JPS5984905A - Olefin polymerization catalyst, manufacture and use - 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 method for polymerizing olefins. In another aspect, the present invention relates to a method for producing a polymerization catalyst. In yet another aspect, the present invention relates to a method for polymerizing alpha-olefins using a catalyst system prepared by a novel method. In yet another aspect, the present invention relates to a novel method for producing catalysts that can be used in conjunction with cocatalysts to form catalyst systems for alpha-olefin polymerization. In yet another aspect, the invention relates to catalyst precursors.

It is known to polymerize α-olefins and mixtures thereof under low pressure using coordination catalysts. Catalysts used in these processes are those of the first VB, VB, VIB of the periodic table.
It is produced from a mixture of a compound of a subgroup transition element and a hydride or an organometallic compound of an element of groups 1 to 2 of the periodic table. The periodic table referred to here is manufactured by Chemical Rubber Company (C!h
The cost of issuing a chemical rubberoo,
Hanabook of Chemistry and Physics
d Physics) 45th edition (1964) B-
It is published on page 2. Polymerization is generally carried out in suspension, in solution, and sometimes in the gas phase.

In an inert diluent at a temperature such that the resulting polymer does not go into solution and can therefore be recovered without a complicated step of removing the catalyst, resulting in a significant saving in process costs. It is desirable to carry out olefin polymerization reactions, particularly those involving ethylene and copolymers containing predominantly ethylene. In order for this type of process to become more economically viable from a practical point of view, the catalyst must be able to produce the polymer with high productivity and the residual catalyst content in the final polymer must be very low. It must be of a standard. Therefore, the activity of catalysts for olefin polymerization is one of the important factors that is always the subject of research for catalysts useful for polymerization of α-olefins. It is also desirable that the method used to form the catalyst be one that is easy to manufacture and allows control over the final catalyst formed.

It would also be desirable to provide a catalyst for producing &IJ olefins suitable for use in rotational molding processes.

In addition to catalyst productivity, the properties of the resulting polymer particles are another important factor for polymerization methods and catalysts. Strength,
It is desirable to produce polymer particles that are characterized by dimensional uniformity and relatively low fines production. Although polymer fluffs containing relatively high titers and fines can be handled by modification of the equipment, it is highly desirable to produce polymers with a low fines content at high productivity.

According to an embodiment of the invention, a first reactant selected from the group consisting of an aryl silanol, a secondary amine, and an organophosphorus compound which may be a hydrocarbylphosphine oxide or a hydrocarbyl phosphite, said arylsilanol is represented by the formula % (wherein each R represents a substituted or unsubstituted aryl group having 6 to about 20 carbon atoms, and they may be the same or different) and the secondary amine has the formula (wherein each R' represents a substituted or unsubstituted hydrocarbyl group having 1 to about 2 carbon atoms, which may be the same or different The total number of carbon atoms must be sufficient to make the amine soluble in the hydrocarbon solvent), and the carbylphosphine oxai P has the formula
R'3F==0 (wherein each R' represents a substituted or unsubstituted hydrocarbyl group having 1 to about 20 carbon atoms, which may be the same or different from each other, The number of carbon atoms must be sufficient to make the phosphine oxide soluble in the hydrocarbon solvent, and the hydrocarbyl phosphite is expressed in the formula % (formula %) (wherein each R' represents a substituted or unsubstituted hydrocarbyl group having 1 to about 20 carbon atoms, which may be the same or different from each other; a second reactant selected from the group consisting of halogenated transition metal compounds and organometallic compounds, wherein the halogen A transition metal compound having the formula % (wherein M represents a transition metal selected from Group ⅢB or VB of the periodic table, preferably titanium, zirconium or hafnium, and R/ represents a carbon number of 1 to about 20 a hydrocarbyl group, preferably an alkyl group having 1 to about 20 carbon atoms,
From cycloalkyl or aryl groups! 2, v=0.
1.2 or 6;
a catalyst precursor obtained by combining said organometallic metal with said second reactant, represented by The body is provided.

When the second reactant consists of a halogenated transition metal compound, the obtained catalyst precursor is combined with an organometallic compound containing a metal selected from Groups 1 to 2 of the periodic table, preferably magnesium. The polymerization catalyst of the present invention can be obtained in this manner. The catalyst can be further activated by treating it with a halide ion exchange source which may be the same or different from the halogenated transition metal compound used as the second reactant.

When the second reactant consists of an organometallic compound, the obtained catalyst precursor and the formula % (wherein M is a transition metal selected from Group IB or VB of the periodic table, preferably l:> made of titanium, zirconium or hafnium, R/ is a hydrocarbyl group having 1 to about 20 carbon atoms, p, v=0.1.2 or 6, υ;
X consists of a halogen selected from chlorine, bromine or iodine, preferably chlorine, w=1.2 or 6, and v
+w+1 is equal to the valency of M) can be combined with a transition metal compound, and the resulting complex can be further combined with a ride ion exchange source to provide a good You can get results.

Although not limited thereto, in order to facilitate the following discussion, the catalyst precursor obtained from the arylsilanol halogenated transition metal compound will be represented by the formula % (formula %); A monomer in a product or an intermediate product from which the product is obtained. It's just that. In the above formula, R is an anol radical having 6 to about 20 carbon atoms, C , R /
is a hydrocarbyl group having from about 1 to about 20 carbon atoms, preferably alkyl or aryl', and M is VB or V of the periodic table.
a transition metal selected from group B, preferably titanium, zirconium or/and titanium, most preferably titanium, t=2 or 6, u=0 or 1, V=0, 1, 2 or 6
, w=1, 2 or 6, X is a location selected from chlorine, bromine, iodine, preferably chlorine [, z=1
or 2. v+w+l is equal to the valence of M, and t+u+z=4. The reaction product is a precursor of a highly active polymerization catalyst. This composition of the invention comprises:
contacting 1 mole of an arylsilanol with at least 1 mole of a )-lodenated transition metal compound, preferably a tetravalent transition metal compound, optionally having one or more hydrocarbyl oxide moieties as substituents; It can be manufactured by forming a catalyst precursor. The resulting catalyst precursor is contacted with an organometallic compound to form an organometallic treated composition, and the organometallic treated composition is contacted with a non-active ion exchange source to form a highly active polymerization compound. Organometallic and/or ride-treated materials can be formed that can be used as components of catalyst systems.

The shape of the polymer particles produced by the method using catalyst components is different from that of the catalyst particles, so it is difficult to use organometallic compounds and polymer particles.
It is preferred that the catalyst precursor be deposited on a particulate diluent during treatment with a ion exchange source. It is desirable to utilize the catalytic component as part of a catalytic system that also utilizes a cocatalyst selected from catalytic converters and organometallic compounds. When the catalyst component is supported on particulate material, the catalyst system has exceptional activity in polymerization processes for polymerizing alpha-olefins. It is desirable to carry out the polymerization in the presence of diluent, added hydrogen and ethylene.

In some embodiments of the invention, the first compound selected from arylsilanols, hydrocarbylamines or organophosphorus compounds
arylsilanol, hydrocarbylamine or organophosphorus compound) contacting the reactant with a second reactant which may optionally be a hylogonated transition metal compound having at least one oxyhydrocarpyl substituent. The arylsilanol subjected to the above contact treatment under conditions such that a chemical reaction is carried out with the transition metal compound has the formula RtSi(OH)u+□, where R, and U have the same meanings as above. ) is desirable. Examples of arylsilanols include diarylsilanediols such as diarylsilanediol, triarylsilanols such as triphenylsilanol, and mixtures thereof.

Desirably, the hydrocarbylamine reactant has the formula where R' is as defined above. An example of a suitable arylamine is diphenylamine.

The organic phosphorus compound preferably has the formula % (in which R' has the same meaning as above). It is preferable that R'=R from the viewpoint of solubility. Examples of suitable organophosphorus compounds are trinoenylphosphine oxide and hydriphenylphosphite.

The halogenated transition metal compound utilized as the second reactant in this embodiment has the formula %, where MXR', X, v and W are as defined above.
It is desirable that the compound is represented by

By combining an arylsilanol and a halogenated transition metal compound, a composition is obtained which can be assumed to have the formula %. In the above formula,
R is an aryl group having about 6 to about 20 carbon atoms; R'
is a hydrocarbyl group having from about 1 to about 20 carbon atoms, preferably alkyl or aryl, and M is a group from V of the periodic table.
Group B, VB or VIB, preferably No. tv B or VB
a transition metal selected from the group preferably titanium, zirconium or hafnium, most preferably titanium;
= 2 or 6), Ki14 Sakise41 gutter →= u=O
or 1), v=0.1.2 or 6, and w=
1.2.6, X is a halogen selected from the group consisting of chlorine, bromine, iodine, preferably chlorine, z = 1 or 2 and F), v + w + 1 is equal to the valence of M, And t+u+z=4.

In the above formula, M represents titanium, R is an aryl group having about 6 to about 10 carbon atoms, υ is 2 or 6, u is 0 or 1, and V is O. , W is 6, X is chlorine, and 2 is preferably 1 or 2, because it is expected that particularly good results will be obtained with compositions having such a formula. Most preferably, OR represents a phenyl group, t equals 2 or 6, and U equals 0 or 1, since the test results for these compositions were good. by.

Typically, the reaction of an arylsilanol, hydrocarbylamine or organophosphorus compound with a halogenated transition metal compound is
It is carried out in a suitable solvent or diluent, for example a hydrocarbon such as toluene. The conditions are not critical. The concentration of each component can range from about 1 to about 10 by weight, based on the weight of the solution, and the temperature is, for example, about 20° to 40°C.

Contacting the catalyst precursor in this embodiment, in which a halogenated transition metal compound is used as the second reactant, with an organometallic treating agent to form an organometallic treated composition; Once the composition is contacted with a halide ion exchange source to form a catalyst, the catalyst precursor can be activated. The catalyst treated with an organic metal and Halai V in this manner can be used as a component of a highly active polymerization catalyst system.

In this embodiment, in which a halogenated transition metal compound is used as the second reactant, the metal contained in the organometallic treatment agent to which the catalyst precursor is treated is generally selected from metals belonging to Groups 1 to 2 of the Periodic Table. .

Some organometallic compounds suitable for use as organometallic treatment agents are those whose metal content is selected from the metals of Groups 11 and 2 of the Periodic Table. Organometallic compounds suitable for use include, for example, thiium alkyls, Grignard reagents, dihydrocarbyl magnesium compounds, dihydrocarbyl zinc compounds, organoaluminum compounds, mixtures thereof, and the like. Preferably, the organometallic is selected from dialkylmagnesium compounds, mixtures of dialkylmagnesium and trialkylaluminum compounds, and Grignard reagents in which each hydrocarbon group has from about 1 to about 10 carbon atoms. The preferred Grignard reagent herein is represented by RMgX, where R has 1 to 1 carbon atoms.
o is hydrocarbyl, and X is halogen. The most preferred organometallic is di-n-butylmagnesium because it has been used to produce a highly active component of the catalyst system. The amount of organometallic used can vary within a wide range. In general terms,
The molar ratio of Group 1, 2, or III metal to transition metal in the catalyst precursor is from about 0.01:1 to about 10=1.
Within the range of, generally about 0.1:1 to about 1
: within the range of 1, preferably about 0.4 : 1 to about 0
．． Sufficient amount of organometallic is used to achieve a ratio of 6:1, but the last molar ratio range is preferred because it always yields a catalyst that can be used as a particularly active catalyst for ethylene polymerization. .

In this embodiment, where a halogenated transition metal compound is used as the second reactant, the treatment of the catalyst precursor with the organometallic compound is carried out under conditions such that a reaction occurs between the organometallic compound and the catalyst precursor. be done. For example, an organometallic compound in the form of a solution can be prepared at about room temperature (
26° C.) with a catalyst precursor in a hydrocarbon diluent such as n-hebutane. A dilute solution may be used, for example 0.1 mole precursor and 0.3 mole organometallic. The organometallic treated composition can then be contacted with a halide ion exchange source. This treatment can be accomplished by contacting the reaction product to be treated with a halide ion exchange deep compound at a temperature sufficient to cause the reaction to occur. Preferred, suitable halide ion exchange deep compounds have the formula M'Xa(OR" b
-a is a halogenated metal or a halogenated nonmetal compound. In the above formula, M' is selected from the group consisting of zirconium, titanium, vanadium, silicon and tin, b is the valence of M', and X represents haloke9 selected from bromine, chlorine or iodine. , aba1.2.6.
hydrocarbyl, such as an alkyl, cycloalkyl or aryl group which may be 4 or 5 and b is also smaller or the same as b and R' contains from 1 to about 20 carbon atoms; represents a group. a and b are 2
．． The same number of 6 or 4 is even more preferred. Specific examples of suitable compounds include titanium tetrachloride, tooled titanium dichloride, titanium iodide trichloride, n-butoxytrichlorotitanium, chlorotriP-decyloxytitanium, bromotricyclohexyloxytitanium, dienoxydichloro Titanium, zirconium tetrachloride.

Mention may be made of vanadium pentabromide, vanadium tetrachloride, silicon tetrachloride, etc., and combinations thereof.

A presently preferred compound is titanium tetrahalide of the formula TiX, where X represents a halogen atom, such as chlorine or bromine. Titanium tetrachloride is currently preferred due to its ready availability and relatively low cost.

Generally, the treatment of the organometallic treated catalyst with a halide ion exchange source is carried out in a suitable diluent such as n-pentane, n-hebutane, cyclohexane, benzene, xylene, etc. to facilitate the treatment. carried out in a hydrocarbon diluent such as Processing temperatures can be selected over a relatively wide range, typically from about 0°C to about 20°C.
0°C, but the commonly used temperature is about 8°C.
The range is from 0° to about 180°C.

The first reactant is R251(OH)2, R3EIiOHXR
'2NH.

selected from the group consisting of R'3F==O and (R'0)3F, and when the second reactants are organometallic compounds, these first reactants are the same compounds as mentioned above. . The organometallic compound employed as the second reactant is from the same class of materials as previously described as compounds useful in treating catalyst precursors obtained using halogenated transition metal compounds as the second reactant. To be elected. The preferred organometallic is sialkylmagnesium, with di-n-butylmagnesium being most preferred. The reactants can be contacted in solution, dilute solutions can be used, and the reaction can be carried out at room temperature. The amount of organometallic used per mole of first reactant is: about 0.01 to about 10 moles, usually about 0.2 to about 5 moles, and most preferably about 0.7 moles.
and about 1.5 moles.

The resulting precursor can then be treated with the same type of halogenated transition metal compound used as the second reactant. It is preferred to use the transition metal halide in an excess amount, e.g. 2 moles or more per mole of first reactant residue in the reaction product, since using the procedure This is because a highly active catalyst can be obtained without a separate washing step with a curing agent. A preferred halogenated transition metal compound is Ti(44) due to its easy availability and low cost, as well as good results with its use.

It is advantageous to support the catalyst precursor on the particulate material before treatment with the organometallic compound and/or halide ion exchange source. By choosing a suitable particulate diluent with suitable characteristics, the particle properties of the polymer obtained with the final catalyst composition can be controlled. Typically, a catalyst precursor is impregnated onto the particulate component. Particulate components include polyolefins such as silica, silica-alumina, silica-titania, silica-boria, silica-thoria, silica-zirconia, aluminum phosphate, magnesium dichloride, magnesium oxide, polyphenylene sulfide, polyethylene, and polypropylene. and mixtures thereof. Preferred particulate materials are generally characterized by containing surface hydroxyl groups. Therefore, among the above, silica, aluminum phosphate, silica-alumina, silica-titania, silica-boria, silica-thoria and silica-zirconia and mixtures thereof are particularly preferred, and the content of silica or aluminum phosphate is from about 80 to about 100% by weight
It is even more preferable that The activity of the final catalyst system depends on the calcination temperature of the particulate material. Generally, when a particulate material containing silica is used, the material is calcined at about 260° to about 1000°C, usually about 5 (10
It is carried out at a temperature within the range of 0.degree. C. to about 1000.degree.

Generally, the support to catalyst precursor molar ratio is from about 5=1 to about 75:1, more preferably from about 10:1 to about 50
:1. In practicing this aspect of the invention, the resulting composition can be slurried in a suitable solvent and then treated with an organometallic compound and a halide ion exchange source. There is no relationship between the amount of organometallic compound and halide ion exchange source used and the amount of catalyst precursor as described above.

Although it is not necessary to always use the catalyst of the present invention in conjunction with a co-catalyst, a co-catalyst should be used in order to obtain good results. Therefore, the reaction product after halai treatment is preferably combined with a cocatalyst to form a catalyst system useful for the polymerization of olefins. Usually the co-catalyst is preferably from JA of the periodic table.
, [O consisting of a hydride or an organometallic compound of a metal belonging to group A and ll1A.
[Can be hydrides of metals of groups A and IIIA or organocompounds of these metals.

The promoter component of the catalyst system has the formula Aj! R'oy,, -o
In the formula, R' represents a hydrocarbyl group having 1 to about 20 carbon atoms, and Y represents a monovalent group selected from the group consisting of hydrogen and... and C is 1.2 or 6. Exemplary compounds include trihydrocarbyl aluminum such as trimethylaluminum, triethylaluminum, tridodecylaluminum, trieicosylaluminum, and triphenylaluminum, dihydrocarbylaluminum halides such as diethylaluminum chloride, dibutylaluminum bromide, and methylaluminum dichloride V1. Included are hydrocarbylaluminum cybarides, such as isopro2aluminum zobromide, and mixtures thereof, such as hydrocarbylaluminium sesquihalides, such as ethylaluminum sesquichloride. Trialkylaluminums of the formula AfR"3, where R" represents an alkyl group of about 2 to about 8 carbon atoms, are presently preferred. The adjuvant is a polar organic compound, i.e. a Lewis base (electron donating compound) in combination with titanium tetrahalide, or a cocatalyst component,
It is within the scope of the present invention to use - which is or both. Compounds suitable for this purpose are described in US Pat. No. 3,642,746, which is incorporated by reference herein. Among them are alcoholates,
aldehyde, acetamide, arsine, ester, ether, ketone, nitrile, phosphine, phosphite,
Included are phosphoramide, sulfone, sulfoxyr and stibine. Illustrative compounds include sodium ethoxide, benzaldehyde, acetamide, triethylamine, trioctylarsine, ethyl acetate, diethyl ether, acetone, benzonitrile, phenylphosphine, triphenylphosphite, triamy hexamethylphosphate, dimethylsulfone, dibutyl Included are sulfoxide, triethylstibine and N,N-dimethylaniline.

Preferred esters are lower alkyl (1 to 4 carbon atoms per molecule) esters of benzoic acid, -F,
-Cl! , -Br, -technical, -0H3, -oR7/
/, -OC)O,R", -8H, -NH,,, -NR"
'2, -NHOOR'', -NO2, -ON, -0
HO, -COR''', -00OR", -0ONH2, -
0ONR"'2, -8o2R" and -aF3 (However, R
It may further have a nonavalent substituent selected from the group consisting of (/// represents hydrocarbyl having 1 to 10 carbon atoms) at the position para to the carboxyl group.

Exemplary compounds include ethyl acetate (ethyl p-methoxybenzoate), methyl p-toluate, methyl benzoate, ethyl benzoate, ethyl p-dimethylaminobenzoate, ethyl p-)lifluoromethylbenzoate, methyl p-hydroxybenzoate,
Methyl p-acetylbenzoate, methyl p-nitrobenzoate, ethyl p-mercaptopene f:r-
- and mixtures thereof are included. Generally, adjuvants are used when polymerizing propylene. In preferred embodiments of the invention in which ethylene is polymerized, no adjuvants are generally used.

The molar ratio of organoaluminum compound to adjuvant is generally within the range of about 1:1 to about 300:1. The molar ratio of titanium compound to adjuvant is generally from about 1=1 to about 2
It is within the range of 00:1. The atomic ratio of aluminum to titanium can range from about 20:1 to about 10,000:1, and from about 75:1 to about 5,000:1.
Preferably, the ratio is 0:1. The atomic ratio of aluminum to magnesium can range from about 0.1:1 to about 4:1, and from about 0.5:1 to about 2
It is preferable that =1.

Although any alpha-olefin or mixture thereof can be polymerized in the presence of the catalyst of the present invention, the preferred monomer is ethylene, or ethylene plus another 6 to 1 carbon atom.
0 higher aliphatic mono-1-olefin. The catalyst polymerizes ethylene or copolymerizes ethylene with a small proportion of propylene, butene-1, or hexene-1 in an inert hydrocarbon diluent at a temperature at which the resulting polymer does not dissolve in the diluent. It is particularly useful for By small proportion is meant that the total amount of comonomers is up to 20 moles.

Broadly speaking, the polymerization conditions used in the present invention are similar to those in known processes in which catalyst systems consisting of titanium tetrachloride and organoaluminium compounds are used. Polymerization of alpha-olefins is achieved by contacting with the catalyst system of the present invention in solution, suspension or gas phase.

In the preferred polymerization of ethylene in particulate form,
In the presence of a diluent, the diluent maintains a liquid phase and
The polymerization is carried out under temperature and pressure conditions such that the resulting polymer does not dissolve therein.

The polymerization temperature is generally within the range of 00 to 150°C, preferably about 40' to 112°C. Any convenient partial pressure of ethylene can be used.

The partial pressure is generally about 10 to 5 oopθig (69 to 5
450 kPa). Diluent 1 during polymerization
The titanium compound concentration per equivalent can be in the range of about 0.0005 to 10 mmol, but about 0.001 to 10 mmol.
Preferably it is 2 mmol.

The diluent for polymerization may be an excess of monomer,
Or it may be a diluent that is non-reactive under the conditions employed. Preferably, the diluent is a hydrocarbon, such as inbutane, n-pentane, cyclohexane, and the like.

As is known in the art, the molecular weight of the polymer can be controlled by the presence of hydrogen in the reactor during polymerization. Since the catalyst of the present invention has a high degree of activity, the amount of transition metal contained in the resulting polymer is generally 100%
It is not uncommon for the score to be below 50,
When using this catalyst, Ha? There is no need to purify the remer.

The polymerization process used to produce the ethylene polymers according to the invention can be any known process, including batch and continuous processes. For example, when performing the polymerization of ethylene on a laboratory scale,
℃ reactor temperature and about 290 p81a (2,0MP
Polymerization in batch mode in a stirred reactor using dry hydrocarbon diluents inert to the reaction, such as isobutane, n-hemethane, methylcyclohexane, benzene, toluene, etc., under the reactor pressure of a). It is convenient to do this. Ethylene is fed into the reactor as needed to maintain the desired pressure. To control the molecular weight of the polymer, a molecular weight control agent such as hydrogen can be pumped into the reactor, as is known in the art.

When a predetermined polymerization time has elapsed, the flow of ethylene and, if comonomer is used, is stopped to terminate the reaction, and the unreacted monomer and diluent are evacuated to recover the polymer. . If desired, the recovered product is treated to deactivate and remove residual catalyst, such as by washing with alcohol, stabilized by addition of antioxidants, and remove residual solvent, if any, by drying. The product can be processed by other methods known in the art. The resurfacing product can be further processed into pellets and/or converted to a final shaped product.

In the case of a continuous process, a suitable reactor, such as a loop reactor, is continuously charged with appropriate amounts of solvent or diluent, catalyst, cocatalyst, ethylene, hydrogen (if used) and comonomer (if used). Enter. The reaction product is removed continuously and the solid polymer is recovered from the product by suitable means, for example by 7 lashings.

The catalyst of the present invention can also be used to produce homopolymers and copolymers of conjugated diolefins. Generally, conjugated diolefins contain 4 to 8 carbon atoms per molecule. Examples of suitable conjugated diolefins include 1.6
-butadiene, isoprene, 2-methyl-1,6-butadiene, 1°6-pentadiene and 1,6-octadiene. In addition to these conjugated diolefins, examples of suitable comonomers include the mono-1-olefins and vinyl aromatic compounds mentioned above in general. Some suitable vinyl aromatized metals are those containing about 8 to 14 carbon atoms per molecule, such as various alkylstyrenes such as styrene and 4-ethylstyrene, and 1-vinylnaphthalene. things are included in it.

The weight percent of conjugated diolefin in the copolymerization mixture is
You can choose from a relatively wide range 〇 Generally ~
The weight percent of the conjugated diolefin is about 10 to about 95 weight percent.
The other comonomer is about 90% by weight to about 5% by weight. However, the weight percent of conjugated diene is preferably about 50
from about 90% by weight and the other comonomers from about 50 to about 10% by weight in a dry box under an inert atmosphere such as argon.
A series of catalysts were prepared by reacting certain components at room temperature (25° C.). When the resulting composition was further treated with TiCJ4, 20% by weight in n-heptane
The above treatment was carried out by reacting the composition with a solution containing TiC^ at about 100° C. for about 5 to 10 minutes.

Generally, a toluene solution containing the reaction product of the organic compound and Ti(44) was mixed with a slurry of activated silica and toluene, if activated silica was used. The toluene was evaporated from the mixture. and the solid content was
The slurry was reslurried in hebutane and contacted with a hydrocarbon solution containing the organometallic compound. Usually, the organometallic compound used is Texas Alkyrus Corporation (Te
xaθAlkyls) from the trademark Magalp (Magalp
n-hebutane solution of di-n-butylmagnesium triethylaluminum (Mg
:A1 molar ratio 7:1). The resulting solid was recovered by evaporating the solvent, washing with n-hexane and drying to obtain the catalyst.

When T i Cf 4 treatment was performed, the recovered solids were contacted with a Tlci,/n-heptane solution as described above. The recovered solid to be treated was washed with n-hexane to remove unreacted T i (J 4 ) and then dried to obtain a catalyst.

The amounts of the components used in the composition in preparing the catalyst are as listed in Table I below. The approximate range of the amount used of each component is shown in millimoles. Silica: 0-140; Organic compounds 20, 6-9; Initial Ti (J4: 0-17; Di-n-butylmagnesium (Bu2Mg) as magara) +
0.2-4.5: ) ethyl aluminum (TEA
): 0.03~2.0; Final T1cz, : O~1
90 toluene was used in the range of about 15-40 ml and n-hexane was used in the range of about 865-60 ml. silica(
(if used), organic compounds and initial Ti (440) The amount of T1 added to the catalyst, based on the weight, ranges from about 1 to about 10 or more, such as up to about 20, by weight, preferably from about 1.5 to about 10.

Furthermore, as shown in Table 1, a catalyst precursor can be obtained by reacting a diarylamine with a halogenated transition metal compound, and this can be mixed with silica. This composition is then treated with an organometallic compound consisting of a dihydrocarbylmagnesium compound, and the same or different type used above.
It can be treated sequentially with a lodenated transition metal compound.

To prepare catalyst 18, 4.99 (81.7 mmol) of precalcined silica at 750 DEG C. is reacted with Nisla')-L[ in toluene. 20ml of toluene, 0.35.
9 (2,07 mmol) of diphenylamine (φ2N
H) and 0.41 g (2.18 mmol) of TiCJ
, 4 was prepared and mixed with the silica slurry described above. The solvent was evaporated off, the product was reslurried in n-hebutane, and the solvent was evaporated off again. The dried product was slurried in n-hebutane and 12
．． A black reaction mixture was obtained by mixing with 8 ml (4.48 mmol) of Magala.

φ2NH:Ti (J4: Magara molar ratio is approximately 1:1:
It is 2. Evaporate the solvent in the mixture containing Magara and give 3.45 g (18.2 mmol) of dry product.
of Ti (J4 and 8.0 ml of n-hebutane was added.

The mixture was heated, the product was washed with n-hebutane, and the solvent was evaporated as before to give the catalyst.

The final molar ratio of TicJ4:φ2NH:Magara is 9.8
21:2.2.

Also, as shown in Table I, a catalyst precursor can be formed by reacting an organometallic compound comprising a dihydrocarbylmagnesium compound with a diarylamine in the presence of silica. This precursor is then treated with a halogenated transition metal compound to form a catalyst.

As one example, to make catalyst 17, 4.72.
9 (78,7 mmol) of sieved silica (140
~200 mesh) slurry in all toluene, 20
m1! A solution formed from 0.59 g (3.49 mmol) of φ2NH and 10.0 m (3.5 mmol) of Magara dissolved in toluene (φ2NH:Magara molar ratio 1:1) was mixed with 23 m7. A green mixture was obtained. The solvent was evaporated and the product was reslurried in n-heptane and the solvent was evaporated again. 42.76 g (14.6 mmol) of Ti (J) dissolved in 8.4 ml of n-heptane was added to the product. The mixture was heated to about 100° C. as above and the product was dissolved in n-heptane. to remove unreacted TiCJ,4 and/or soluble by-products, and then remove the solvent to obtain the catalyst.TiCj',
The molar ratio of 4:φ2NH:magara is 5.5:1:
It was 1.

In yet another embodiment summarized in Table ■, an organometallic compound comprising a dihydrocarbylmagnesium compound and a triarylphosphine oxide are reacted;
A catalyst precursor can be produced. The composition formed by mixing this precursor with silica is then treated with a halogenated transition metal compound to form a catalyst.

As an example, to make catalyst 15, 1 g (6,
6 mmol) of trinoenylphosphine oxide (φ
3PO) was slurried in a small amount of toluene, 1' 0.2 ml (3.6 mmol) of Magara was added without stirring (molar ratio of φ3PO: Magara 1:1), and then 6
3.4 g (56.7 mmol) of silica precalcined at 00° C. were mixed into the slurry. The solvent was evaporated from the reaction mixture. The product was reslurried in n-hebutane and the solvent was again removed by evaporation. 9.0ml n-
1,7y (9,1 mmol) T1C mixed with hebutane
f4 was added to the above dry product and the mixture was heated to about 100° C. for about 5-10 minutes with stirring. The treated mixture is then collected and washed with n-heptane at about 25°C to remove unreacted T i (44 and/or
After removing the soluble by-products, the product was dried to obtain the catalyst.

In yet another aspect of the invention summarized in Table I:
The catalyst can be prepared by treating an intermediate composition formed by combining a triarylphosphite and a halogenated transition metal compound in the presence of silica with an organometallic compound.

As an example, to make catalyst 16, 3.4 g
(56,7 mmol) of sieved silica (140-20
0 mesh) was slurried in n-pentane and 1.5
ml (5,73 mmol) notrinoenyl phosphide (φo) 3p. slurry 3.10/
1 (16.3 mmol) of Ti(J4) to give a red reaction mixture and the solvent was evaporated from the mixture.8
．． Oml (2.8 mmol) of Hemlock was added to the product to obtain a reddish-brown product with a molar ratio of 2.8 mol of Tlcz: 1 mol of (φ0)3F: 20.49 mol of Hemlock. Wash the above product with n-hebutane to remove unreacted T.
i CJ 4 and/or soluble by-products were removed and the solvent was removed by evaporation to obtain the catalyst.

The nature of the catalyst precursor formed, the weight percent of initial T1 relative to the silica and precursor used, and the various molar ratios used are detailed in Table I below.

(Note to table ■) (a) Triphenylsilanol.

(b) Diphenylsilanol 0 (0) φ3 is triphenyl, and R is n-butyl.

(d) Arylsilanol, silica and initial Ti
(After contacting with
1 mol) of final T1Cf4 at about 80°C.
After heating for about 1 hour to room temperature and cooling to room temperature, the product was washed with an appropriate amount of n-hexane to remove any unreacted final T i CJ,4
was removed. The solid catalyst was recovered by evaporating the solvent under argon or nitrogen.

(e) Triethylaluminum (
TBA) is used.

(f) molar ratio of st compound: TEA. □(ω
Silica, TPS, R2Mg and final Ti (by weight of 44; actual amount of T1 is unknown, but unreacted T1
Since it was removed in the cleaning process, the amount of Ti is probably about 10% by weight.
or less may be 0(h) Silica, Organic Compound, Weight % based on Ti(J,) (1) Triphenylphosphine oxide.

(j)　　　) Riphenyl phosphite.

(k) Diphenylamine.

Example 2 (Ethylene Polymerization) Ethylene polymerization was carried out using weighed amounts of each of the catalysts described above in each experiment ranging from about 0.02 to about 0.51 g. Unless otherwise specified, 100 psi (0,69
Ethylene partial pressure (MPa), hydrogen partial pressure (100 psi)
(if hydrogen is used), pounds per square inch absolute (psi
The total reactor pressures shown in Table H, measured in a), and T containing 15 wt.
Each experiment was conducted using one solution of A in n-hebutane at 80° C. for 1 hour.

terminating the reaction by discontinuing heating the reactor;
Gas in the reactor was evacuated. The polymer is collected, dried, and weighed to determine the yield. From this yield, the productivity of the catalyst composition is calculated as the number of polymers per hour (I) per 11 parts of catalyst per hour.
g, Q! (catalyst/hour). The dried recovered polymer was stabilized with a conventional antioxidant system and the melt index (M) and high load melt index (HLM) were determined according to ASTM D 1238 conditions E and F, respectively.

The catalyst precursor used, the weight of the catalyst composition used, the observed reactor pressure and the results obtained are shown in Table 1.

Table ■ Experiment −〕−−(−−Reactor pressure Polymer furrow Protection〈Earberry p11 wall Jv; −”11i, 2 towns−’Iy, L gl
φ3SiOMgR10,5657390119,72
φ2si(oH)oT1a13 2 0,045
0 385 5026 φ2Si(OH)O
TiO1320,0190280(a) 5104
φ2s1(oH)oT1c133 0,3394
385 82,65 φ, l5iOTiO
1340,14673853856φ3SiOTiO1
340,0428285(a)553,57 φ3S
iOTiC! 13 5 0.1718 385
158 φ3SiOTiO1360, 20743
95869φ3SiOTiO1370,5136,40
03510φ3SiOTiO1380,192139'
5 33511 φ3SiOTiO1390,
199439530012φ3s1oT1c1310
[], 1756 385 10116
φ3s1oT1a1311 0.3534 3
90 3814 φ3SiOTiO13'
12 0,3191 390 40
715 φ3SiOTiO13130, 15293
905116φ2s1(oH)oT1c1314
[], 0578 390 27017 φ3
POMgBu2 1s 002327
385 77.018 (φ0)3PTj
, 01. 16 0.4684 405
20.619 φ2NTiO13170,75
27385111,520φ2NMgBu
18 0.4461 390 4
12 Calculated value of polymer productivity
3.3 141 46 Comparative experiment 11.
120 2.1 75 3653.68
0 (b) 0 (0) 02462.0
67 34 2.620 6.0 240 4012930
0(0)0 76 nd(li)nd - Comparative experiment 4
15 na 36 68 2.3 104 45 Comparative experiment 1.740 6.0 214 361
．． 500 20 743 37575
4.3 183 43108 6.0
265 441.280 7.6 2
59 34334 2.8. 121
434.670 0°81. 36
45331 5.3 177 3344
0.3 23.6 78148 0
0 792 2.9 124 42 (Notes to Table H) (a) No hydrogen present in the reactor.

(b) Shiborimer 26,840 per gram of catalyst per 0.5 hours in a 60-minute experiment! Since the productivity of i+ has been calculated, assuming that the activity is linear, the table shows 26,
It showed a value of 840 x 2, or 53,680.

(C) Too low to measure.

(d) Indicates that no measurement was taken.

The results in Table (1) show that in all cases, catalysts with ethylene polymerization activity were obtained. It is well known in the art that the use of hydrogen during the polymerization process allows the molecular weight of the polymer to be controlled and the melt index to be increased; however, as expected, the activity of the catalyst decreased slightly. These phenomena are clearly seen when comparing the melt index and productivity values for Experiments 2 and 6 and Experiments 5 and 6. HLMx/MI values of about 40 generally indicate that polymers with reasonably narrow molecular weight distributions were obtained in all cases, but the molecular weights of polymers obtained using transition metal catalysts of conventional techniques are The distribution range is not particularly narrow. The latter polymers usually have an HLMx/Mx in the range 28-60.
Show value. In other words, the catalyst of the present invention appears to produce polymers with a slightly broader molecular weight distribution range than conventional polymerization catalysts.

Generally, productivity calculations for the most active catalysts of the present invention range from about 240 to about 4700.9 polymer per gram of catalyst per hour in the presence of silica and hydrogen; In the absence of F, about 54,000 sibolimer per gram of catalyst per hour can be reached. The catalyst of Experiment 1, in which organosilanol and R2Mg were reacted prior to contact with Ti (M4), exhibits relatively low activity. It is preferable to react with i CJ 4. The catalyst used in Experiment 7 has relatively poor activity, and R2Mg-TEA was used in the production of other catalysts.
Without the combination, this catalyst was prepared using TFiA. In catalyst production, R2Mg and TE
It seems that it is not equivalent to A. The low productivity values seen in Runs 9 and 16 are due to the fact that around 1 M
The cause is thought to be a low titanium concentration below 30%.

When using silica for catalyst production, Experiments 1 and 4~
From the polymerization results of No. 16, about 260° to about 1000°C,
It has been suggested that the silica should be previously calcined (activated) in air, preferably at a temperature in the range of about 700 DEG to 1000 DEG C., to increase the catalytic activity.

Although the productivity of the catalyst in the presence of silica appears to be relatively low, if these values were to be expressed based solely on the active components of the catalyst, the same values would be obtained as in Runs 2 and 2. An advantage of using silica in the production of catalysts is that the particle size of polymer particles produced using such catalysts tends to be relatively large and the particle size distribution is relatively narrow. These properties make the polymer easy to process. For example, the polymer produced in Experiment 14 was sieved using a US sieve size screen.

As a result, about 86% by weight of the polymer remained on the 60 mesh sieve, about 10% by weight remained on the 50 mesh sieve,
Approximately 2.6% by weight remains on the 80 mesh sieve and 1
The total amount remaining on each part of the 00 mesh and 200 mesh was about 1.6% by weight.

Run 19 was combined with a cocatalyst as defined herein, even though there was a substantial amount of hydrogen in the reactor such that the partial pressure of ethylene and the partial pressure of hydrogen were equal. This shows that Catalyst 17 produces a very high molecular weight ethylene polymer.

Run 20 shows that the activity of catalyst 18 in combination with the same cocatalyst as in run 19 under the same reaction conditions was higher than that of catalyst 1.
This shows that the activity is about 5 times that of No. 7. The molecular weight of the ethylene polymer produced is also lower than in Experiment 19, making it easier to process in conventional secondary processing equipment, such as extruders and injection molders. It is therefore clear that the order in which the reactants are contacted is important in the preparation of the catalyst, and that depending on the method chosen for the formation of the catalyst, the catalyst behaves quite differently.

Experiment 17 shows that under the same polymerization conditions, catalyst 15 combined with the same cocatalyst as above had almost twice the activity of catalyst 17, and was also slightly easier to process than the ethylene polymer produced by catalyst 18. This shows that it is possible to obtain a polymer with excellent properties. For example, the melt index of the polymer with catalyst 18 is 2.0, while the melt index of the polymer with catalyst 15 is 5.6.

Run 18 shows that the activity of catalyst 16 in ethylene polymerization under the same polymerization conditions and in combination with the same cocatalyst was substantially lower than catalysts 15, 17 and 18.

Agent Asa Mura Hao

Claims (1)

[Claims] (1) A secondary amine represented by the formula R'2NH, or a secondary amine represented by the formula R
A first organophosphorus compound represented by '3P==O or (R'0)3F (R' in each of the above formulas represents a hydrocarbyl group having from 1 to about 20 carbon atoms)
The reactants are defined by the formula %, where 1M represents a transition metal of group 1 VBXVB or VIB of the periodic table, R' represents a hydrocarbyl moiety having from 1 to about 20 carbon atoms, and X represents chlorine, bromine, and iodine, where ■ is equal to 0.1.2 or 6, W is equal to 1.2.6 or 4, and v+w+1 is equal to the valence of M). A catalyst component or its precursor, characterized in that it is brought into contact with a second reactant to produce a catalyst component precursor, or brought into contact with a second reactant that is an organometallic compound to produce the entire catalyst component. Production method. (2) The method according to claim (1), wherein the first reactant is R'2NH. (3) The first reactant is R'3PO or (R' 0)3P. A method according to claim (1). (4) A method according to claim (2) or (3), wherein each R' is aryl having from 6 to about 10 carbon atoms. 5) Claim (4) wherein each R' is a phenyl group.
). (6) The method according to claim (3), wherein the first reactant is triphenylphosphine oxide. (7) the first reactant is trinoenyl phosphite;
The method according to claim (3)v-. (8) the second reactant is a halogenated transition metal compound;
The method according to any one of claims (1) to (7). (9) A claim in which R' is an aryl group having from 6 to about 10 carbon atoms, M is titanium, v is equal to O, W is equal to 6, and X is chlorine. The method described in scope (8). α() Treating the catalyst precursor with an organometallic treatment agent that is a dialkylmagnesium compound or mixture thereof, a trialkylaluminium compound, or a Grignard reagent in which each hydrocarbon group contains about 1 to about 20 carbon atoms to form the catalyst component. The claims further comprising producing (
8) or the method described in (9). 0υ The resulting catalyst component is defined by the formula %, where M/ is zirconium, titanium, vanadium, silicon or tin, and R/ is a hydrocarbyl having from 1 to about 20 carbon atoms. , a is 1.2.6.
4 or 5, b equals the valence of M', and or represents chlorine, bromine or iodine. . 1.1 Li Any one of claims (1) to [7), wherein the second reactant is an organometallic compound consisting of a lithium alkyl, a Grignard reagent, a sialkylmagnesium compound, a sialkylzinc compound, or an organoaluminium compound. The method described in Section 1. α→ The method according to claim α→, wherein the second reactant is a sialkylmagnesium compound or a mixture thereof. αYU The obtained catalyst component is mixed with the formula % (wherein M represents titanium, zirconium or hafnium, R/ is a hydrocarbyl group having from 1 to about 20 carbon atoms, and X is chlorine, bromine). and iodine, where ■ is equal to 0, 1.2 or 6, W is equal to 1.2.6 or 4, and is equal to the valence of v + w +1 id M). The method according to claim q or (1:3), further comprising treating with
Claims for depositing catalyst precursors or catalyst components on particulate material consisting of silica-boria, silica-thoria, silica-zirconia, aluminum phosphate, magnesium dichloride, magnesium oxide, polyphenylene sulfide, polyethylene or polyzolopyrene. range (1) to 0
4. The method according to any one of 4. α→ A first reactant having the formula R251(○H)2 and R351oa (wherein R represents an aryl group having from B to about 20 carbon atoms) is combined with the formula % formula % (wherein M represents a transition metal of group ■BXvB or VIB of the periodic table, R' consists of a hydrocarbyl moiety having from 1 to about 20 carbon atoms, or represents chlorine, bromine or iodine, and ■ represents 0.1. equals 2 or 6, W is 1
．． 2.6 or equal to 4 and equal to a valence of v+-w+1idM). 0 αη Claims αQ in which each R' consists of an aryl group having 6 to 10 carbon atoms, M consists of titanium, V equals O, W equals 6 and X consists of chlorine. The method described in. 0→ The method according to claim 〇〇, wherein the first reactant is diphenylsilanol. The method of claim 0Q, wherein the first reactant is triphenylsilanol. (a) Treating the catalyst precursor with an organometallic treatment agent consisting of a dialkylmagnesium compound or a mixture thereof, a trialkylaluminum compound, or a Grignard reagent in which each hydrocarbon group contains about 1 to about 20 carbon atoms to prepare the catalyst component. A method as claimed in any one of claims 1 to 3, further comprising producing .alpha.Q-.alpha.. 01) Using an organometallic treatment agent consisting of a dialkylmagnesium compound or a mixture thereof, a trialkylaluminum compound, or a Grignard reagent in which each hydrocarbon group contains about 1 to about 20 carbon atoms, , each R is an aryl group containing from 6 to about 20 carbon atoms, R/ is a hydrocarbyl group containing from 1 to about 20 carbon atoms, υ, t is equal to 2 or 6, and U is O or 1 , M is a transition metal of group 1 VB, VB or VI B of the periodic table, and ■ is 0, 1.2 or 6
or represents chlorine, bromine or iodine, and W is 1.
2. equals 6 or 4, 2 equals 1 or 2, v+w
+1 equals the valence of M and t+u+z=4) to produce a catalyst component. The method described in section. (a) The resulting catalyst component is converted to the formula % (% formula %) (wherein M' is zirconium, titanium, vanadium, silicon or tin, and R' is a hydrocarbyl group having from 1 to about 20 carbon atoms). 1.2.6.4 or 5, b equals the valence of M', and X represents chlorine, bromine or iodine). The method described in claim (e) or Q]). ) silica, silica-alumina, silica-titania,
Particulate matter consisting of silica-boria, silica-zirconia, aluminum phosphate, magnesium dichloride, magnesium oxide, polyphenylene 7-ide, polyethylene or polypropylene, and secondly, catalyst components or catalyst precursors. Claims (1) The method according to any one of claims (i) to (b), further comprising depositing the A method for polymerizing at least one α-olefin to form a polymer product, characterized by using a catalyst component or a precursor thereof. R' represents a hydrocarbyl group containing from 1 to about 20 carbon atoms; t is equal to 2 or 6; u is equal to 0 or 1; M is fVB or V of the periodic table
Is not a transition metal belonging to group B, ■ is 1.2 or 6, X represents chlorine, bromine or iodine, W is 1.2.6
or equal to 4, 2 equals 1 or 2, v −4−
w + 1 equals the valence of M, and t + u, +z
= 4), or a precursor thereof. (c) R represents aryl having 6 to about 10 carbon atoms, t is equal to 2 or 6, u is equal to 0 or 1, M is titanium, ■ is equal to 0, and X is chlorine; and W is equal to 6 and 2 is equal to 1 or 2. equal and 2 equals 1, % tolerance (
Composition O according to c) (c) R represents a phenyl group, t is equal to 5, and U
is equal to 0 and 2 is equal to 1.