JPS5915407A - Polymerization of 1-olefin - Google Patents

Abstract

PURPOSE:To produce a polyolefin of a wide MW distribution and high activity, by using a catalyst prepared by combining an organometallic compound with a solid component prepared by allowing an inorganic oxide to support a reaction product of a specified Cr component, an Mg component and a Ti (or V or Zr) component and calcining the oxide. CONSTITUTION:A 1-olefin is polymerized by using a catalyst comprising (A) a solid component prepared by allowing an inorganic oxide carrier (e.g., SiO2) to support a reaction product of a trivalent chromium compound containing the water of crystallization (e.g., hydrated chromium acetate or hydrated chromium nitrate), a magnesium alcoholate, e.g., Mg(OC2H5)2, and an alcoholate or oxyalcoholate of a transmition metal selected from Ti, V and Zr, e.g., Ti(O-n-C4H9)4, VO(O-n-C4H9)3, or Zr(O-n-C4H9)4, and calcining the carrier, and (B) an organometallic compound (e.g., triethylaluminum). This catalyst can show extremely high catalytic activity even at temperatures as low as below 100 deg.C and provide a polymer of an easily moldable MW and a wide MW distribution.

Description

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

More specifically, solid components (e) are made by supporting reaction products of specific chromium components, magnesium components, and titanium (or vanadium, zirconium) components on inorganic oxides such as silica and firing them, and organometallic compounds such as organoaluminum. Q3) This relates to an olefin polymerization method characterized by using a novel catalyst with high activity and a wide molecular weight distribution of the produced polymer.

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. In order to produce with
It was necessary to raise the temperature to 200°C. When polymerization is carried out in such a temperature range, the produced polymer will be dissolved in the reaction solvent, so the viscosity of the reaction system will increase significantly, and as a result, the concentration of the produced polymer will increase to 20% or more. was difficult. Therefore, there has been a strong demand for the development of a catalyst that exhibits high catalytic activity at a polymerization temperature of 100° C. or lower, at which polymerization becomes so-called slurry polymerization. In addition, in order to reduce production costs, it is important these days to be able to omit the catalyst removal step in the post-polymerization process, and this requires the development of catalysts that exhibit even higher activity. coming.

As a result of various studies from the above viewpoint, the present inventors found that
A catalyst is a combination of a reaction product of a specific chromium component, magnesium component, -Flin (or vanadium, zirconium) component supported on a carrier such as silica and activated by firing, and an organometallic compound. The present inventors have discovered that it is possible to easily produce a polymer that exhibits extremely high catalytic activity not only in polymerization at low temperatures of 100° C. or lower, but also has a molecular weight that is easily molded and has a wide molecular weight distribution, and has thus arrived at the present invention.

That is, the present invention comprises: (1-1) a trivalent croto compound containing water of crystallization; (1=+) magnesium alcoholade;
(1-iii) a reaction product of a transition metal selected from the group consisting of titanium, vanadium, and/or zirconium with an alcoholate or oxyalcoholade;
This invention relates to an olefin polymerization method characterized by using a catalyst consisting of ρ) a solid component supported on an inorganic oxide carrier and fired, and ρ) an organometallic compound.

The catalyst of the present invention is a combination of a solid obtained by supporting a reaction product of a specific chromium component, magnesium component, titanium (or vanadium, zirconium) component on a carrier such as silica and activated by firing, and an organometallic compound. In the polymerization method, as is clear from the examples and proportions described later, the molecular weight is lower (MI is higher) than when no magnesium component is included, and the molecular weight is suitable for molding. In addition, the molecular weight distribution is wider than when both magnesium and titanium components are not included.
It has more suitable liquidity. In any case, the use of the catalyst of the present invention has even higher activity and is therefore suitable.

The present invention will be explained in detail below.

As the inorganic oxide carrier used in the present invention, silica, alumina, silica-alumina, doria, zirconia, etc. can be used, but silica and silica-alumina are preferable, and silica is particularly preferable.

Examples of the crystal water-containing trivalent chromium compound used in (1-1) of the present invention include hydrated salts and double salts such as chromium acetate, chromium oxalate, chromium chloride, and chromium nitrate, and preferably (C) I, c, 'oo) aCr・11-
1.0, Cr(NO3), -9H,0, CrCt, -
6H, 0 can be mentioned. It is important that the chromium compound used in the present invention (along with the magnesium alcoholade) contains water of crystallization. The effects of the present invention cannot be achieved with anhydrous materials.

The magnesium alcoholade used in (1-It) of the present invention includes Mg(QC)7, Mg(OCj(s)
)y, M5((Q i s o -C,H,), etc., and preferably Mg
(OCtHs)t is used.

The transition metal alcoholade or oxyalcoholate selected from the group consisting of titanium, vanadium, and zirconium used in (1-tri) of the present invention is, for example, 'l'i (On -C4H,), Ti ( U
i5o-C,IA,f),.

VO(On C4HO)s,zr(On -C4H
o ) 4, Z ro (n C4 搗) t, etc., preferably Ti (On -04H,) 4, VO (
OnC4H9)! ,7. r(Qn-C4H,)4 is used.

Examples of organometallic compounds used in the invention include organoaluminum compounds, organoboron compounds, organozinc compounds, organolithium compounds, hydrocarbon-soluble organomagnesium compounds, and complex inclusions, such as triethylaluminum, triethylaluminum, isobutylaluminum, trir1--\gysolaluminum, tridecylaluminum, diethylaluminum hydride, aluminiraj isoprenyl, diethylaluminum etogindo,
Diethyl methyl ethylhydrosiloxyaluminum and mixtures thereof, triethyl boron, diethyl masticate, n-butyl lithium, di11-buty/l/magnesium-triethyl aluminum complex, n-butyl 5
Examples include ec-ferdelmagnesium, 11-butyl ethylmagnesium, and the like. vr-i containing at least one of an alkoxy group or a siloxy group
A aluminum compound I proboscis is used.

Next, the chromium compound (1-1), the magnesium compound (1-it), and the titanium compound (or vanadium or zirconium compound) (1-i*) are reacted, and then J I will explain about [1 have-)ru jin.

(1-i) trivalent chromium compound containing crystal water;
The reaction between the magnesium alcolade (+) and the titanium (or vanadium, zirconium) alcolade (or oxyalcolade) (1=t+) can be performed using carbon tetrachloride, chloroform, chlorinated hydrocarbons such as methylene chloride, benzene, etc. , aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, and isooctane, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. It can be carried out in a medium mixed with alcohols. Preferably, the reaction is carried out in a chlorinated hydrocarbon such as carbon tetrachloride or chloroform. There is no restriction on the order of reaction, but preferably (1-1+) magnesium compound and (1-+
++ ) titanium (or vanadium, zirconium) compound is first mixed and stirred, and then (1-i) chromium compound is added, or (1-1) chromium compound and (1-++ ) is first mixed and stirred, and then (1-tri) of titanium (or vanadium, zirconium) compound is added. There is no particular restriction on the molar ratio of the mixed reaction, but preferably (1-1) Cr, (1-H) and (1-+++ > TI (or ↓V, Zr) mo/ L/ratio is Mg/Cr"=1~l O1'l"i(
It is recommended that V, Z[)/Cr2 be in the range of 0.25 to 10. There are no particular restrictions on the reaction temperature and reaction time, but in view of the progress of the reaction, preferably 0 to 200 °C, preferably 30 to 120 °C, and 0.5 to 120 °C.
Temple 1 River reacts. The state of the reaction mixture is the solvent, anti+,
= Depending on the conditions, it becomes a slurry state or solution in which chromium, magnesium, titanium, etc. are partially or mostly dissolved.

The reaction mixture j containing chromium, magnesium, titanium, etc. expanded in this way is mixed with an inorganic oxide support such as silica, silica-alumina, etc., and supported. At this time, it is preferable to support the particles while stirring. There are no particular restrictions on the temperature, time, etc. for supporting, and the solvent is removed by filtration or distillation. When the solvent is removed by distillation to deposit and support black fat, etc., it is desirable to carry out the reaction at a temperature of 200° C. or lower. Regarding the amount of metal to be supported, the chromium content in the solid after being supported is 0.02 to 2.5% by weight.

It is preferable that the weight is in the range of 05 to 1.5% by weight. Incidentally, it is preferable that silica, silica-alumina, etc. used as a carrier be heated and dried in advance, for example, under a stream of spirit gas.

Next, firing activation of the supported body 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 an inert gas or reduced pressure. Preferably, air substantially free of moisture is used. The firing temperature is 300°C or higher, preferably ld
The reaction is carried out at a temperature of 400 to 900° C. for several minutes to several tens of hours, preferably 30 minutes to 10 hours. During firing, it is recommended to blow in enough dry air to activate firing in a fluidized state.

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 of combining the solid component (a) (ie, a solid containing chromium, magnesium, titanium, etc. supported on a carrier and activated by firing) with the organometallic compound of 8) will be described.

The solid component (c) and the organometallic compound 63) may be added to the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. It is also possible to carry out a method in which the solid component is previously treated with the organometallic compound and then combined with the organometallic compound and fed into the polymerization system. The ratio of both components to be combined is (organometallic)/C molar ratio of 0.01 to 3000, preferably o, 1 to io.

range is recommended.

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

The olefins that can be polymerized using the catalyst of the present invention are α-olefins, particularly ethylene1, and the catalyst of the present invention can also be used to copolymerize ethylene with monoolefins such as propylene, pupoon-11hexene-1, etc. Alternatively, it is also possible to use it for polymerization in the coexistence of a diene such as butadiene or imprene.

By carrying out copolymerization using the catalyst of the present invention, it is possible to produce a polymer having a density in the range of 0.91 to 0.97 y/atl.

As the polymerization method, usual suspension polymerization, solution polymerization, and gas phase polymerization are possible. In the case of suspension polymerization and solution polymerization, the catalyst is used as a polymerization solvent, such as aliphatic hydrocarbons such as propane, butane, pentane, hexane, and heptane, benzene,
Aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane were introduced into a reactor, and ethylene was injected to a concentration of 1 to 200/I under an inert atmosphere, and the mixture was heated to room temperature. Polymerization can proceed at temperatures between 320°C and 320°C. In addition, using a tubular reactor, an autoclave reactor, an autoclave tubular reactor, etc., a pressure of 200 to 200
It is also possible to apply the so-called high-pressure polymerization method in which polymerization is carried out under conditions of 00 kf/d and a temperature of 150 to 300°C.On the other hand, in gas phase polymerization, ethylene is polymerized at a pressure of 1 to 501 kf at a temperature of room temperature to 120°C. Polymerization can be carried out under the following conditions, using methods such as a fluidized bed, moving bed, or stirring to ensure good contact between ethylene and the catalyst.
It is J-Noh.

The catalyst of the present invention has high performance and exhibits sufficiently high activity even under relatively low temperature and low pressure polymerization conditions of about 80° C. and 10 ks/m. In this case, since it exists in a slurry state in the branched polymer system to be produced, the increase in viscosity of the polymer system is extremely small. Therefore, the polymer concentration in the polymerization system can be increased to 30% or more, which has great advantages in terms of production efficiency and the like. Furthermore, due to its high activity, 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 a normal one-stage polymerization,
It is extremely suitable for blow molding and extrusion molding applications. ``Multi-stage polymerization in which polymerization is carried out under more than 62 different reaction conditions''
It is possible to produce polymers with even wider molecular weight distributions.

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 carry out the 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 mm.
represents the polymer production j1 (r) of the catalyst solid component 1f/1 hour time υ. Also, MI stands for melt index, and according to A, 9TM D-1238,
It was measured at a temperature of 190°C and a load of 2.16 kt. Fl (, is the quotient obtained by dividing the value measured at a temperature of 190° C. and a load of 21.6 wheels by MI, and is known to those skilled in the art as an index representing the breadth of molecular weight distribution.

Example 1゜(1) Synthesis of solid components 100% carbon tetrachloride and 11.4 W (100 tnmol
) was prepared. Tj (On -C4H,
) 46.8 F (20 mmol) was added thereto, and the mixture was stirred for 5 hours while heating under reflux.

Then crcz, -6H405,3F (20mTn
ot)iJI], j, and the mixture was further stirred under heating and reflux for 8 hours. Next, add 80 − of carbon tetrachloride to dilute 17, Cr
A reaction mixture containing , Mg, and i'i was obtained.

The inside of another 2t flask was replaced with dry nitrogen, and 100F of silica gel (manufactured by Fuji Davison, grade 952), which had been previously dried under dry nitrogen flow at 300°C for 2 hours, and 1t of dehydrated and degassed carbon tetrachloride were charged. The entire reaction mixture containing Cr, Mg, and rlTi was added to the mixture at room temperature while stirring, and the mixture was stirred for 1 hour. Next, the solvent carbon tetrachloride was removed by distillation, followed by vacuum drying at 60° C. for 5 hours to obtain a chromium-magnesium-titanium phase-supported solid.

Next, the supported solid was placed in a quartz firing tube and fired at 800° C. for 5 hours under dry nitrogen flow to obtain a catalyst solid component. The obtained solid component contained 1.0 times chromium and was stored at room temperature under a nitrogen atmosphere.

(2) Solid component (to) 20■ synthesized in polymerization 0) and diethylaluminum ethoxide 0.1 as organometallic compound 43)
mm01 and 0.8 t of dehydrated and deoxygenated hexane were placed in a 1.5 t autoclave whose interior was vacuum degassed and replaced with nitrogen. Keep the internal temperature of the autoclave at 80℃, add ethylene to 10℃, and add hydrogen to bring the total pressure to 14℃.
ψ− Toshida. By replenishing ethylene, the total pressure was increased to 14
Polymerization was carried out for 2 hours while maintaining the pressure at ~16 (l
A polymer of f was obtained.

Is the catalyst activity 4000F poly? -/y 5olid
ehr.

The Ml of the polymer was 0.61 and Fl( was 102).

Comparative example.

In the synthesis of solid components (conversion), Mg ((
was not used, and everything else was the same as in Example 1,
Catalyst synthesis and polymerization were performed. The polymerization results are 1. l?
+17-yield 77102 f, catalyst activity 2550, 841
It was 0.21 and FR100.

Comparative example B.

In the synthesis of the solid component (e), Mg (QC, H crystal and 'l
Catalyst synthesis and polymerization were carried out in the same manner as in Example 1 except that '1(On-04H,) was not used. The result is that the polymer storage is 84 and the catalyst is old note 210.
0, MlO, 20, Fl (85).

Comparative Example C0 In the synthesis of the solid component (a), the calcination operation after loading was not performed, and the catalyst synthesis and polymerization were carried out in the same manner as in Example 1.
28693). The polymerization results were as follows: polymer yield: 249, catalyst activity: 600. Mlo, 84, F
Examples 2 to 8 The synthesis conditions for the solid component (E) in Example 1 were changed, and the results shown in Table E.1 were obtained.

Examples 9 to 16 The type and amount of organometallic compound (13) in Example 1 were changed to obtain the results shown in Table E.2. Regarding the siloxy organoaluminum compounds in the table, according to Japanese Patent Publication No. 46-40334 filed by the present applicant,
Comparison of organic aluminum and alkyl hydrogen robot +1
The organomagnesium complex compound synthesized from siloxane is disclosed in Japanese Unexamined Patent Publication No. 50-1574 filed by the present applicant.
1 synthesized from the corresponding organomagnesium and organoaluminium according to Japanese Patent Application No. 90 and JP-A-50-154388, Example 17. Using a gas mixture, add isobutyne instead of hexano as a polymerization solvent and 1. te Jti, 8
Mixed gas partial pressure 10 kp/m at 0°C, hydrogen outside +-r:
1 kv/ffl, total pressure including solvent vapor pressure 23 kg/
crl and polymerization was carried out in the same manner as in Example 1 using the catalyst of Example 1 except for the catalyst. The polymerization result shows that the polymer yield is 1
181, Catalytic activity 2950, ML O, 67, Bo? The density of Zuma was 0932.

Claims (1)

[Claims] 1. (to) (1-1) a trivalent chromium compound containing crystal water;
(1-1+) magnesium alcoholade and (l-i
) A reaction product of a transition metal selected from the group consisting of titanium, vanadium, and zirconium with an alcollade or an oxyalcollade, (2) a solid component supported on an inorganic oxide carrier and fired, and CB) an organometallic compound. A method for polymerizing olefins using a catalyst comprising. 2. The polymerization method according to claim 1'1, wherein the inorganic oxide carrier in (2) is selected from the group consisting of silica, silica-alumina, and alumina. 3. The polymerization method according to claim 1, wherein the inorganic oxide carrier in (2) is silica. 4. Claims 1 to 4, wherein the crystal water-containing trivalent chromium compound of (1-1) is selected from the group consisting of chromium acetate aqueous salt, chromium nitrate aqueous salt, and chromium chloride aqueous salt; - Polymerization method described in Section 3. 5. (1-I+) magnesium alcoholade is Mg
(QC!H1)t. The polymerization method according to claims 1 to 4, wherein (QC!H1)t. 6. (1-+i1) transition metal alcoholade or oxidial alcoholade is Ti (On C4) VO
(On-CaH,)s, Zr(On-C4H, In) The polymerization method according to Claims 1 to 5JJ, wherein the polymerization method is selected from the group consisting of (On-CaH, )s, Zr(On-C4H, 8. The polymerization method according to claims 1 to 1-6, which is carried out in a neutral atmosphere. 8. The organometallic compound in [F]) is an organoaluminum compound, an organoboron compound, an organozinc compound, an organolithium compound, The polymerization method according to claims 1 to J-7, wherein the polymer is selected from the group consisting of hydrocarbon-soluble organomagnesium compounds or complex compounds. 9. The polymerization method according to claim 8, wherein the organometallic compound is an organoaluminum compound containing at least one of an alkoxy group and a hydroxyl group.