JPS6011045B2 - Polymerization method of α-olefin - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyolefins using a novel catalyst. More specifically, the present invention uses a novel catalyst consisting of a special organomagnesium compound, a specific metal halide, and a titanium compound to polymerize ethylene or ethylene and other Q-olefins by a solution polymerization method, and then molds and processes them. The present invention relates to a method for producing polyethylene with excellent properties. Solution polymerization is already known as a suitable method for producing polyethylene. The advantages of this solution polymerization include the following. {
1' ethylene polymerization is an exothermic reaction, and deripening is a major problem in the process, but solution polymerization has a high reaction temperature, so a large temperature difference between the internal temperature and the jacket can be maintained, resulting in good heat removal efficiency. This becomes more advantageous as the polymerization temperature becomes higher.

[2-
The degree of polymerization of ethylene, that is, the molecular weight of polyethylene, can be controlled relatively accurately by changing the reaction temperature, and molecular weight control can be achieved by using a small amount of hydrogen. '3' Since there is a correlation between the molecular weight of polyethylene and the viscosity of the reaction solution, it is possible to estimate the molecular weight of polyethylene by measuring the viscosity of the solution in the reactor and take prompt action. '4; Polyethylene is used in the form of pellets, and polyethylene produced by suspension polymerization and gas phase polymerization is in the form of powder, and extra energy is required to form it into pellets using an extruder. . In solution polymerization, the heat of polymerization is used,
Since the solvent can be evaporated and the polyethylene in a molten state can be introduced into the extruder, it is extremely advantageous in terms of effective use of energy. To take advantage of this advantage, higher polymerization temperatures are desirable. On the other hand, the problem with solution polymerization is that
If the solution concentration is increased or the molecular weight of polyethylene is increased, the viscosity of the solution increases, making it difficult to implement on a factory scale. To solve this problem, it is necessary to raise the polymerization temperature and lower the solution viscosity. However, when the polymerization temperature is raised, the catalyst efficiency decreases and a large amount of catalyst residue remains in the polyethylene. For this reason, the polyethylene becomes colored and the product after molding deteriorates, and it is difficult to remove the catalyst residue. Therefore, there is less catalyst Zenizumi in polyethylene,
Catalysts with high catalytic efficiency at high temperatures such that a removal step is not required are needed. In the suspension polymerization method, many Ziegler type catalysts with high catalytic efficiency are known. However, the catalyst efficiency of these catalysts generally decreases as the polymerization temperature is raised, and the decrease is particularly significant at temperatures above 150° C., and the performance is insufficient for eliminating the catalyst residue removal step in solution polymerization. On the other hand, solution polymerization catalysts for olefins using organomagnesium rust bodies, halides, and titanium compounds have been disclosed (Tokukan Sho 47-11372, JP 50-14* Powder 3).
No., Tokukan Floor No. 51-144397. ) Although these catalysts have high catalytic efficiency compared to conventional catalysts, their catalytic efficiency is still insufficient, especially at high temperatures. As a result of studying solution polymerization catalysts, the present inventors discovered that a catalyst component consisting of a titanium compound containing at least one halogen atom brought into contact with a reaction product of a special organomagnesium compound and a specific metal halide was developed. By combining organoaluminum compounds, the catalyst efficiency is extremely high.
The inventors of the present invention have discovered a catalyst that exhibits little reduction in catalytic efficiency even at temperatures of 60° C. or higher, particularly 1200 qo or higher, and is stable and can be stored for a long period of time. That is, the present invention provides (i) the general formula MQ Mg8R also has R cost
M group metal atom, 3 is a number greater than or equal to 1, Q, p, q, r,
s is 0 or a number greater than 0, p10q0r1s! mQ+2
8, OS (r+s)/(Q+3)≦1.5, m is the valence of M, R1 and R2 are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, X1, X2 is the same or different group, hydrogen atom, OR3, OSjR4R5
R6, NR7R8, SR9 groups, R3 to R9 represent a hydrocarbon group having 1 to 20 carbon atoms, R4
(R6 may be a hydrogen atom) soluble in a hydrocarbon solvent and (i
i) Boron, silicon, germanium, tin, lead, phosphorus,
U
ii) A reaction product obtained by contacting a titanium compound containing at least one halogen atom under conditions where the ratio of Mg and Ti is in the range of 3 to 5 oo, and the concentration of Ti is 2 mol/or less. This relates to a method for polymerizing Q-olefins, using [A] and an organoaluminum compound [B], and carrying out polymerization in a solution state in one stage or in multiple stages in the range of higher than 15 and 0 to 32,000. The features of the present invention will be explained below. The first feature of the present invention is that the catalyst efficiency is high. As is clear from the examples described later, the catalyst efficiency is 500k.
It is possible to reach 9' Ti or more, and it is possible to omit the process of removing bamboo grass after the catalyst. The second feature of the present invention is that it is stable even at high temperatures. As is clear from the examples below, the catalyst efficiency is 5 even at temperatures above 200°C.
00k9/taTi can be achieved. The third feature of the present invention is that a polymer with a very narrow molecular weight distribution can be obtained. As shown in the examples below, it is possible to produce a polymer with a narrow molecular weight distribution suitable for injection molding. The fourth feature of the present invention is that the catalyst can be stored for a long period of time. As shown in Example 16, no significant decrease in catalyst efficiency was observed even after one month of catalyst synthesis. This means that a homogeneous catalyst can be used for a long period of time, and facilitates long-term stable operation of polymerization. The general formula MQ MgBR used in the catalyst of the present invention also has the following formula: M, R1, R2, X1,
The organomagnesium compound (i) (X2, Q'8'P, q, r, s have the above-mentioned meanings) will be explained. Although (i) is shown as an organomagnesium compound, it includes all R2Mg and complexes of these with other metal compounds. In the above formula, M can be a metal element belonging to Group 1 to Group M of the periodic table, such as lithium, sodium, potassium, beryllium, calcium, strontium, barium, zinc, boron,
Examples include aluminum, but lithium, beryllium, boron, aluminum, and zinc are particularly preferred because they facilitate the production of organomagnesium bodies that are soluble in hydrocarbon solvents. Furthermore, aluminum is preferably used. The ratio of magnesium to the metal atom M may preferably include a dialkylmagnesium derivative in which Q=0. Kushami 50, especially o. A Q-organomagnesium key body soluble in a hydrocarbon solvent of 5 mmA is preferred. The hydrocarbon group represented by RI to R9 is an alkyl group, cycloalkyl group, or allyl group having 1 to 2 q carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl, etc. , benzyl group, etc. In particular, R1 and R2 are preferably alkyl groups, and R4, R5, and R8 are hydrogen atoms.On the other hand, when Q=0, organic To obtain a magnesium compound, R1,
The hydrocarbon group of R2 is limited. For example, the first is RI
and/or R2 is secondary or tertiary having 3 or more carbon atoms
In the case of an alkyl group of
This is the case where the alkyl group of 6, R2, is an alkyl group having 4 or more carbon atoms, and the difference in the number of carbon atoms between RI and R2 is 2 or more. Specifically, (sec-C4 is) 2
Mg, (sec-C4 day 9) Mg (n-C4 day 9), (
iso-C3 days 7) Mg (n-C4 days 9), (C2 days 5
)Mg-(n-C44) etc. are used. Also, R2M
In order to reduce the viscosity of the receiving liquid, it is advantageous to use small amounts of organometallic additions. The relational expression P+q+r+s=mQ+28 of the symbols 〇, 3, p, q, r, s indicates the stoichiometry between the valence of the metal atom and the substituent, and the preferable range is 0≦(r
+s)/(Q+B)≦1.5 is X for the sum of metal atoms
Indicates that the sum of I and X2 is 0 or more and 1.5 or less. In order to increase the stability of the catalyst component [A] and increase the catalyst efficiency at high temperatures, containing XI or X2 as a substituent,
In other words, (r+s)>0 is recommended. Preferably 0.
The range is 1≦(r+s)/(Q+3)≦1.3, particularly preferably 0.2≦(r+s)/(Q18)≦1.0. These organomagnesium compounds have the general formula RIM
A compound represented by gQ,R Mg (RI has the above meaning and Q is a halogen atom) and a compound represented by the general formula M
Kyumine X is also Shigeru, MQaX ball, (M, R2, X1, ×2,
Q, m have the above meanings, a, b, c = a+b+c=
m) in an inert hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, etc. at a temperature of 0°C to 150qo, and if necessary, further Alcohol, this
Synthesized by reacting siloxanes, amines, imines, thiols, or dithio compounds. Furthermore, organomagnesium compounds include MgX, RIMg
XI and M old ax, MR Nen-, day, or RIMgX1
, R room Mg and R climbing MX sudden n or RIMgX1,R
Mine Mg and X MX Mine a (in the formula M, R1, R2, X1,
X2 and m have the above-mentioned meanings, and can be synthesized by reaction with X1 and X2, including the case where X1 and X2 are halogens, and a is a number from 0 to m. In general, organomagnesium compounds are immovable in inert hydrocarbon solvents, and organomagnesium compounds where Q>0 are soluble. In the present invention, it is necessary to use a soluble organomagnesium compound. In addition, certain organomagnesium compounds, such as (sec-C4) Mg, (C2 ratio) Mg (n-C
Although compounds such as 4-day 9) have Q=0, they are soluble in hydrocarbon solvents, and such compounds can of course be used in the present invention to give preferable results. Next, boron, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth,
Or mercury halide (ii) will be explained. The halide refers to a compound in which at least one halogen atom is directly bonded to the above atom, and preferably boron, silicon, or germanium chloride is used. These compounds are desirably soluble in a hydrocarbon solvent in order to allow the reaction to proceed uniformly. Specifically, these compounds include BC13, C2day5BC12,
(C2 ratio) 28CI, SIC14, C ratio SIC1
3, (CH3)2SIC12, (C6 day 5)2SIC1
2,WCl4,(CH3)2QCl2,SnCl4,P
Cl3, SbCl5, (C2 is)2S is 1, HgC12
etc. In order to achieve high catalytic efficiency at a polymerization temperature of 200 qo or more, the general formula SICI rainbow bR2-
Particularly preferred are the silane compounds (a and b) (R0, a, and b have the above-mentioned meanings). For example, SIC 13th, SIC 12th (CH3), SI
CIH2 (C ratio), SICIH (CH3)2, SIC1
2nd (CHCH2), SIC12th (C2th day 5), SI
C12 days (C3 days 7), etc. are used. The titanium compound side containing at least one halogen atom will be explained. As titanium compounds, TIC14, TiBr4, Ti
14, TIC13(OC2&), TIC13(0i-C
3rd 7) 9, TIC13 (0m-C4) 2, TIC
12 (OC2 day 5) 2, TIC12 (0i-C3H?)
2, TIC12 (0m-C4 public) 2, TIC1 (OC2
&), TIC1(0i-C3H?)3, Tic1(〇m
-C4 day 9) 3, Tic12. 2C2day3)2,Ti
Halides such as c12 (ratio 02)2, alkoxy halides, carboxy halides, and acetylacetonate halides may be used alone or in mixtures.
Preferably, titanium chlorides are recommended, particularly preferably titanium tetrachloride. The reactions of compounds (i) and (ii) are carried out using inert reaction solvents, e.g. aliphatic hydrocarbons such as hexane, heptane, octane, aromatic hydrocarbons such as benzene, toluene, fatty acids such as cyclohexane, methylcyclohexane, etc. It can be carried out in a cyclic hydrocarbon or a mixture thereof. In terms of catalyst performance, aliphatic hydrocarbon solvents are preferably used. (i), (ii) Various methods can be considered for the reaction order of blood, but in order to exhibit highly active catalytic performance,
It is necessary to prevent (i- and (ii) from coming into contact with each other in advance.) To be more specific, a solid component is generated by the reaction of (i1 and (ii)), and the solid component is effectively coated on the solid surface.
By contacting ii), the surprising effects of the invention are achieved. ... and (ii) can be carried out by a simultaneous addition method in which two components are simultaneously introduced into the reaction zone and reacted, or one component is charged into the reaction zone in advance and the remaining component is introduced and reacted. Any of the so-called forward (reverse) addition methods, in which the The reaction temperature is not particularly limited, but is preferably 0 in view of reaction progress.
It is carried out at a temperature of 150°C to 150°C, particularly preferably 2000°C to 150°C. There is no particular restriction on the reaction ratio of the two components, but preferably (for 1 mol of component 11, component (ii) is added to 0.01 to 1 hol, particularly preferably 0.1 mol).
A range of mol to 2 blood 01 is recommended. A solid component is produced by the reaction of (i) and (ii), but
This can be isolated by filtration, or washed by decantation, and then subjected to reaction with seeds. In order to simplify the reaction operation, after the reaction between (i) and (il) is completed, it is preferable to introduce (iii) into the reaction solution to further proceed with the reaction. (iii) The amount of 1 used is within the range of 3≦general≦5oo, preferably 5≦temp≦2oo, particularly 1, and the concentration of Ti in the reaction solution is 2mol/Z. It is necessary to carry out the following reaction temperature: Although there is no particular restriction on the reaction temperature, from the viewpoint of reaction progress, it is preferable to
The temperature is preferably 0°C to 95°C. Although the catalyst component [A] of the present invention is useful as a catalyst for ethylene polymerization as it is, it becomes an even more excellent catalyst when combined with an organoaluminum compound. As organoaluminum compounds, AI (C2 day 5) 3, Yama (C3 day 7) 3, AI (C4 day 9)
3, AI (C, .) 3, AI (C6 days, 3) 3, Mountain (
C8 day, 7) 3, AI (C, oH) 3 etc. trialkyl aluminum, AI (C2 day 5) 2 CI, mountain (C2&
)CI2,AI(i-C4 ratio)2CI,AI(C2
Day 5) Alkylaluminium halide such as 2Br, N
(C2 day 5) 2 (OC2 horse), mountain (i-C4) 2 (O
Alkoxyalkyl aluminum such as C49), AI
(C2 day 5) 2・(OSjHCH3C2 day 5), AI(
i-C4 day 9) 2・(OSi(CH3)2i-C4 day 9)
), and mixtures thereof are used. Catalyst components [A] and [B] may be added into the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. Also, the ratio of both components to be combined is T in the [A] component.
It is defined by the molar ratio of i, M in the [A] component, and N in the [B] component, preferably (M+AI)/Ti is 3/1 to
1000/1, more preferably 5'1 to 500
/1 range is used. The catalyst of the present invention is suitable for the polymerization of ethylene, including propylene, butene-1, isoptene, hexene-1,4-methylbentene-1, octene-1, decene-1, butadiene, isoprene, etc.
- It is also possible to carry out copolymerization with ethylene in the presence of olefin or diolefin, especially when 1 mol of ethylene is copolymerized.
It is preferable to use the Q-olefin ear hole or less. Density 0.975-0.9 by homopolymerization and copolymerization
It is possible to produce a range of 10 polyethylenes. Polymerization is carried out at a temperature of 150° C. to 320 qo by a solution polymerization method. As the polymerization solvent, aliphatic hydrocarbon solvents such as hexane, hebutane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are used. The catalyst is introduced into the reactor together with the polymerization solvent, and ethylene is heated at 0.1 Mpa to 4 mMpa, preferably Imp.
It is possible to carry out the polymerization by introducing a partial pressure of a to 29 MPa and mixing with a strainer to ensure good contact between ethylene and the catalyst. The polymerization may be carried out in a single-stage polymerization using one reaction zone, or it is also possible to carry out a so-called multi-stage polymerization using a plurality of reaction zones. Although this catalyst yields polyethylene with a narrow molecular weight distribution in one stage polymerization, it is also possible to produce polyethylene with a wide molecular weight distribution through multistage polymerization. Furthermore, in order to control the molecular weight, it is also possible to change the temperature of the reactor or add hydrogen or an organic 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 adjust the density. Examples of the present invention are shown below, but the present invention is not limited to these examples in any way. In these examples, MI stands for melt index, which was measured using ASTM D-12 paper at a temperature of 19 pi and a load of 2.16 k9. FR means the quotient obtained by dividing the value measured at a temperature of 19 mm and a load of 21.6 kg by MI, and is one of the measures of molecular weight distribution, and the lower the value, the narrower the molecular weight distribution. The catalyst efficiency is T
It is expressed as the polymer production amount k9 per i/night. Example 1 1 Hydrocarbon solvent soluble organomagnesium compound (i)
5 days of magnesium powder was added to a 200-meter desk flask that had been purged with nitrogen. Of the desktop mixture of 20.8' of n-butyl chloride and 60' of n-octane, 20' was introduced into the flask. The flask was heated and refluxed, and after the reaction started, the remaining n-butyl chloride was added dropwise under reflux for 2 hours, and after the reaction was completed, it was allowed to worship for another 1 hour. In addition, AIC12
(0n-C8 day 7) containing 30 hmol n-octane 2
0' was added and the reaction was carried out for 70°C to obtain an organic magnesium compound solution. As a result of analysis, the composition of this key body was NMg3 (n-C4 day 9)8. , (0n-C
3 days 7) It is small $, and the organometallic concentration is 0.92 hol'
It was a sleeve. In addition, A] CI2 (0n-C3 day 7) is
Aluminum powder, AIC13, n-C3 days 70 days n
- Synthesis was carried out in octane at a molar ratio of 1:2:3. D Capacity 250 equipped with catalyst component [A] synthesis dropping funnel and water-cooled reflux condenser
Oxygen and moisture inside the flask were removed by nitrogen substitution, and 0.1 mol of trichlorosilane was added under nitrogen atmosphere.
/ 20 parts of n-octane solution and 30 parts of n-octane
The temperature was raised to 70 qo. Next, 2.17 g of the component (i) and 20 g of n-octane were weighed into the dropping funnel. The mixture was added dropwise at 70° C. over a period of 1 hour, and the reaction was further allowed to proceed at this temperature for 1 hour. The reaction solution became a white suspension. This white suspension contains 27 n-octane containing 0.08 mol of titanium tetrachloride.
．． 8 secretion was introduced, and the reaction was carried out for 1 hour at 70:00. m
Polymerization of ethylene

Catalyst component [A] synthesized with [0] 2.0
0.043 hmol of trioctylaluminum and 0.6 hmol of dehydrated and degassed n-octane were placed in an autoclave whose interior was vacuum degassed. Next, after charging 18 hmol of hydrogen, the autoclave was kept at 210 qo, and 4.0 qo of ethylene was added. Polymerization was carried out for 30 minutes while maintaining the total pressure constant by applying pressure to the dish Mpa and replenishing ethylene. As a result, a polymer of 80 ml was obtained. The catalyst efficiency was 980k9/taTi, the MI was 4.3, and the FR was 23 and the density was 0.971. Examples 2 to 16 Ingredients (i), (ii) and (i) shown in Table 1 and (
Catalyst component [A] was synthesized in the same manner as in Example 1 except that the reaction conditions of i) were used. Next, polymerization was carried out under the same conditions as in Example 1, and the results shown in Table 1 were obtained. Satoshifune Example 16 The catalyst component [A] synthesized in Example 1 was stored under a nitrogen atmosphere for one month. Using this, ethylene was polymerized in the same manner as in Example 1, and skin 8. A polymer of FR24 was obtained. Catalyst efficiency was 948. Examples 17 to 24 Oxygen and moisture inside a 250-volume flask equipped with a dropping funnel and a water-cooled reflux condenser were removed by nitrogen substitution, and trichlorosilane 1. Hexane solution containing shoe mol 5
0' was added and the temperature was raised to 60 qo. Next, AIMg6 (n-C6 days, 3) 8 (0n-C4 ratio) 72. 20 hmol of hexane was weighed into the dropping funnel. Under condensation at 60℃ 1. It took hours to drip. Hexane 30' containing component Qii) shown in Table 2 was introduced into this reaction solution, and the reaction was carried out under the conditions shown in Table 2.
Ethylene polymerization was carried out in the same manner as in Example 1 except for this component [A], the catalyst component [B] shown in Table 2, and the polymerization conditions, and the results shown in Table 2 were obtained. Ship Examples 25-30 In the same manner as in Example 17, C2 ratio M Yanagi C442. enemy hmol and SjHC134 enemy hmol 6
The reaction was carried out at 0°C for 3 hours. Hexane 3 containing the components shown in Table 3 in this reaction solution
0 secretion was introduced and the reaction was carried out under the conditions shown in Table 3. Ethylene was polymerized according to the method of Example 1 using the catalyst component [A] synthesized in this manner and the catalyst component [B] shown in Table 2 under the polymerization conditions, and the results shown in Table 3 were obtained. Vertical Example 31 Using catalyst component [A] 2' synthesized in Example 1 and 0.04 mmol of triethylaluminum, ethylene pressure was 2.
．． According to the method of Example 1, 1.2 mmol of ethylene was polymerized under the conditions of 0 MPa, 2 hmol of hydrogen, and a polymerization temperature of 14 mmol. Next, 9 hmol of hydrogen was introduced and the temperature was raised to 220 qo, and then again under the condition of an ethylene partial pressure of 2.0 Mpa,
Polymerization of 1.5 hol of ethylene was carried out. As a result, blood is 0
．． A polymer of 9FR97 was obtained. Example 32 Example 2
2.0 of the catalyst component [A] synthesized above and 0.03 hmol of tridecylaluminum were dehydrated and degassed using hexane 0.0.
After 5 days, the inside was vacuum degassed and the mixture was placed in an autoclave. After introducing hydrogen mol, ethylene 6. After pressurizing the bait at a pressure of Mpa, the reactor temperature was raised to 270 oo and 1
Polymerization was carried out for 0 minutes. As a result, the skin 6. Polymer 35 of FR24 was obtained. Example 33 AIMg7 (C2 day 5). (n-C4day9)72hmol, SiHC12
(CH3)3. Wind mol and TICl (0n-
Catalyst component [A] was synthesized in the same manner as in Example 1 except that 30.08 mmol of C4 was used. The inside of this was vacuum degassed with 3' and 30.07 mmol of N (i-C4 day 9) dehydrated and degassed and 0.6 hexane.
It was introduced into a quartclave. Next, 15 hmol of hydrogen
and 1,3 hmol of butene were added, the temperature was raised to 160 oo, and 2. (2) Pressure was applied at a partial pressure of Mpa. Polymerization was carried out for 30 minutes while maintaining the total pressure by replenishing ethylene. As a result, M18.5, FR27, density 0.952
A polymer with a catalyst efficiency of 926 was obtained. Example
34-39 AIM & (n-C 4th day 9) 6 (0n-C 6th day, 3) 32
hmol, SiHC131.8hmol and TIC1
Catalyst component [A] was synthesized in the same manner as in Example 1 except that 40.1 hmol was used. The inside of this was vacuum degassed with 2' and 0.6 kerosene which had been dehydrated and degassed 30.08 hmol of N (C2 day 5).
It was introduced into a quartclave. Next, after adding the hydrogen number mol and the olefin shown in Table 4, the temperature is raised to 20,030 ml. 3. Ethylene. The polymerization was carried out for 3 nights while maintaining the total pressure by pressurizing the polymer in a manner similar to that of the previous experiment and supplementing with ethylene, and the results shown in Table 4 were obtained. Table 4 Comparative Example 1 1 Synthesis of catalyst component [A] Oxygen and moisture inside a 250' flask equipped with a dropping funnel and a water-cooled reflux condenser were removed by nitrogen substitution, and trichlorosilane was added under a nitrogen atmosphere. Fifty volumes of a hebutane solution containing 5 hmol was added and the temperature was raised to 5,000 °C. Next, AIMg4 (n-C4 day 9) 8 (0n-C3 day 7
) 50' of hebutane containing 35 mhmol was weighed into a dropping funnel and added dropwise over 2 hours at 90 o'clock. As a result, the reaction solution became a white suspension. A white solid was isolated, washed and dried. This white solid and 40% of titanium tetrachloride were charged into a pressure-resistant ampule purged with nitrogen and heated to 130°C.
After contacting under Nada Azusa for 2 hours, the solid component was isolated. As a result of analyzing this solid component, 2. It contained Ti in an amount of 1.5% by weight. Polymerized solid component of Roetylen 20 female and tri-isobutyl aluminum 0.4 m
Polymerization was carried out under the same conditions as in Example 1 except that the polymerization was carried out at 160° C. to obtain polyethylene of 66 mmol. Catalyst efficiency is 114k9/ta Ti, Mi is 4.2, FR3
0, the vinyl group was 0.79 hardness per 100 mm. Comparative Example 2 Polyethylene was polymerized under the same conditions as in Comparative Example 1, except that the polymerization temperature was 19 mm, to obtain polyethylene of 0.7 mm. The catalyst efficiency was 1.3 kg'Ti. Comparative example 31
Synthesis of catalyst component [A] The synthesis of catalyst component [A] was carried out under the same conditions as in Example 1 except that titanium tetrachloride 200 mm and vanadyl trichloride 200 mm were used. At this time, the Mg/(Ti+V) molar ratio was 0.90. Polymerization of Roetylene This catalyst component [A] 5 [Toyama (C2 day 5) 30.4 m
When polymerization was carried out according to the method of Example 1 except that mol was used, only a faint amount of polyethylene was produced.

Claims (1)

[Claims] 1 (i) General formula MαMgβR^1_pR^2_qX^
1 _ r ,0≦
(r+s)/(α+β)≦1.5, m is M
valence, R^1, R^2 are hydrocarbon groups having 1 to 20 carbon atoms which may be the same or different, X^1, X^2 are the same or different groups and are hydrogen atoms, OR^3, OSiR ^4R
Indicates the group ^5R^6, NR^7R^8, SR^9,
R^3 to^9 represent a hydrocarbon group having 1 to 20 carbon atoms, R^4 to R^6 may be a hydrogen atom); an organomagnesium compound soluble in a hydrocarbon solvent; (ii) a reactant of one or a mixture of two or more selected from halides of boron, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, and mercury; (iii) at least one halogen A titanium compound containing atoms has a molar ratio of Mg and Ti of (Mg)/
(Ti) in the range of 3 to 500, and the concentration of Ti is 2 m
Reaction product [A] obtained by contacting under conditions of ol/l or less
and organoaluminum compound [B] at 150°C.
A method for polymerizing α-olefins, characterized by carrying out polymerization in a solution state in one stage or in multiple stages at a higher temperature up to 320°C. 2 In the organomagnesium compound of component (i), M
The method for polymerizing α-olefin according to claim 1, wherein is a lithium, beryllium, boron, aluminum, or zinc atom. 3 Claim 1 in which the ratio β/α is 0.5 to 10
The method for polymerizing an α-olefin according to item 1 or 2. 4. The method for polymerizing an α-olefin according to claim 1, wherein the compound in component (i) is an organomagnesium compound in which α=0 and is soluble in a hydrocarbon solvent. 5 The compound in component (i) is 0.1≦(r+s)/
The method for polymerizing α-olefin according to any one of claims 1 to 4, which is an organomagnesium compound soluble in a hydrocarbon solvent with (α+β)≦1.3. 6 X^1 or X^2 is OR^3 or OSiR^
4R^5R^6, and 0.2≦(r+s)/(α
+β)≦1.0 Claims 1 to 5
The method for polymerizing an α-olefin according to any one of the above items. 7. α- according to any one of claims 1 to 6, wherein the compound in component (ii) is a chloride of boron, silicon, or germanium that is soluble in a hydrocarbon solution.
Method for polymerizing olefins. 8 The compound in component (ii) is SiClaHbR^0
Claims 1 to 7 are silicon compounds represented by _4-(a+b) (wherein R^0 is a hydrocarbon group having 1 to 20 carbon atoms, and a and b are numbers of 1 or more) The method for polymerizing an α-olefin according to any one of the above. 9. The method for polymerizing α-olefin according to any one of claims 1 to 8, wherein the compound in component (iii) is a titanium compound containing at least one chlorine atom. 10. The method for polymerizing α-olefin according to claim 9, wherein the compound in component (iii) is titanium tetrachloride. 11 The reaction between component (i) compound and (ii) compound is 0
Component (i) per mol of component (i) at a temperature of ℃ to 150℃
The method for polymerizing α-olefin according to any one of claims 1 to 10, wherein ii) is carried out in an amount in the range of 0.01 to 100 mol. 12 In contacting the reaction product of the compound of component (i) and the compound of (ii) with the compound of component (iii), the temperature is -
30-150°C, (Mg)/(Ti) molar ratio 3-50
The method for polymerizing α-olefin according to any one of claims 1 to 11, wherein the α-olefin polymerization method is carried out in a range of 0. 13 In contacting the compound of component (iii) with the reaction product of the compound of component (i) and the compound of component (ii), (Mg)
13. The method for polymerizing α-olefin according to claim 12, which is carried out at a molar ratio of /(Ti) in the range of 5 to 200. 14 In contacting the compound of component (iii) with the reaction product of the compound of component (i) and the compound of component (ii), the temperature is 0°C to 95°C, and the (Mg)/(Ti) molar ratio is 10 to 1.
14. The method for polymerizing α-olefin according to claim 13, which is carried out within the range of 0.00. 15 In contacting the compound of component (iii) with the reaction product of the compound of component (i) and the compound of component (ii), Ti
The method for polymerizing α-olefin according to any one of claims 1 to 14, which is carried out at a concentration of 2 mol/l or less. 16 Polymerization of ethylene at a temperature range higher than 150°C up to 320°C with an ethylene partial pressure of 1.0 to 25 MPa (
16. The method for polymerizing α-olefins according to any one of claims 1 to 15, wherein the method is carried out using Mpa). 17 Using [A] and [B], and (M+Al)/
The method for polymerizing α-olefin according to any one of claims 1 to 16, wherein the Ti molar ratio is from 3/1 to 1000/1. 18 Any one of claims 1 to 17, in which ethylene is copolymerized using [A] and [B] in the presence of 5 mol or less of α-olefin having 3 or more carbon atoms per 1 mol of ethylene. The method for polymerizing α-olefin described in .