JPS59168002A - Polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain a polymer having an MW at which it is easily moldable and a wide MW distribution, by polymerizing an olefin in the presence of a catalyst prepared by combining a specified solid component containing Cr, Ti, Mg and an inorganic oxide with an organometallic compound. CONSTITUTION:An olefin is polymerized in the presence of a catalyst comprising (A) a solid component prepared by copulverizing (i) a hydrocarbon-insoluble solid obtained by reacting (a) a hydrocarbon-soluble organomagnesium compound or complex compound with (b) a halogen atom-containing titanium or vanadium compound with (ii) a solid prepared by impregnating an inorganic oxide carrier with a chromium compound and calcining the impregnated carrier, and (B) an organometallic compound. The titanium or vanadium compounds which can be used desirably include those having three or more halogen atoms, especially titanium tetrachloride. The inorganic oxide carriers which can be used desirably include silica and silica-alumina, and commercially available highly active catalyst silica is particularly desirable.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for polymerizing ethylene or ethylene and other 1-olefins.

More specifically, (1) a hydrocarbon-insoluble solid obtained by the reaction of (a) a hydrocarbon-soluble organomagnesium compound or complex compound and (b) a titanium or S sodium compound containing at least one halogen atom; 11) A novel, highly active, molecular weight distribution of the resulting polymer, which combines a solid component (A) obtained by co-pulverizing a chromium compound supported on an inorganic oxide carrier and a fired solid, and an organometallic compound (B). The present invention relates to an olefin polymerization method characterized by using a wide range of catalysts.

The ethylene polymerization catalyst obtained by supporting a chromium compound such as chromium oxide on an inorganic oxide support such as silica or silica-alumina and firing it is widely known as a so-called Phillips type catalyst, and generally the molecular weight of the produced polymer is low. Because of its wide distribution, it is prized for producing polymers suitable for blow molding and extrusion applications, for example.

However, when using this catalyst, the activity of the catalyst and the average molecular weight of the polymer greatly depend on the polymerization temperature, and commercially suitable polymers with molecular weights of tens of thousands to hundreds of thousands can be produced with sufficient catalytic activity. In order to achieve this, the polymerization temperature is generally 100-20
It was rarely necessary to bring the temperature to 0°C.

When polymerization is carried out in such a temperature range, the produced polymer is dissolved in the reaction solvent, so the viscosity of the reaction system increases significantly, and as a result, the concentration of the produced polymer decreases by 2.
It was difficult to raise it above 0chi. Therefore, there has been a strong demand for the development of a catalyst that exhibits deep catalytic activity at a polymerization temperature of 100° C. or lower, at which polymerization becomes so-called slurry polymerization. Furthermore, in recent years, in order to reduce production costs, it has become important to be able to omit the catalyst removal step in the post-polymerization step, and for this purpose, it has become necessary to develop catalysts that exhibit even higher activity.

As a result of various studies from the above viewpoint, the present inventors found that
A catalyst that combines specific solid components including chromium, titanium, magnesium, and inorganic oxides with an organometallic compound,
We have discovered that it is possible to easily produce a polymer that exhibits high catalytic activity even at low temperatures of 00° C. or lower, has a molecular weight that is easily molded, and has a wide molecular weight distribution, and has thus arrived at the present invention.

In other words, the present invention provides (A) (t) a compound obtained by the reaction of (a) a hydrocarbon-soluble organomagnesium compound or complex compound and (b) a titanium or nonadium compound containing at least one halogen atom. (11)
The present invention relates to an olefin polymerization method using a catalyst consisting of a solid component obtained by co-pulverizing a chromium compound supported on an inorganic oxide carrier and a calcined solid, and (B) an organometallic compound.

According to the method of the present invention, the molecular weight is lower (M, I
(increased FR), resulting in a molecular weight suitable for molding and a wide molecular weight distribution (increased FR), resulting in fluidity suitable for blow molding and extrusion molding, and further increased activity. , is truly suitable.

The present invention will be explained in detail below.

The hydrocarbon-soluble organomagnesium compound or complex compound used in the present invention (4)(+)(a) has the general formula M, tMg, R1, R29X, Y, (wherein α is o'-1 or A number greater than 0, β plus a number greater than O, p
+, Q+ r+” is a number smaller than 0, p +q
+ r + a = mα + 2β, M is an atom selected from aluminum, zinc, boron, beryllium, and lithium, m represents the valence of M, and R1,
R2 is a hydrocarbon group having the same or different number of carbon atoms, X
, Y are the same but different groups), OR3, O8i
R'R5R6゜NR7R8,SR9 represents a group, R
3, R9 hydrocarbon group, R4, R6, R6, R7, R8
represents a hydrogen atom (represents a hydrocarbon group).

Preferably, M is aluminum'1 x, Y is OR3 or OS i R'R5R6, β/α>1. (r+s
)/(α1β)≦1 is recommended. The synthesis of these hydrocarbon-soluble organomagnesium compounds or complex compounds is generally known, and may be carried out, for example, in accordance with the publications, gazettes, documents, etc. listed below.

In other words, if M is aluminum and α>0, the JP-A-5
0-139885, JP-A-48-18235, JP-A-47-24009, Annarenderhiemi vol. 605, pp. 93-97 (1957), JP-A-50-154388, JP-A-50-154388, JP-A-50-154388, Showa 50-157490
It may be synthesized from the corresponding organomagnesium and organoaluminium with reference to JP-A No. 53-40696, and M is zinc, boron, beryllium, etc. and α>0
The ones are JP-A-50-150786 and JP-A-51.
It may be synthesized from corresponding organomagnesium, organozinc, etc. with reference to JP-A-97687, JP-A-51-107384, and JP-A-52-71421. In addition, α-〇 substances that are soluble in hydrocarbons include n-butylethylmagnesium, n-dityl 5ee-butylmagnesium, n-butyl 1so-propylmagnesium, etc. , Japanese Patent Publication No. 1983
-26893, U.S. Patent No. 4127507, U.S. Patent No. 3646231, U.S. Patent No. 3
No. 766280, Journal of Organic Chemistry, Vol. 34, pp. 1116-1121 (1969)
The compound may be synthesized using a corresponding Grignard compound or alkyllithium compound with reference to Journal of Organometallic Chemistry, Vol. 64, pp. 25-40 (1974).

Examples of the titanium or vanadium compound containing at least one nitrogen atom used in the present invention (A) (+) (b) include titanium tetrachloride, titanium tetrabromide,
Ethoxybutane trichloride, cytoxytitanium trichloride, dibutoxytitanium dichloride, nonadium tetrachloride, vanadium oxytrichloride, etc., 710 titanium and nonadium compounds, oxynologenides, alcoholado rognides, etc. alone or A mixture is used. Preferably, it is a compound containing three or more ions, and titanium tetrachloride is preferably used as the material.

The chromium compounds used in the present invention (4)(n) include chromium oxides, and compounds that at least partially form chromium oxide upon calcination, such as chromium halides, oxyhalides, nitrates, and acetates. , sulfate, oxalate, alcoholade, etc., specifically chromium trioxide, chromyl chloride, potassium dichromate, ammonium chromate, chromium nitrate, chromium acetate, chromium acetylacetonate, ditertiary chromate. etc. Chromium trioxide, chromium acetate, and chromium acetylacetonate are particularly preferably used.

As the inorganic oxide finger used in the present invention (A) (ii), silica, alumina, silica-alumina, zirconia, doria, etc. can be used, but silica and silica-alumina are preferable, and commercially available highly active Catalytic silica (high surface area, limited porosity volume) is particularly preferred.

Examples of the organometallic compound used in the present invention 03) include organoaluminum compounds, organoboron compounds, organozinc compounds, organoboron compounds, hydrocarbon-soluble organomagnesium compounds or complex compounds, such as triethylaluminum, triisobutylaluminum, etc. ,
Tri-n-hexylaluminum, tridecylaluminum, diethylaluminum hydride, aluminum isoprenyl, ethylaluminum ethoxide, methylethylhydrosiloxyaluminum diethyl and mixtures thereof, triethylboron, diethylzinc, n
Examples include -butyllithium, di-n-butylmagnesium triethylaluminum compound, n-dityl 5ee-phthylmagnesium, and n-butylethylmagnesium. Preferred examples include organoaluminated compounds and hydrocarbon-soluble organomagnesium compounds.

Next, catalyst synthesis will be explained. 1su, (4) (1)
Obtaining a solid by reacting the hydrocarbon-soluble organomagnesium compound or complex compound (,) with the halogen-containing titanium (or vanadium) compound (b) will be explained. This reaction can be carried out in an alicyclic hydrocarbon such as an inert hydrocarbon, an aromatic hydrocarbon such as benzene, toluene, xylene, or a mixture thereof, but preferably an aliphatic or alicyclic hydrocarbon. It takes place inside.

The reaction temperature is preferably below zooc, particularly preferably 5
It is carried out at a temperature below 0°C. The reaction ratio of the two components is 0.05 to 50 mol, especially 0.05 to 50 mol of the organometallic component (a) to 1 mol of the titanium (or sodium) component (b).
A range of 2 to 10 moles is preferably used. Regarding the reaction method, there is a simultaneous addition method in which two components are simultaneously introduced into the reaction zone and reacted, or a so-called direct addition method in which one catalyst component is charged into the reaction zone in advance and the remaining one component is introduced and reacted. (Ren) Any of the addition methods can be used.

Next, supporting of the chromium compound in (A)(ii) will be explained. The chromium compound can be supported on the inorganic oxide support by known methods such as impregnation, solvent distillation, and sublimation deposition. Depending on the type of chromium compound, it may be supported by an appropriate method, either aqueous or non-aqueous.
For example, when using chromium trioxide or chromium acetate, water may be used, and when using chromium acetylacetonate, a non-aqueous solvent such as toluene may be used. The amount of chromium supported is 0.0% by weight of chromium atoms on the support.
It is in the range of 5 to 5%, or 0.2 to 2 inches.

Next, firing activation of the supported solid in (A) (li) will be explained.

Firing activation is generally carried out in the presence of oxygen in a non-reducing atmosphere, but it can also be carried out under reduced pressure using an inert gas. Preferably, air substantially free of moisture is used. The firing temperature is 300°C or higher, preferably 400°C
Several minutes to several tens of hours at a temperature range of ~900°C, preferably 1 to 3
It is carried out for 0 minutes to 10 hours. During firing, it is recommended to blow in sufficient dry air and activate firing under fluidized conditions.

Of course, it is also possible to use a known method of controlling activity, molecular weight, etc. by adding fluorine-containing salts during supporting or firing.

Next, a method for obtaining the solid component (4) by co-pulverizing the solid obtained in (A) (+) and the solid obtained by firing in (A) (ii) will be described. As a method for co-pulverization, a known mechanical pulverization method such as a rotary ball mill or a vibrating mill can be used. There are no particular restrictions on the co-pulverization conditions, but preferably the atomic ratio of Cr/Ti is 1/1.
A range of 0.1 to 115 is recommended.

Next, a method of combining the solid component (A) and the organometallic compound (B) will be explained.

The solid component and the organometallic compound (B) may be added to the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. It is also possible to treat the solid component with the organometallic compound in advance, and then feed the solid component into the polymerization system in combination with the organometallic compound. The ratio of both components to be combined is (organic metal) / Cr
molar ratio of 0.01 to 3000, preferably o, i to 1
A range of 00 is recommended.

Next, a method for polymerizing olefin using the catalyst of the present invention will be explained.

The olefins that can be polymerized using the catalysts of the invention are alpha-olefins, especially ethylene. Furthermore, the catalyst of the present invention is ethylene, propylene, zothene-1, hexene-1
Copolymerization with monoolefins such as IA? Furthermore, it can also be used for polymerization in the coexistence of dienes such as butadiene and imprene.

By carrying out copolymerization using the catalyst of the present invention, it is possible to produce polymers with a density in the range of 0.91 to 0.97 g/crrt.

As the polymerization method, usual @turbidity polymerization, solution polymerization, and gas phase polymerization are possible. In the case of suspension polymerization and solution polymerization, the catalyst is a polymerization solvent such as aliphatic hydrocarbons such as pro-ξ, butane, intane, hexane, and heptane, benzene,
Aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylsoclohexane are introduced into a reactor, and ethylene is added at 1 to 200 K9/cn? under an inert atmosphere. Press it into the room temperature or 3
Polymerization can proceed at a temperature of 20°C. For example, using a tubular reactor, autoclave reactor, autoclave tubular reactor, etc.
Q ~2000 Kf/cm2, @degree 150~300
A so-called high-pressure polymerization method in which polymerization is carried out under conditions of .degree. C. can also be used.

On the other hand, in gas phase polymerization, ethylene is mixed at a pressure of 1 to 50 Kq/crn2 at a temperature of room temperature to 120°C using a fluidized bed, moving bed, or stirring to ensure good contact between ethylene and the catalyst. It is possible to carry out the polymerization using various means.

The catalyst of the present invention has high performance, and at 80°C, 10 to 2/cr
It exhibits sufficient anti-inflammatory activity even under relatively low temperature and low pressure polymerization conditions of about n2. In this case, since the produced polymer exists in the polymerization system in a slurry state, the increase in viscosity of the polymerization system is extremely small. Therefore, the polymer quality of the polymerization system can be increased to 30% or more, which has great advantages in terms of production efficiency and the like. Since the activity is still high, the step of removing catalyst residue from the produced polymer can be omitted.

The polymerization may be carried out in a conventional one-stage polymerization using one reaction zone, or in a so-called multi-stage polymerization using a plurality of reaction zones. The polymer polymerized using the catalyst of the present invention has a wide molecular weight distribution even in normal one-stage polymerization,
Extremely suitable for blow molding and extrusion molding applications. Multistage polymerization, in which polymerization is carried out under two or more different reaction conditions, makes it possible to produce polymers with a broader molecular weight distribution.

Adjustment of polymerization temperature to adjust the molecular weight of the polymer,
Of course, it is also possible to use known techniques such as adding hydrogen to the polymerization system or adding an organometallic compound that is likely to cause chain transfer. Furthermore, it is also possible to perform polymerization by combining methods such as adding a titanate ester to control density and molecular weight.

Examples of the present invention will be shown below, but the present invention is not limited to these Examples in any way.

In addition, the catalytic activity in the examples refers to monomer pressure of 10 to 7
7cm2, represents the amount of polymer produced (g) per hour per gram of catalyst solid component. Also, MI stands for melt index, and according to ASTM-D71238, the temperature is 190°C and the load is '2. ．． Measured at 16Ks+. FR is temperature 190℃, load 21.6K9
The quotient obtained by dividing the value measured by MI by MI is known to those skilled in the art as an index representing the breadth of molecular weight distribution.

Example 1 (1) Synthesis of solid component (A) 13.8 g of di-n-butylmagnesium and 1.9 g of triethylaluminum were placed in a flask with a volume of 500 ral together with 200 g of n-hebutane, and the mixture was heated at 80°C. By reacting for 2 hours, the composition AAMgs (C2H5)
A hebutane solution of an organomagnesium complex compound of 3(n-C4H9)+2 was obtained. Next, this organomagnesium complex compound 40rnmoIV, n containing (Mg + An standard)
- Hebutane solution 8 (Jrrtl and titanium tetrachloride 40 mm
80 d of the n-hebutane solution containing oβ was added dropwise into a 300 d 72-ml solution in which water and acid accumulation had been removed by purging with dry nitrogen, and the mixture was reacted at -20° C. with stirring for 4 hours. The resulting hydrocarbon-insoluble solid was isolated and washed with n-hebutane to obtain 10.6 g of solid (1).

Separately, 4 mmoβ of chromium trioxide was dissolved in 80 m of distilled water, and silica (Grad
e 952) 20 g was immersed and stirred at room temperature for 1 hour, the slurry was heated to distill off water, and then heated to 120°C.
After drying under reduced pressure for 10 hours, the mixture was fired at 80° C. for 5 hours with dry air flowing through it to obtain a solid (11).

Solid (11) was stored at room temperature under nitrogen atmosphere.

Next, 0.2 g of solid (1) and 3.8 g of solid (I+)
g and 25 stainless steel balls with a diameter of 9 holes were placed in a stainless steel ball mill with a diameter of 10 CJ under a nitrogen atmosphere, and co-pulverized for 5 hours in a vibrating ball mill at 1000 vib/min. A solid component (A) was obtained.

The obtained solid component (4) contained 0.9% by weight of titanium and 0.9% by weight of chromium, and was stored at room temperature under a nitrogen atmosphere.

(2) 20 mg of the solid component (4) synthesized in polymerization (1) and 0% diethylaluminum ethoxide as the organometallic compound (B).
．． 1 mmoj2, dehydrated and deoxidized hexane 0.8f
! , the inside was vacuum degassed and nitrogen was placed at 1.5℃.
was placed in an autoclave. The internal temperature of the autoclave is 8
While maintaining the temperature at 0°C, 1'OK97cm2 of ethylene was added, and hydrogen was added to bring the total pressure to 1'4Kg/cm2. Polymerization was carried out for 2 hours while maintaining the total pressure at 14%/cm2 by replenishing ethylene to obtain 100 g of polymer. Is the catalyst activity 2500g poly? -/g Sol 1
d-hr, polymer IviI is 0.78, FR is 8
I missed it at 7.

Comparative Example In the synthesis of solid component (A), solid (1) containing titanium and magnesium was not used, and solid (11) 4.
Only 0 g was pulverized, and the synthesis and polymerization were otherwise carried out in the same manner as in Example 1. Polymer yield is 70g1
Catalyst activity is 1750. The MIo was 45, and the FR was 80, and the catalyst activity, MI, and FR were all lower than those of Example 1.

Examples 2 to 9゜The raw materials and composition of the solid component (A) and the S types and amounts of the organometallic compound (B) in Example 1 were changed, and everything else was carried out in the same manner as in Example 1. The results shown in Tables 1 and 2 were obtained. Regarding the siloxy organoaluminum compounds in the table,
The organomagnesium complex compound was synthesized from the corresponding organoaluminium and alkylhydropolysiloxane according to Japanese Patent Application Laid-open No. 157490-1989 and Japanese Patent Application Laid-Open No. 1983-1989 filed by the present applicant.
It was synthesized from the corresponding organomagnesium and organoaluminum according to Japanese Patent No. 154388.

Example 10 Using a mixed gas of ethylene and butene-1 containing 15 moλ of butene-1 instead of ethylene, and using inzothene as a polymerization solvent instead of hexane, the mixed gas was heated at 80°C. Partial pressure 10K47cm”, hydrogen partial pressure IK9/C
m2, the total pressure including the solvent vapor pressure is 231'47 cm2,
Other than that, polymerization was carried out in the same manner as in Example 1 using the catalyst of Example 1. The polymerization results were as follows: polymer yield: 92g1 Catalyst activity: 2300, Mll: 12, polymer density: 0.93
It was 9.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] 1. (A) (+) Obtained by reaction of (a) a hydrocarbon-soluble organomagnesium compound or complex compound and (b) a titanium or nocenadium compound containing at least one norogen atom Olefin polymerization method 2 using a catalyst consisting of a solid component obtained by co-pulverizing a hydrocarbon-insoluble solid and (n) a solid obtained by supporting and calcining a chromium compound on an inorganic oxide carrier, and (B) an organometallic compound;
The hydrogen ash soluble organomagnesium compound or complex compound of (a) has the general formula M, MSR1pR2,X, Y,
(In the formula, α is 0 or a number larger than 0, β is a number larger than 0, PIQlrl' is 0 or 1 a number larger than 0,
p 1q + r + :s = mα + 2β, M is an atom selected from aluminum, zinc, boron, beryllium, and lithium, m represents the valence of M, and R1 and R2 are the same or different. Hydrocarbon having a carbon atom number of 4, X and Y are the same or different groups, OR
3,O8i R'R5R',NR'R8, SR9 represents a group, R3 is a hydrocarbon group, R', R',
R6, R7, and R8 are hydrogen atoms (representing hydrocarbon groups).In the polymerization method 3 according to claim 1, the titanium or... sodium compound of (b) is Polymerization method 4 according to claim 1 or 2, which is a compound containing three or more of
Polymerization method 5 according to claims 1 to 3, wherein the chromium compound of (it) is chromium trioxide or a compound that at least partially forms chromium oxide upon calcination; Polymerization method e according to claims 1 to 4, wherein the oxide carrier is silica,
The polymerization method according to claims 1 to 5, wherein the organometallic compound (B) is an organoaluminum compound or a hydrocarbon-soluble organomagnesium compound.