JPS5810403B2 - Shiyokubaisosabutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improved catalysts for the polymerization of olefins such as ethylene.

More particularly, the present invention relates to supported catalysts of the Ziegler type for use in the polymerization of olefins to produce high yields of polymers with particularly desirable properties.

Polymerization of ethylene and other olefins alone to form homopolymers or in combination to form interpolymers or co-electropolymers at relatively low pressures and temperatures by using so-called Ziegler catalysts It has been known for a long time that this can be done.

Ziegler catalysts are broadly defined as strong reducing agents such as organometallic compounds of alkali metals, alkaline earth metals, zinc, earth metals or rare earth metals and various reducible heavy metal compounds such as Nos. NB, VB, and ■ of the periodic table. B.

■B and group ■ metal halides, alkoxides,
It can be described as consisting of various combinations with acetylacetonate and others.

Among the preferred types of catalysts for this reaction are those consisting of a vanadium compound and an organoaluminium compound as an activator, such as an aluminum alkyl or alkyl aluminum halide.

Such catalysts are described, inter alia, in U.S. Pat. No. 12,962,451 and U.S. Pat.
No. 57,332.

Particularly preferred are vanadium oxychloride combined with alkyl aluminum compounds such as triethyl aluminum,
It is a catalyst containing ethylaluminum dichloride, diethylaluminum chloride and others.

For these catalysts, very small amounts of vanadium compounds are used to give high yields of polymer per unit of catalyst, which can be recovered from the reaction mixture by simple separation techniques such as filtration, centrifugation, evaporation or displacement. It can then be processed without the need for further purification or chemical treatment.

The catalyst comprises a suitable material, such as a finely divided or granular polymer (preferably of the same type as the polymer produced by the process of the invention), and the catalyst components thereon. Supported on any inert anhydrous material suitable for adsorption and/or deposition (e.g. anhydrous silica, alumina, alumina-silica mixtures, calcium carbonate, calcium chloride, sodium chloride, charcoal, carbon black, etc.) It may be unsupported or unsupported.

Such supports are particularly useful in gas phase polymerizations, but they can be used in slurry type polymerizations as well.

Generally, polymers made using the catalysts are of high density, ie, 0.95 and higher.

The molecular weight of the polymers so produced lies within a wide range.

2,000-300,000 and 3,000,000
It is possible to produce polymers having molecular weights as high as or even higher.

Control of molecular weight can be achieved, to some extent, by controlling process variables, but in view of the general interdependence of process variables, such control usually involves the addition of varying amounts of modifiers, e.g. No. 3,051,6
This is done by adding hydrogen or haloalkanes as described in No. 90.

However, when hydrogen is used in large amounts, such as greater than 50% by volume, as is required in some cases to obtain the desired molecular weight control, the polymerization reaction rate decreases and the productivity per unit time decreases. This results in a decrease in

Furthermore, when using the catalyst system described, only a certain degree of control can be achieved depending on the hydrogen.

Depending on the particular catalyst system, there is an upper limit beyond which further hydrogenation has little further effect.

Means for overcoming the drawbacks or disadvantages discussed above with respect to vanadium-containing catalysts are described in U.S. Pat. No. 3,784,539, which is incorporated herein by reference. .

Therein, catalysts are described that enhance the ability of hydrogen to act as a chain transfer agent in controlling the molecular weight of olefin polymers.

The catalysts prepared as described there can be used in unsupported form or supported on suitable materials.

Supported catalysts are particularly suitable in gas phase polymerizations.

The inventors hereby disclose that the use of such catalysts supported on silica gel treated with certain materials, namely organoaluminum compounds, does not result in any deterioration in the desired physical properties of the resulting polymers. It has been discovered that a substantial increase in yield can be obtained without the use of

It has also been recognized that the polymers produced using the prior art vanadium catalysts do not have a sufficiently broad molecular weight distribution to make them generally suitable for processing into bottles by blow molding. There is.

This apparent disadvantage is that when such catalysts are supported on inorganic materials and prepared in a particular manner, they have a constant V3 in the range of 50 to 95 kilopoise (kp).
It is highly effective in producing ethylene polymers with a relatively broad molecular weight distribution as measured by the ratio of the apparent viscosity of 3 s-1 to the apparent viscosity of 300 s-1 in value (3/V300). This was overcome by this discovery.

This measurement is widely used by polymer processors using conventional plastic molding machines for blow molding.

Viscosity measurements were performed using a Monsanto capillary extrusion rheometer (manufactured by Instron Engineering Corporation) with a diameter of 0.05024 inches, a length of 2.006 inches, and an entrance angle of 90° at a temperature of 200°C. Use and 'Encyclopedia of
Polymer Science and Technology (published by Interscience Publishers) Volume 8 No. 607~
This was done using the method described on page 611.

Generally, suitable resins for milk bottles are V3. It has a V3/v3oo with an f6 pitch of 9 to 11.5.

Resin suitable for detergent and general purpose bottles is 65-95kp
It has a v3 in the range and a V3/v3oo of 9-12.

The lower ratio corresponds to the lower ■3 value and vice versa.

According to the invention, silica gel is used as a catalyst support and said silica gel is combined with an organoaluminum compound (
Enhanced activity towards polymerization and copolymerization of ethylene in the presence of hydrogen as molecular weight controlling agent, for example by treatment with alkyl aluminum, alkyl aluminum halide, alkyl aluminum alkoxide or mixtures thereof. Certain supported catalyst compositions of the Ziegler type having a Other Ziegler type catalysts are provided.

That is, after the reaction, a compound of essentially vanadium, a trialkylaluminum and a compound of the formula RnAl(OR)3-n, where R is about 1, is deposited on the reacted silica gel.
a hydrocarbyl group containing ~12 carbon atoms and n varies from 0.5 to 20) or a mixture of such compounds, said composition comprising (prepared by combining a vanadium compound with the aluminum alkoxide and subsequently combining the reaction mixture with the trialkylaluminum).

Although the catalysts so prepared are suitable for use in gas phase or slurry phase polymerizations and copolymerizations of ethylene, they are particularly preferred for gas phase polymerizations.

The invention is illustrated by the following examples.

However, these do not limit the invention in any way.

All parts are parts by weight unless otherwise specified.

Example 1 The polymerization of ethylene in a gas phase series using hydrogen as a molecular weight control agent was carried out in a laboratory scale unit to prepare a raw material as a support for a vanadium oxychloride-alkylaluminium-alkylaluminum alkoxide catalyst. The effect of using silica gel and silica gel treated by reacting it with an alkyl aluminum or an alkyl aluminum alkoxide is shown.

Silica gel (with an average particle size of about 50-65μ (US standard sieve series 230-270 mesh size))
MS ID grade 952. W, R.

Brace & Compagnie) was dehydrated in a fluidized bed at 200° C. for about 12 hours using dry nitrogen as the fluidizing gas.

The dry silica contained about 1.4 mmoles of available hydroxyl groups per gram on its surface, as determined by reaction with triethylaluminum.

An approximately 24 g portion of this dehydrated gel was charged into a small fluidized bed catalyst production unit and fluidized with oxygen-free dry nitrogen at a temperature of approximately 40°C, while a 2M solution of triethylaluminum (TEA) in hexane was added to the silica gel. Added drop by drop on top.

The amount of TEA used was equal to 1 mmol/g of silica gel.

After the TEA addition was complete, the hexane was evaporated from the fluidized bed.

Similarly, two other separate 24 g portions of dehydrated silica gel were each treated with diethyl aluminum ethoxide (D
EAE) and ethylaluminum shedoxide (E
ADE).

Polymerization catalysts were prepared using three treated silica gel samples and one untreated sample of dehydrated silica gel as supports.

In a glass container covered with nitrogen while stirring, add 100
ml of hexane and the amount of pure VOCl3.ml necessary to give the predetermined molar ratios of each component. EADE or ethylaluminum sesquiethoxide (EASE)
and TEA in hexane were charged in that order.

The mixture was stirred for 10 minutes before it was fed to a catalyst production unit where the catalyst support was fluidized with dry nitrogen.

The catalyst solution was thus deposited onto this support and fluidization was continued until all the hexane had evaporated and the catalyst was dry.

Each catalyst was then tested in a series of ethylene polymerizations.

The catalyst was charged to a polymerization reactor in a laboratory scale unit containing the reactor, heat exchanger and necessary accessories.

The jacketed reactor was cylindrical in shape and sized to contain a fluidized bed of catalyst and product particles approximately 4 inches in diameter and 2.5 to 3 feet deep.

At the top of the bed section, the reactor extends in an inverted cone shape into a larger diameter separating section in which any particles entrained in the unreacted gas are separated and removed from the bed. It was dropped and returned.

Unreacted or recycle gas is continuously withdrawn from the top of the separation zone and passed through a heat exchanger to maintain the front plate at a defined temperature and to keep the particles in the bed in a highly fluidized state. was introduced into the bottom of the reactor at a rate sufficient to maintain the

Make-up ethylene and hydrogen were introduced into the recycle gas line while fresh catalyst particles were fed into the reactor below the top of the bed.

The polymer product was removed at the bottom of the bed.

Additional TEA was added during the polymerization at a rate of about 2-3 mmol TEA per hour.

In one experiment, halogenated alkanes were introduced into the reactor along with ethylene in separately metered streams to provide an amount of halogenated alkanes equal to about 100 mmol per millimeter of vanadium per hour.

The reactor pressure was approximately 36.2 mmH.

The product polyethylene was removed continuously at a rate of about 1 pph to maintain a constant bed level as described above.

The polymer samples produced were evaluated for their physical properties.

In measuring the properties of the polymers, the following method was used.

Melt index (I2) is 2,160
Measured by ASTM test D-1238-65T using g weight.

Melt extrusion rate (110) was measured using the same method used for melt index measurements except that the sample weight was 10 kg.

ASTM test D-1895-A- for bulk density measurements
67 were used.

The results of these tests, shown in Table 1 along with the polymerization conditions, show that pretreatment of the silica gel support with an aluminum alkyl leads to higher polyethylene yields under equivalent polymerization conditions than that obtained using untreated silica gel as the support. It shows that the polymer properties are not adversely affected in any way.

Table 1 Catalyst Composition Heavy Properties Silica Gel VOC1 Alkoxy Milli TEA Temperature Halogenation H2 Yield Bulk Density Modifier Millimoles Side Mol Millimoles (°C) Alkanes % kyP
,t&#V I2 Ito/12(ky/d none 2 EASE12 6105 none
5.3 25 1.4 11.3381D, EA,
E 2 tt 12 6106
None 4.9 33 1.4 10.6374 None I II 6390CC13F5.9218
4.111.3318TEA 1/l
6 3 89 CCl3F 6.1274
4.8 11.5352DEAE 1/l
6 3 90CClsF6.45014.11
2.1:33buEADE 1 tt
6 3 89 CC1jsF 6.02355
．． 1 No 110345 I EADE12121
05 CHCl18.0196.69.6408TEA
1 tt 12 12105
CHCl57.21247-5 9.4442DEA
E 1 u 12 12107
CHCl 5.5325 6.6 9.0426
EADE 1 tt 12 1210
7 CHCl3-5.33868.3 8.641
Example 3 Example 2 A series of ethylene polymerizations similar to those in Example 1 were carried out using treated and untreated silica gel as catalyst supports, except that the polymerizations were carried out in the slurry phase.

25 in a flask with a magnetic stirrer purged with dry nitrogen.
Polymerization catalyst (1) was prepared by suspending 5 g of anhydrous silica gel in ml of hexane.

To this suspension was added an amount of EADE (4.0 mmol) corresponding to 0.8 mmol per g of silica gel, and the resulting mixture was stirred at room temperature for at least 30 minutes.

In a separate nitrogen-purged bottle containing 5.0 mA' of dry hexane, 8 mmol of EADE and 4 mmol of VOCl were stirred together for 5 minutes, then 8 mmol of TEA was added, and the entire mixture was stirred at room temperature. Stir together for 30 minutes.

This mixture was added to the silica gel mixture with stirring.

After about an hour, the hexane layer became completely transparent, indicating complete adsorption of catalyst on the silica gel.

Polymerization catalyst (2) was prepared in exactly the same manner as catalyst (1), except that the silica gel was not first reacted or treated with EADE.

Ethylene was polymerized in hexane medium using the two catalysts prepared as described above.

Polymerizations were carried out in a closed system using a stirred 2,51 stainless steel reactor.

The reactor was prepared by cleaning, drying and purging with hot nitrogen until essentially free of oxygen, and charging with hexane.

The system was flushed with ethylene at atmospheric pressure and the catalyst suspension was introduced into the reactor.

All ethylene introduced into the reactor was first passed through an activated carbon and molecular sieve column for drying and removal of trace impurities.

Hydrogen was then added to approximately 17.5 psig (5% concentration overall).
It was introduced to a pressure of

The ethylene to be polymerized was supplied at 350 ps from a volumetrically calibrated oxygen-free high-pressure cylinder (which was equilibrated to laboratory room conditions through an electric solenoid valve).
ig was fed until the final reaction force was achieved.

The total amount of ethylene introduced was determined by calculating using upstream flow pressure measurements before and after polymerization with an electronic converter.

During the polymerization period of about 2 hours under constant stirring, the temperature was about 85°C.
A small amount of TEA solution (1M) in hexane is kept at a constant temperature (this tends to decrease with time).
was injected into the reactor to maintain the

At the end of the reaction period, the contents of the reactor were allowed to cool.

Unreacted ethylene was evacuated and replaced with dry nitrogen.

The reaction slurry was poured into a receiver and then passed through a large Buchner funnel.

The phenolic antioxidant solution was thoroughly mixed with the polymer, after which it was dried in a vacuum oven overnight.

The physical properties of the polymer were determined using samples of the dried stabilized material.

The results provided in Table 2 were consistent with those obtained with the gas phase polymerization of Example 1.

The yields obtained using the catalyst supported on EADE-treated silica gel were significantly higher than those obtained with the catalyst supported on untreated silica gel under comparable polymerization conditions.

The polymers in both cases had the same number of physical properties.

It is also seen that the catalyst supported on treated silica gel provides a polymer with a higher bulk density than the polymer obtained with the catalyst on untreated silica gel.

Table 2 Catalyst composition
Polymer properties catalyst VOC73EADE
TEA halogenation yield
Bulk density production (mmol) (mmol) (mmol) Alkane 1yPE/, 9V, I2 1
1o/I2 k'i/1111 4
8 8 None
132.2 0.14 10.9 230
1 4 8 8
None 118.1 0.3
10.6 2541 4 8
8 None 123
．． 9 0.17 10.5 2071
4 8 8 CHC#
396 0.18 10.6 178
2 4 12 8
None 51.2 0.2
10.9 1132 4 12
8 None 93
．． 0 0.2 10.0 1512
4 12 S
None 81.7 0.17
8.2 11527 4
12 8 None
98.0 2.1 11.0 178
2 4 12 8 C
) IC6221,60,1510,0126* 10%
Processing the silica gel catalyst support to obtain the benefits shown in the hydrogen examples is relatively easy to accomplish.

This is because the only requirement is to remove physically adsorbed water.

The silica gel may be dried at a temperature of about 150 DEG to 260 DEG C. under atmospheric pressure for at least 4 hours, and preferably for about 6 to about 12 hours.

This drying step is conveniently carried out by passing hot nitrogen through a fluidized or fixed bed of silica gel.

Alternatively, the silica gel can be heated at about 100° to about 100° under vacuum.
It can be dried at a temperature of 200° C. for the same time, but without nitrogen purge.

After drying has taken place, a solution of the desired organoaluminum compound in a solvent such as hexane can be slowly loaded onto the silica gel, while it is being mixed by a flowing gas or by mechanical means.

Depending on the solvent used, ambient temperatures of 25-50°C are generally suitable.

This solvent evaporates while the reaction with the organoaluminium compound takes place.

However, temperatures as high as 80°C or higher can be used.

Alternatively, the dry silica gel can be suspended in a suitable solvent such as hexane and the organoaluminum compound added to the suspension or slurry for reaction therewith.

Stirring is necessary for good contact and mixing.

Contact time should be about 5 minutes to about 2 hours to ensure reaction.

If the catalyst is used for slurry phase polymerization, it is not necessary to remove the solvent.

However, it can be removed by conventional techniques such as filtration, centrifugation, evaporation, nitrogen bubbling, etc. to produce a dry catalyst useful in gas phase polymerizations.

Preferably, this processing step is carried out in an inert atmosphere.

The organoaluminum compounds that can be used to form the catalysts of the present invention are those commonly used as reducing agents for Ziegler type catalysts.

These include (1) the formula RnAlX3-n (wherein R is a saturated acyclic hydrocarbon group, a saturated cyclic hydrocarbon group, or an aromatic hydrocarbon group containing 1 to 10 carbon atoms;
X is halogen and n is 1, 2 or 3)
and mixtures thereof, and (2) compounds of formula RnA
Al(OR)3-n, where R is a hydrocarbyl group containing about 1 to about 12 carbon atoms and n is 1,2
or 3) and mixtures thereof.

The hydrocarbyl group is a hydrocarbon group such as alkyl,
It can be any selected from aryl, alkaryl, aralkyl, alicyclic, bicyclic, and others.

Suitable groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, impentyl, tertiary pentyl, hexyl, cyclohexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, cyclohexyl. Methyl, nonyl, decyl,
Mention may be made of dodecyl, benzyl, vinyl, vinylmethyl, phenethyl, p-methylbenzyl, phenyl, tolyl, xylyl, naphthyl, ethylphenyl, methylnaphthyl or any such similar hydrocarbon group.

Preferably, these R groups directly bonded to the aluminum atom are alkyl groups containing 1 to 8 carbon atoms, and they can be the same or different.

Specific examples of suitable compounds of formula (1) include triethylaluminum, tributylaluminum, triisobutylaluminum, tripropylaluminum, triphenylaluminum, trioctylaluminum, tridodecylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum chloride, These include propylaluminum fluoride, diisobutylaluminum chloride, ethylaluminum dichloride, and others.

Mixtures of aluminum compounds of the aforementioned types can also be used.

The formation of such compounds, i.e. the total reaction mixture obtained by treating aluminum metal with an alkyl halide to produce mixtures such as dialkylaluminum halides brass monoalkylaluminum dihalides, referred to as alkyl aluminum sesquihalides, is also suitable. It is.

Preferred compounds for use as treatment agents are those that are not halogenated.

The reason is that if these are used, there will be no problem of halogen remaining in the polymer.

Particularly preferred among the non-halogenated compounds is triethylaluminum.

Examples of suitable compounds of formula (2) are ethylaluminum shedoxide, diethylaluminum ethoxide, ethylaluminum sesquiethoxide, ethylaluminum, diisopropoxide, and others.

Particularly preferred is diethylaluminum ethoxide.

The amount of alkyl aluminum compound used depends on the amount of available hydroxyl groups on the silica gel surface.

This amount can be determined, for example, by reacting the support material with excess TEA and measuring the amount of ethane formed.

The actual amount of organoaluminum compound used in treating the silica gel will vary from about 0.3 to 1.0 moles of aluminum compound per mole of available hydroxyl groups as determined by the method described above.

The preferred amount of organoaluminum compound is 1
It ranges from about 0.50 to about 0.75 moles per mole.

The particle size of the silica gel used as catalyst support is not critical.

However, in gas phase polymerization, the particle size used depends on the desired particle size of the polymer being produced.

The reason for this is that, as disclosed in U.S. Patent Application No. 341,837, it has been established that product particle size may be controlled by using catalyst support materials having a specific range of particle sizes. This is because

Generally, for efficient operation, the catalyst support has an average particle size ranging from about 30 to about 600 microns, depending on the melting index of the polymer being produced.

Higher melting index polymers (~5 and above) require supports with larger average particle sizes, while lower melting index products (~1 and below) require smaller particle size required.

The catalyst composition deposited on treated silica gel in the context of the present invention is a vanadium-containing Ziegler-type catalyst as described in US Pat. No. 3,784,539, which is incorporated herein by reference.

These are preferably vanadium halides, but
However, it consists of compounds of vanadium, trialkylaluminums and alkylaluminum alkoxides, which may also be alkoxides, organic salts or complexes of this metal.

The vanadium in the compound used should be in a higher valence form than the lowest possible valence, and this should preferably be in a valence state of 3 and above.

Mixtures of tetrahalides, trihalides and di-, tri- and tetrahalides and others can be used.

Particularly preferred is vanadium oxytrichloride.

Vanadium compounds other than halides which can be used include vanadium triacetylacetonate, vanadium oxydiacetylacetonate, vanadium naphthinate, vanadium benzony t4 or vanadium esters such as VO(OC4H9-1)3°VO(OC3
H7-1)3. VO(OC2H5)C12゜VO(OC
2H5) 2Cl and others.

In addition to TEA shown in the examples, trialkylaluminum compounds include tributylaluminum, trimethylaluminum, triisobutylaluminum,
Examples include tripropyl aluminum, trioctyl aluminum, tridodecyl aluminum, and others.

The aluminum alkoxide used in the catalyst composition has the formula RnAl(OR)3-n, where R is a hydrocarbyl group containing from about 1 to about 12 carbon atoms, and n is from 0.5 to 2.0 and preferably varying from 1 to 1.5).

The hydrocarbyl group can be any selected hydrocarbon group such as alkyl, aryl, alkaryl, aralkyl, cycloaliphatic, bicyclic, etc.

Suitable groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, impentyl, tertiary pentyl, hexyl, cyclohexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, cyclohexyl. Methyl, nonyl, decyl,
Mention may be made of dodecyl, benzyl, vinyl, vinylmethyl, phenethyl, p-methylbenzyl, phenyl, tolyl, xylyl, naphthyl, ethylphenyl, methylnaphthyl or any such similar hydrocarbon group.

Preferably, these R groups directly bonded to the aluminum atom are alkyl groups containing 1 to 8 carbon atoms, and they can be the same or different.

A method for making alkyl aluminum alkoxides is described in US Pat. No. 3,784,539.

The active components of the catalyst are deposited on the treated silica gel as described above, or alternatively the catalyst is prepared as a solution or slurry and thoroughly mixed with the support;
Meanwhile, the latter is kept in a blended state in a suitable device.

The solvent or carrier liquid is evaporated and the catalyst is dried on the support.

Deposition can be carried out at atmospheric pressure, under elevated pressure or under reduced pressure.

Alternatively, a catalyst solution or suspension can be prepared by combining the vanadium-containing compound and the alkoxide and then adding an alkyl aluminum in a suitable reaction medium.

The resulting mixture is then mixed with treated silica gel and the resulting slurry is charged to a reactor.

The amounts of the components of the catalyst system of the invention can vary.

Generally, the molar ratio of organoaluminum compound to vanadium compound ranges from 0.3:1 to 500:1;
And this can be up to 1000:1 or even higher.

A preferred Al:V ratio of organoaluminum compound to vanadium compound is between 1:1 and 500:1.

In these compositions containing alkyl aluminum alkoxides, the alkoxide:vanadium ratio is
Similarly, it may vary from about 1=10 to about 100:1.

For most efficient operation, about 1:2 to about 50:1
The ratio of is used.

The amount of catalyst required is relatively small.

Generally 0.01 to 5.0 based on the total weight of monomers charged
The amount in weight percent is satisfactory.

However, amounts as low as 0.001% are sometimes acceptable, and larger amounts, for example up to 20%, can also be used.

The polymerization reaction can be carried out over a wide range of temperatures from 0 DEG to 120 DEG C. and, if desired, higher.

Preferably, the reaction temperature is maintained between about 65° and 115°C.

Similarly, atmospheric and subatmospheric pressures can be used, but
Pressures above atmospheric pressure are preferred.

The applicability of the present catalyst is not limited to any catalyst suspension medium or to any temperature and pressure conditions under which the polymerization reaction itself is carried out.

However, gas phase reactions are preferred.

The catalysts of this invention are equally useful with or without polymerization modifiers such as hydrogen, haloalkanes such as dichloromethane, chloroform, carbon tetrachloride, and the like.

Generally, when the vanadium-containing catalyst of the present invention is used in the polymerization of olefins, only a small amount of catalyst is required, and the catalyst residue in the polymer is at such a low level that it is not significant and subsequent Does not cause problems in polymer processing.

If the polymerization is carried out in the gas phase, quenching is usually not necessary.

However, when slurry phase technology is used, it may be necessary or desirable in some cases to deactivate the catalyst and remove catalyst residue from the polymer.

All alkyl alcohols containing 2 to 8 carbon atoms can be used for quenching or decomposition of the catalyst after the polymerization is complete and before separation of the polymer from the reaction mixture.

Among suitable alcohols, including ethyl alcohol, propyl alcohol, isobutyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, and others, isopropyl and tertiary butyl alcohol are preferred quenching agents.

The amount of alcohol used for quenching is critical only in the sense that it must be sufficient to completely destroy all catalyst activity, and this is critical only in the sense that the reaction mixture of the polyolefin slurry being treated may vary widely from about 0.001% to about 300% by weight.

The optimum amount used will vary depending on the amount of catalyst present in the polymerization product.

Generally, an amount of approximately equivalent to the total number of aluminum-carbon bonds in the catalyst component up to about 25% by weight of the polymer slurry is satisfactory.

However, this amount can be controlled, if desired, to provide sufficient alcohol to produce a slurry of satisfactory fluidity while remaining within the limits of economical operation and Recovery can be carried out according to well-known conventional methods.

The improved catalyst produced as described herein is broadly applicable for use in the production of all solid polymers commonly produced by the use of Ziegler type catalysts.

It is an ethylenically unsaturated hydrocarbon or olefin such as ethylene, propylene, butene-1, as mentioned in the examples.
heptene-1, octadecene-1, dodecene-1,3-
Polymerization of methylbutene, 4-methylbutene-1, styrene, vinylcyclohexene, etc., alone or with each other or with other monomers, especially diolefins such as butadiene, isoprene, piperylene, cyclopentadiene, 1,4-pentadiene, etc. It is particularly suitable for use with polymers produced by.

Claims (1)

[Claims] 1 Silica gel is prepared from (a) the formula RnAlX3-n (in the formula R
is a saturated acyclic hydrocarbon group, a saturated cyclic hydrocarbon group or an aromatic hydrocarbon group containing 1 to 10 carbon atoms, X is halogen and n is 1°2 or 3) and (b) compounds of formula RnA
An organic compound selected from the group consisting of l(OR)3-n, where R is a hydrocarbyl group containing 1 to 12 carbon atoms and n is 1, 2 or 3, or mixtures thereof. was reacted with an aluminum compound, and then a vanadium compound of the formula Rn was applied onto the reacted silica gel.
Al(OR)3-n, where R is a hydrocarbyl group containing about 1 to about 12 carbon atoms and n is about 0.
depositing a vanadium compound-containing catalyst formulation prepared by combining a trialkylaluminum with a mixture obtained by combining an alkyl aluminum alkoxide of 5 to 2.0
Ziegler type supported catalyst composition for olefin polymerization.