obtained as a hexane solution from JNC, Inc. Butylethylmagnesium is Texαs Alkyls.

Inc. as a 0.640 molar hebutane solution. Tetraisoglovir titanate is AlfaProd
Obtained from ucts. Isoparaffin mixture Ewxon
Obtained from I Exxon Co.

Commercially available product names from USA, l5opAR@p, and I
SPAR Gl, purified with 7 elemental parts and molecular sieve to remove oxygen and water. Hexane has a ph
pgtraleum Co. and purified with molecular sieves and nitrogen to remove oxygen and water. All catalyst preparations were carried out in an inert atmosphere.

Example 1 A catalyst was prepared by reacting PMIIS (3.4 mt, 56 mmol silicon) with a stirred solution of 0.715M subbutylmagnesium 35- and hexane 215-. This solution became cloudy in about 2 minutes.

The mixture was heated to about 70°C for 1 hour, then cooled to 25°C. Stir the mixture and add 1.0 M tetraisoderovir titanate (2-0-12.0 mmol) in hexane,
Next, 1°149m49m ethylaluminum chloride 9 chloride 8f+++00 mmol) was added dropwise to form a slurry.

A portion of the resulting catalyst slurry was diluted with hexane.

1 of this diluted catalyst containing 0.001 mmol of titanium.
Parts were stirred with nitrogen containing TOO ml of anhydrous oxygen-free hexane and 0.10 M) ethylaluminum 2.0 - 1,8! was added to the reactor. The reactor was pressurized to 5 opsig with hydrogen and ape
I degassed to ig. This operation was repeated three times. The pressure in the reactor was increased to 3 (lp8jg) with water, then 1 with ethylene.
Adjusted to 100psi. The contents of the reactor were heated to 80°C. Add ethylene to maintain a constant reaction pressure of 150 psig. After 1 hour the reactor was cooled and degassed. The contents of the reactor are filtered and the recovered polyethylene is
It was dried in a true nitrogen oven at 40° C. until no hexane was present. The recovered polyethylene was 103.4. r and ASTM
It had a melting index of 0.09 as determined under Condition E of 1238. The ratio IIo/I could be determined as 15.6. Here, It is the melting index under ASTM 123B condition E, and 11o is the high load melting index (ASTM 123B condition 7v). The higher the 11o/12 ratio, the broader the molecular weight distribution of the offshore body. Catalyst efficiency was polyethylene ziso per titanium ly, ooog.

The efficiency of the co(1') catalyst was 4,430,000 when hydrogen was not used in the polymerization reaction.

Example 2 0.715M Subbutyl Magnesium 35. o- and l5
Polymethylhydride 70xane (3.4 mL 56 mmol silicon) was added to a stirred solution of 215 tnl of opar@E and heated to about 75°C. This mixture - from 70 hours to
Heat schiff to 100°C, then cool to '0'C. After cooling, 5fnl of 1.0 M tetraisopropyl titanate Z in hexane was added, followed by 87 tnl of 1.149 M ethylaluminum isochloride.

The polymerization was carried out exactly as described in Example 1, using the catalyst of Example 2, except that 0.593 &) ethylaluminum 1.7 tne and 50p8iQ of water* were used.

The recovered polyethylene was 20.9 and had a melt index of 0.80. The ratio of Iro/I is 13.7,
The catalyst moving part is polyethylene 41 & OOO per 1g of titanium.
It was lj. The efficiency was low due to the high hydrogen pressure of polymerization.

The catalyst supports used in Examples 1 and 2 were not soluble in aliphatic hydrocarbons. However, by using these methods, it was possible to solubilize luminium alkyl in aliphatic hydrocarbons. Example 3 illustrates solubilization of a magnesium siloxide support using an aluminum acetate.

Example 3 To a stirred solution of Tubdelmagnesium 1121 nl IMQ 80.0 mmol) and hexane 88-
, 5m1i Si 8.2 mmol) was gradually added.

The solution was heated to about 70°C for one hour and cooled to 30°C. The mixture remained in solution. Start stirring, then PNH5O,Td, (Sj l 1.5 mmol)
was added. Heat this solution to about 70°C for -H hours (7,
Cooled to 35°C. The mixture was one part of the solution.

Two portions of PMH5L (Sj 19.7 mmol) were added to the stirred solution at a thrust of 1 liter, and the solution layer was heated to about 70°C for 1 hour and then cooled to 35°C. The resulting solution has a concentration of 0.49,
It had an atomic ratio of 5 i/Kg. The mixture was first of solution.

2.5 m of PMBS (Si 41.0
The solution was heated to about 70°C for 1 hour and cooled to 25°C. The obtained/this solution breaks the Si/Mg atomic ratio of 1.0, and due to the heating process, the chemical species in the solution change to RMgOSi (R1(Hl
(C1131 (in the formula, R is a butyl group)).

An additional 4.0-4.0% of PMBS was added to the stirred solution and S
The atomic ratio of i/Mg was 20KL. The reaction was exothermic and the mixture was heated from 25°C to 35°C. The mixture solidified into a clear gel. At an atomic ratio of 2 for Si7Kg, P
The chemical species present in the gel produced from the reaction of MBS and JigR are magnesium isosiloxide, Mg (05
4(R1(Hl (CH31).

It seems to be.

13.5 ml (8.01 mmol) of 0.593Sf triethylaluminum was added to the solid gel.

The gel started to dissolve immediately and a solution was obtained after mixing.

Example 4 This example demonstrates the effect of aluminum alkyl present during the reaction of PMBS and noalkylmagnesium. In this experiment, pMH5 (25.6 ml 1.5i 420 mmol) was mixed with 0.715 M subbutylmagnesium 280 m
l (200 mmol Mg) and 0.593 M) ethylaluminum 33.7 WLl (20 mmol Al)
was added slowly to the stirred solution. The PMMS was added to prevent the reaction exotherm from heating the entire mixture above 85°C. Then, the stirred solution was heated to 70-80'G.
I kept it for 1 hour. After cooling to room temperature, the solution was diluted to 500% with oxygen-free anhydrous hexane to obtain a 0.40M magnesium solution.

Example 5 An experiment was conducted to demonstrate the effect of aluminum trialkyl present during the reaction of pulls with an alkylmagnesium alkoxide. In this experiment, hexane 1
00m! ! reagent grade n-f lobil alcohol (250
A solution of 118.8 mmol was added dropwise to a stirred solution of 390+++1 (250 mmol) of 0.650M butylethylmagnesium.

To this slurry was added a solution of 211 ml (125 mmol) of 0.593 Jfl-ethylaluminum.

This solution was evaporated to a volume of i5007 to obtain a 0.5M alkylmagnenium peroxide solution.

Add 200 portions of this solution to pMIIs (6,4 td, 5
z105 milJ mol) was added. The exotherm of the reaction heated the solution to about 50°C. After cooling to room temperature, a solution was obtained.

In the wood experiment? A complete series of reactions was carried out: preparation of a solution of magnesium isosiloxide with L=0.05, subsequent preparation of a catalyst, and polymerization of ethyl 1/one.

PMBS (420 mmol of 25,6meXSi) was dissolved in 380 ml of 0.715 M subbutylmagnesium (M
7200 S IJ mol) and 33.7 ml (120 mmol A) of 0.593 M IJ ethylaluminum. This PMH
=β was added so that the exotherm of the reaction did not heat the mixture above 85°C. The stirred solution was then heated to 70-
' Maintained at 80°C for 1 hour. After cooling to room temperature, the solution was diluted with 5 oofnlt of hexane to obtain a 0.40M magnesium isosiloxide solution. 1 in hexane. A solution of 2.0-(2 mmol) of OJf tetraisoglovir titanate was mixed with 125 mg of magnesium disiloxide (&g
50 mmol) to prepare a catalyst. This melting W
, 1.149M ethylaluminum dichloride solution in Hemason 87 rn7! (,4t100 mmol)
Hair: Added dropwise. The resulting catalyst slurry was stirred for 1 hour.

The catalyst was then used to polymerize ethylene. One i-minute of the catalyst slurry was diluted with hemolysate. This rare'$＜Ij
j, a portion of the catalyst containing 1 mmol of titanium, was added to 1.7 mp of anhydrous, oxygen-free hexano 5 (l OmB and 0.593 M) ethylaluminum, which had been annealed with nitrogen. Stirring containing 1,81
was added to the reactor. The reactor was heated to 50 ps i with hydrogen.
The pressure was increased to 100 g, and the air was degassed using 07] sig. This operation was then repeated three times. The reactor pressure was then adjusted to 3 opsig with water and then 1100 p84 with ethylene. The reactor contents were heated to 80°C and then ethylene was added to maintain a constant reactor pressure of 15 opsig km. After 1 hour, the reactor was completely cooled and degassed.

The contents of the reactor were filtered and dried at 40° C. in an empty furnace until the polyethylene and hexane were removed. Polyethylene is 1'1ON and has a melting index of 136 (
ASTM 1238, condition L') was met. The catalyst efficiency was 3.550.000.9 polyethylene per 1 y of titanium. The II0/I2 ratio of the polymer was 94.

Example 7 1.0 M Tetraisoglovir Titanium in Hexane-5
, o mp (titanium 5.0 mmol 1, catalyst 10
The method of Example #8 was repeated for the preparation of a stripped catalyst used to have a magnesium to titanium atomic ratio of .

The procedure of Example 6 was then repeated using a portion of the catalyst prepared in this example containing 0.001 mmol of titanium and using 3 opsio of hydrogen to 1 portion of ethylene. Example 6 using 3 opsirt hydrogen
After carrying out the polymerization as described in
123B condition E). Catalyst point ratio is 1.950% of polyethylene per 1g of titanium. It was OOO&. Polymer σ]I,. //l2Jt was 8.5.

Example 8 1.0M Tetraisoprovir Titanium in Hessakusan) Lo
ng (1069 moles of titanium) during the catalyst preparation such that the resulting catalyst had an atomic ratio of magnesium to titanium of 5.

Revisiting the polymerization method of Example 7, Q) A part of the catalyst from Example 4111 (70.0 titanium (containing 617 moles of l t ) was used. What was obtained from the polymerization?' (Bo1) Ethylene is 16.8 and has a melting index (AST) of 1.18.
Mx2&8, condition E). Catalyst efficiency is 1g of titanium
Polyethylene 351,000. ! It was l'.

The 0/I ratio of the polymer was 8.7. This catalyst efficiency is one order lower than that of Example 7 because the Mg/Ti atomic ratio in the catalyst has decreased from 10.0 to 5.0.

Example 9 A dichloromagnesium chloride catalyst support was prepared and compared to a disilane magnesium chloride support.

A. Preparation of catalyst Instead of magnesium siloxide carrier solution,
No. 3,907.759, a toluene carrier solution (125me, magnesium 0,4
The method of preparation of the catalyst set forth in Example 7 was repeated except that M l was used.

B. Polymerization of ethyl/n! Titanium 0.02 described in Part 7 of 5L Example
By using a fraction of the catalyst containing mmol
The polymerization process described in Example 7 was repeated.

The obtained polyethylene was 116.7 g, 0514
(AsTM1238, Condition E). Catalytic efficiency is 886.00 r of polyethylene per gram of titanium.
It was 1,9.

Example 10 Hydrogen y, (for only 1 s p s i g - and butene -
The procedure of Example 7 was repeated except that 30M of 1 was added to the reactor along with the ethylene. The butene-ethylene copolymer obtained has a melt index IA of 110.5.9 and 0.99.
STM123B, with condition E1. Catalyst efficiency is 2,308,000 polymer per 14 titanium. ? Met. A.S.
A sample was prepared according to TM D-1928 and was
- The density of the polymer was determined according to ASTM D-1505 to be 0.9317 #/cc.

Example 11 The catalyst preparation process of Example 7 was repeated by using twice as much ethylaluminum isochloride so that the catalyst had a Cl/Mg atomic ratio of 8.

By repeating the polymerization process of Example 7 using the above catalyst and H,30ysig, polyethylene 42-7. ? I got it. Catalyst efficiency is titanium 19B polyethylene 891. +l 00 /i.

The polymer had a ratio of 0/I of 1Z5. When the catalyst of Example 7 was used in an undercarriage reaction in the presence of sufficient hydrogen to produce polyethylene with a melt index of 0.10, the polymer had an I of about 10.4. /I, ratio.

Examples 12-16 A, Preparation of carrier solution 0.715M Subbutylmagnesium 280ffi7! (
PMH5 (25.6 mA, 420 mmol Si) was slowly separated into a stirred solution of 33.1 ml (20 ml J mol) of PMH5 (200 mmol of Mg) and 0.593 &) ethylaluminum (20 mlJ mol of Al). The mixture was added slowly enough to avoid heating the mixture above 85°C.The stirred solution was then heated to 70-80°C.
℃ for 1 hour. After cooling to room temperature, the solution was diluted with V-free anhydrous hexane to 500 ml Ic.
．． A 40M magnesium isosiloxide solution was obtained.

B. Preparation of Catalysts The amounts of 1.149&ethylaluminum nochloride shown in Table 1 were prepared in Example 1. , 4M magnesium solution 125m/! and added dropwise to a stirred solution of 1.0 M tetraisopropyl titanate 50 in hexane. A series of resulting stirs with different C1/Mg atomic ratios were used to polymerize ethylene.

12 3 65 13 4 87 14 5 109 15 6 131 16 8 174 Example 17 A portion of each catalyst slurry from Examples 12-16 was diluted with hexane. This titanium o, ooi or 0.・
A portion of the diluted catalyst containing 0.002 mmol was added to 600 tnl. of anhydrous oxygen-free hexane. A stirred, nitrogen-purged, nitrogen-purged reactor containing 1.0 mmol of hydroethylaluminum and 1.81 was placed at zero thrust. The reactor was pressurized to 5 opsig with hydrogen and degassed to opsig. This operation was NAIed three times. Reactor pressure was increased to 50 or 7 psig with hydrogen and then 1 psig with ethylene.
Adjusted to 100psi. The contents of the reactor were heated to 80'C.

Ethylene was added to maintain a reaction pressure of 15 aps iσ. After 1 hour, the reactor was cooled and degassed. Reactor contents? :The filtered 1-ethylene chloride was dried in a vacuum oven at 40'C until free of hexane. The number of millimoles of titanium used, hydrogen pressure, catalyst efficiency, and polymer properties were determined as follows.
Shown in the table.

i$l:::':': Example 18 To determine the effect of the atomic ratio of Ct/MQ on catalyst efficiency, 11 solutions were performed:A. Preparation of catalyst 01M carrier solution, hexane, 0.1M ethylaluminum isochloride (EADCI, 0.001J tetraisopropyl titanate (T i (OiPr 14 1
and 0. 1M) ethylaluminum (TEAL
+hexane solutions by mixing in the order shown catalyst f. Manufactured. A carrier solution was prepared as described in Blowing Example 4 and diluted with hexane. The hexane added to the catalyst was adjusted so that the final catalyst slurry had a volume of 100-. The correct phase of the catalyst components used! All shown in Table 3.

3rd Table 18, 4 6, 3 62.4 6.3
12518B 6. -3 60.
9 7.8 12518C6,3□ 5
9.3 9.4 12.51BD
6.31 57.8 10.9 12.5
18E 6.3. 56.2 12.5
12.518F 6.3+ 54.
6 14.1 12L51gG6.31
53.1 15.6 1zs1811
6.3' 49,9 18.8 1 Z
5187 6.3' 40.6 2
8.1 12.518J6.3' 31
．． 2 37.5 1'L50, 1 M
Atomic ratio of components EAL ml Mg/Ti CL/Mg I'EAL/
T 1125 50 2.0 1001
25 50 2.5' 100125
50 3.0 100125 50
3.5 10 (1125504,0100 12,550-1,4,5100 115505, OZo.

x2+s so so e, o zo.

12-5 50 9.0 100115
Solza 100B, Ethylene Synthesis The catalyst prepared in A of this example was used in the solution polymerization of ethylene. In this polymerization, titanium 0°0,0025
2 (1 mg portions of the catalyst slurry containing mmol total,
15OpAR■E1゜Oll, stirring site containing about 57+sj1 hydrogen and 150qsi ethylene 1, 8 A
Nitrogen was pressurized into a stainless steel reactor heated at 150°C. The pressure in all reactors was kept constant by adding ethylene.

After 30 minutes of reaction, the contents of the reactor were reduced to 1. Reflux condenser
I moved it to a 3,0/〃 lath resin pot that I made parts with the elements I had. The polymer solution was cooled to room temperature and the solvent was removed. Table 4 shows the weight tPPJ1 medium efficiency of the obtained polymer and the melting index of the polymer.

Table 4 Catalyst C1/M (1 Number Atomic Ratio (IPE kg PE/i Ti
Ml.

□□ko=□□ 18.4 2.0 1 or less Approx. 10 -
-18B15 26.0 217. 4118C3,
049,64141,5 18D3.5 76.8 641 4.518E40
79.8 666 8.618F4.5 86.2 7
20 5.518G5.0 87.9 734 6.4
18B' 6.0 Bo, 5 672 3.818
IQ, 0 26.4 220. 4718J140
15.3 128. The molecular weight distribution as measured by 42'+o/I2 did not widen or diverge in these soluble polymerizations.

This data indicates that the molecular weight distribution for solution polymerization is C1/A.
The optimum C1/Mg atomic ratio for highest catalytic efficiency is about 4-6 (magnenium 1.
0).

Example 19 illustrates the effect of high atomic ratios of S i /lVg on catalyst efficiency.

A. Catalyst Preparation Example 16 with sufficient polymethylhydridosiloxane to give an atomic ratio of S i /J g of 2.5.
The catalyst preparation method was repeated.

B. Catalyst Preparation The catalyst preparation method of Example 16 was repeated using sufficient polymethylhydridosiloxane to give an atomic ratio of S i /Kg of 30.

C. Polymerization of Ethylene The polymerization method of Example 17 was repeated using catalysts A and B of this example and 70 psi of hydrogen. The amounts of titanium used and the results obtained are shown in Table 5. I was determined as described in Example 4.

Table 5 Example 16 2-1 0.002 305
L92 Example 19,4 Z5 0.004
629 3.55 Example 19B 3.0 0
．． 001 1330 3.76 Example 20 A. Preparation of catalyst 1.0M titanium tetrachloride5. ' Oat (Titanium 5.0
The catalyst preparation method of Example 7 was repeated except that tetraisopropyl titanate was used in place of tetraisopropyl titanate.

B. Polymerization of ethylene Present Example A-''C 1 part containing o, no i mmol of titanium as catalyst, hydrogen sopsig
The polymerization process of Example 17 was repeated by using 0.125 mmol of hydryethyl fluorinium. The polyethylene obtained was 74.8 M with a melting index of &08 and a molar mass of 8.3. /I2 ratio.

Catalytic efficiency is 1.560° of polyethylene per titanium lI.
It was oo, v.

Example 21 A. Preparation of catalyst 1.0M titanium tetrachloride5. The catalyst preparation method of Example 11 was repeated except that OmZ (5.0 mmol titanium) was used in place of tetraisopropyl titanate.

B. Polymerization of ethylene Titanium O, f'l O2 Mi IJ produced in Example A
The polymerization process of Example 21 was repeated by using one portion of the catalyst containing mol and 0.25 mmol of triethylaluminum. What about the polyethylene obtained? 0.
4, li', with a melting index of 1.16 and an I of 0.1.
,. /I. The catalyst efficiency was 735,000.9 polyethylene/g titanium.

A comparison of Examples 2G and 21 shows that when halide-containing titanium can be used and the chloride is added with ethylene isochloride, the molecular weight distribution of the polymer is ct
It shows that it changes from narrow to wide depending on the atomic ratio of 7Mg.

Example 22 0.7153/subbutylmagnesium 100100OM
g 715 mmol) and 0.898 & triethylaluminum 79.6-(At 71.5 mmol),
Polymethylhydridone piece sun +91.6d, S? :1
502 mmol) was added slowly. The exothermic reaction was controlled below about 80°C and then maintained by heating to 70°C for 1 hour. #The liquid was cooled to room temperature. Analysis for magnesium shows that the solution is magnesium and 0.6
It showed that it was 32M.

B. Preparation of catalyst Silicon tetrachloride in 100 ml of hexane (11.5 m/, 5 i
A solution of 100 mmol) was added to the solution 79. Oyd (MQ 5-0 mmol), Hezizan 46ml1. and 4.72 mg (ri 5. (1 mmol)) of Tetraingrovir titanate over a period of about 1 hour. A solution formed, but a solid formed over time.

C. Polymerization of Ethylene The catalyst of Example B was aged for two weeks. Titanium o, oos
A portion of the catalyst containing mmol was added to a 1,81 stirred stainless steel reactor containing 1.0 mmol of triethylaluminum and 600 mmol of hyhexane. Pressurize the reactor with hydrogen to 50 psig [7, npsi
It was degassed to g. This operation was repeated a total of three times (7).Then, the hydrogen pressure was increased to 50 psigKttl', and ethylene was added to bring the total pressure to 1 oopsig.The reactor contents were adjusted to 80°. C and the total reactor pressure was adjusted to 150 psig K. Polymerization was carried out for 1.0 hour while the total reactor pressure was maintained at 150 psig K by ethylene thrust 11. After 1.0 hour, the reactor was cooled. , the contents of the reactor were collected, and the polymer was collected by filtration.

After drying under vacuum at 60°C until hexane is gone,
6.7 g of polyethylene was obtained. This polymer has a melt index of 0.71 and a C of 7.2. /I, ratio. The kinetics of the catalyst was 17.000.9 polyethylene per gram of titanium. It shows that it is not the target. Alternatively, the polymer showed a narrow molecular weight distribution even if the atomic ratio of C1/Mσ was 80.

Example 23 A. Preparation of catalyst The method for preparing catalyst 1 of Example 22, B was repeated except that silicon tetrachloride was replaced with 11.77 mmol of tin tetrachloride (100 mmol of Sn). 1. Ta. A slurry of catalyst formed immediately.

B. Polymerization of Ethyl 1/N The polymerization step of Example 22, C was modified by using a portion of the catalyst slurry containing 0.25 mmol of triethylaluminum and 0.002 mmol of titanium from this Example A. It's a return. The resulting polymer was 91.9.9, with a melting index of 401 and an I of 7.0. /I, ratio. Catalyst efficiency is 959 polyethylene per titanium II
．． It was 000#. This example illustrates the use of tin tetrachloride as a halogenating agent to produce a highly efficient catalyst according to the present invention. However, the molecular weight distribution was very narrow.

The molecular weight distribution is Ha. It was determined using the ratio of /I.

In this case, the results are as follows: N1elsen, polymerR
heology, 69-75 hundred, MarceLDeak
er Pub, NY (19771). In this determination, I
, is the melting index, I, as determined by ASTM 123B Condition E. is the melting index as determined by ASTM 1238 condition N.

It is therefore clear that the catalyst of the invention is very efficient, easy to produce, does not require purification or washing techniques, and allows control of the molecular weight distribution of the resulting polymer.

Although certain intangible examples and detailed descriptions have been provided for the purpose of illustrating the invention, it is clear to Nagisa that further changes and modifications may be made while appreciating the spirit or scope of the invention. Dew.

%i IM people E.I. Dupont de Nemo Ryosu & Kanno (1 person excluding Nee)

Claims (1)

[Claims] 1. General formula % Formula % [In the formula, each R1 is independently hydrogen, alkyl having 1 to 20 carbon atoms, 7. Is it a sol group, an acyloxy group or an alkaryl group, and? 1. is greater than 1] containing thereon a transition metal compound and a halide compound, provided that the transition metal compound is selected from the group consisting of titanium, vanadium, chromium and zirconium alkoxide. and the halide and halide compound are soluble in hydrocarbons, and 510
the Mg ratio is at least g 1.0 and the norogen/Mct ratio is at least 2
0, an olefin polymerization catalyst. The catalyst according to claim 1, wherein the Z halogen is chlorine. 3. Catalyst filter according to claim 2, wherein n is about 1 to about 50 4.1) General formula % formula %] [wherein R1 is hydrogen, /.logen, carbon number 1 to 20] an alkyl group, each selected from the group consisting of an aryl group, an acyloxy group, an alkaryl group, and an acyloxy group each having 6 to 20 carbon atoms; 1 is 0↓, and the sum of α and b is 3
[In the formula, each R independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aralyl group, an aralkyl group, and an alkyl group each having 6 to 20 carbon atoms. 2) a reaction product having a SiO molar ratio of at least 1.0 with a soalkylmagnesium or an alkylmagnesium alkoxide of 2) having the general formula % [wherein M is titanium, panadium, Chromium or norconium, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an alkoxy group having 6 to 20 carbon atoms, q is 0 or l, and r is 2 ~4, and 2q+r is equal to the valence of H; p is at least 2; and X+y is equal to the valence of M]; and 3) at least one of A method for producing an olefin polymerization catalyst, characterized in that all halogenating agents are combined to obtain a polymerization catalyst having a halogen/magnesila ratio of 20. 5. The method according to claim 4, wherein the reaction product of +11 is brought into contact with (2J and then reacted with (3). 6. The reaction product of fi+ is brought into contact with (3) and then reacted with (2J). ] 7. The method according to claim 5, wherein α is 0.1 to 2 and b is 1.2 or 3. 8. Hydroboria 0 xane is polymethylhydrosiloxane, 4-ethylhydrone loxane, polymethylhydro-methylsiloxane copolymer, polymethylhydro-methyloctylsiloxane copolymer, polyethoxyhydrosiloxane, tetramethylnosiloxane, sophenylsoxane. Claim 7, which contains at least one substance selected from the group consisting of siloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, polyphenylhydroxychlorosiloxane, and polychlorophenylhydrosiloxane. Method. 9. Soalkylmagnesium is subbutylmagnesium, n-butyl-8ec-butylmagnesium, butylethylmagnesium, butyloctylmagnesium, so-n-hexylmagnesium・0,02) Limethylaluminum, V-n-butylmagnesium・2-triethylaluminum, 0.1-triethylaluminum, n-butylmagnesium, 0.1-triethylaluminum, subbutylmagnesium-triinobutylaluminum, subbutylmagnesium/2-triisobutylluminium, butyloctylmagnesium/2-triisobutylaluminum, butyloctylmagnesium/ 10. The method of claim 8, comprising at least one substance selected from the group consisting of - triethylaluminum, butylethylmagnesium, 01 triethylaluminum, and mixtures thereof. 10. Transition metal alkoxy pieces. Cyto is tetraisopropyl titanate, tetra-synthesis, -butyl titanate, tetrahis(2-ethyl halide)tita, t-, tri-butylpanadate, tetra-n-glopylsorconate and tetra-n- Butyl norconate, iso-C3H
,OCTi (0-iso-C3H7)! −〇〕、. 10. The method of claim 9, comprising at least one material selected from the group consisting of isoC3H, butyl(triisopropoxy)titanium, and mixtures thereof. 11. The method according to claim 10, wherein the halogenating agent is a chlorinating agent. 12- The chlorinating agent is an alkyl aluminum chloride,
Recommendation Mli is at least one substance selected from the group consisting of alkylaluminum chloride, and alkylaluminum sesquichloride, with the proviso that 2 alkyls are independently methyl, ethyl, or isobutyl.
The method described in section. 13. The method according to claim 4, wherein the reaction is carried out in the presence of slowly added aluminum alkyl before the addition of 13, +31. 14. In the 4-8 membrane formula, 8 is 1 to 2 in addition to hydropolysiloxane.
14. The method according to claim 13, wherein 3 is reacted with aluminum alkyl and then contacted with aluminum alkyl. 15, R is C1-C1° alkyl, 8 is 1-3, (1) is carried out using RM(IR・(, AlR23 film, and n is larger than 0) Claim 14
The method described in section. 16. The method of claim 15, wherein n is about 0.1 to about 10.0. 17. Hydropolysiloxane is polymethylhydrosiloxane (PMH5), $ethylhydrosiloxane,
Polymethylhydro-dumethylsiloxane copolymer, polymethylhydro-methyloctylsiloxane copolymer, polyethquinhydrosiloxane, tetramethylsoloxane, zophenyldusiloxane, trimethylcyclothrinloxane, tetramethylcyclotetranoxane, polyphenylhydro 17. The method of claim 16, comprising at least one material selected from the group consisting of siloxane, polyeicosylhydrosiloxane, polyethylchlorohydrosiloxane, and mixtures thereof. 18 Soalkylmagnesium is subbutylmagnesium, n-butyl-5ec-butylmagnesium, butylethylmagnesium, butyloctylmagnesium, so-n-hexylmagnesilla/002 trimethylaluminum, J-n-butylmagnesia/0.1 triethylaluminum , Zinium, Subtylmagnesium/2-triisobutylaluminum, Butyloctylmagnesium/Netsium Th'0. ,! -) ethylaluminum, and mixtures thereof. 19, the transition metal alkoxide is tetraisoglobyl titanate, tetra-n-butyl titanate, tetra(2-
ethylhexyl) titanate, tri-n-butylpanadate, tetra-η-propylsorconate and tetra-
n-butyl solconate, iso-C,It,O[Ti
(0-iso-C,H,I.-0), oisoC811, butyl(triisopropoxy)titanium, and mixtures thereof. The method according to claim 18. 20. The method according to claim 19, wherein the halogenating agent is a chlorinating agent. 21. The m-chlorinating agent is ethylaluminum sochloride, diethylaluminum chloride, ethylaluminum sesquichloride, Inbutyl and methyl congeners, 5nC
14,5iC1,, ECl, HSiCl3, aluminum chloride, ethyl boron sochloride, boron chloride, soethyl boron chloride, 11CC1,, p
ci,, poct, cetyl chloride, thionyl chloride, sulfur chloride, methyltrichlorosilane, nomethylsochlorosilane, TiCl2, and VCl. 21. The method of claim 20, wherein the method is selected from the group consisting of: 22. The method of claim 21, wherein the 2z chlorinating agent is selected from the group consisting of ethylaluminum sochloride, soethylaluminum chloride, ethylaluminum sesquichloride, and isobutyl and methyl congeners thereof. 23, 11 Formula R"8Si(OHI4-8(D) silane is reacted with methylkylmagnesium or alkylmagnesium alkoxide of formula RugR or RMQOR,
A hydrocarbon-insoluble reaction product having a 510Mg1Kg ratio of at least 1.0 is prepared, and the product of 21f1+ is then contacted with an aluminum alkyl of formula Al(R2)3 to convert the product- into hydrocarbons. 3]+2) is contacted with a transition metal alkoxide having at least one of the general formula %) (4) reacting the mixture of (2) and (3) with a halogenating agent; A polymerization catalyst having a halogen to magnesium ratio of at least 2 is obtained, provided that each R and R2 is independently an alkyl group, an aral group having 6 to 20 carbon atoms, and an alkaryl group, and each R2 is hydrogen. or an alkyl group having 1 to 20 carbon atoms, 8 is 1 to 3, g is 0 or 1, r is 2 to 4, p is at least 2, and X+1
is equal to the valence of H, and 2qτ is equal to the valence of M. 24. The method of claim 23, wherein the halogen is chlorine and the catalyst has a chlorine to magnesium ratio of about 3:1 to about 16=1. 25. The process according to item 24, wherein the halogen is chlorine and the ratio of catalyst to magnesium is from about 3=1 to about 16:1. 26. The method of claim 25, wherein the halogen is chlorine and the catalyst has a chlorine to magnesium ratio of about 3:1 to about 16:1. 27. The catalyst support contains magnesium and the polymerization is carried out as a slurry polymerization, catalyzing excess chloride such that the atomic ratio of chlorine to magnesium is at least 2 and the atomic ratio of silicon to magnesium is at least 2. provided that the excess chloride is provided from a compound of aluminum, boron, v or a mixture thereof and the excess chloride represents at least 80 mol% of the total chloride of the catalyst. Compatible olefin polymerization catalyst for controlling the molecular weight distribution of polymers. 28 Excess chlorine is obtained from aluminum compounds,
28. The catalyst of claim 27, wherein the C1,/MQ ratio is from about 4 to about 8. 29. the aluminum compound is selected from the group consisting of alkylaluminum isochloride, soalkylaluminum chloride, alkylaluminum sesquihalide;
29. The catalyst according to claim 28, wherein said alkyl is methyl, ethyl, isobutyl or a mixture thereof. 30. Magnesium is included in the carrier along with excess chlorine such that the atomic ratio of chlorine to magnesium is at least 4 and the atomic ratio of silicon to magnesium is at least 2, and the excess chloride is aluminum. , boron or a mixture thereof, wherein the excess chloride is at least 80 mol % of the total catalyst chloride (corresponding to a supported polymerization catalyst). A method for carrying out slurry polymerization reactions of olefins in which the olefin polymers are controlled in terms of molecular weight distribution.
The method according to item 30 of the mIL section. 32. The aluminum compound is selected from the group consisting of alkyl aluminum isochloride, dialkylaluminum chloride, alkyl aluminum sesquihalide, with the proviso that the alkyl is methyl, ethyl, isobutyl or a mixture thereof. Method. 33. The process of claim 32, wherein at least some ethylene is present and the reaction is conducted at a temperature of about 40 to about 100'C, (i'). 34. The atomic ratio of chlorine and magnesium in the catalyst is about 4 to about 1
34. The method according to claim 33, wherein the method is: 35. The method of claim 34, wherein the atomic ratio of C1 and M (1) is about 8.