JPH03152105A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a polyolefin having narrow distribution of molecular weight because of high activity of catalyst and good durability of catalytic activity by polymerizing an olefin in the presence of a new rare earth catalyst. CONSTITUTION:An olefin expressed by the formula CH2=CH-R (R is H or 1-8C hydrocarbon residue) is polymerized in the presence of a rare earth catalyst to which substituent group having a condensed ring cyclopentadienyl and cyclopentadienyl based substituent groups is bonded through hydrocarbon or Si atom, having substituent group selected from H, alkyl and aryl and consisting of a compound having trivalent metal atom composed of a metal of lanthanoids having 57-71 atomic number of the Periodic table. Furthermore, the above- mentioned catalyst is e.g. obtained by subjecting ethylene bis(indenyl)dilithium to catalytic reaction with bistrimethylsilylmethyllithium and lutetium trichloride.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for producing polyolefins using a novel olefin polymerization catalyst. According to the method of the present invention, a polyolefin with high activity, long-lasting activity, and relatively narrow molecular weight distribution can be produced.

Previously, Zlegler-N was used as an olefin polymerization catalyst.
The Otta catalyst is generally widely known. In addition, research has long been conducted on olefin polymerization reactions using catalysts with rare earth elements as the central metal, but the activity was low (British Patent No. 865.248, French Patent No. 1).
, 323. O (No. 1 specification.

(U.S. Patent No. 3,111,511, etc.).

In recent years, it has been reported that rare earth metal complexes containing pentamethylcyclopentadiene as a ligand have high activity as olefin O polymerization catalysts (J, Amer, Che.
m, Soc, 10), 8(11 (198B) Ace,
Chem, Res, 18.51 (198B), C
hem.

Lett, 1963 (198g), etc.). However, in terms of activity persistence and molecular weight controllability, industrial use is difficult.
Fi is still insufficient.

Physician 11 In order to solve the above-mentioned problems, the present invention has developed a polyolefin with high activity and long-lasting activity, as a result of studies on substituents (ligands) that coordinate and/or bond to rare earth metals. The present invention was completed based on the discovery that it is possible to produce the following.

That is, the present invention provides the following A% B and C constituent elements, A: At least one is a condensed cyclopentadienyl group bonded via a hydrocarbon or silicon atom, and the other is a cyclopentadienyl group. B: has a substituent selected from a hydrogen atom, an alkyl group, and an aryl group; C: 3 selected from lanthanide series metals with atomic numbers 57 to 71 in the periodic table; In the presence of a rare earth catalyst consisting of a compound having a valent metal atom, - general formula 1. = CI-R (where k represents a hydrogen atom or a hydrocarbon residue having 1 to 50 carbon atoms).

Furthermore, in the present invention, in the presence of a reaction product obtained by contacting a contact product of component a and component C with the following components, An object of the present invention is to provide a method for producing a polyolefin, which is characterized by polymerizing an olefin represented by a hydrocarbon residue having 1 to 50 carbon atoms.

Component a: A compound having at least a divalent substituent, one of which is a condensed cyclopentadienyl group and the other is a cyclopentadienyl substituent, bonded via a hydrocarbon or silicon atom. Component B: an alkali metal or alkaline earth metal compound having a substituent selected from an alkyl group and an aryl group, Component C: a lanthanide series having an atomic number of 57 to 71 in the periodic table A trivalent metal halide selected from the following metals.

m and wo! According to the method of the present invention, by using a novel rare earth gold catalyst having a specific substituent (ligand), it is possible to perform polymerization with high activity and excellent activity sustainability, and to produce polyolefins with a narrow molecular weight distribution. can.

Further, since an aliphatic hydrocarbon can be used as a solvent during polymerization, it is possible to produce the easily soluble low molecular weight polyolefin O by-product while reducing the amount.

[Catalyst] The catalyst used in the method of the present invention is a rare earth catalyst consisting of a compound having the constituent elements B and C.

The constituent elements are substituents bonded via hydrocarbon or silicon atoms, at least one of which is a condensed cyclopentadienyl substituent, and the other is a cyclopentadienyl substituent. , Here, the condensed cyclopentadienyl system is a group (ligand) in which adjacent substituents on one ring of the ν-clopentadienyl group are bonded to each other to form a ring structure.
means.

Specifically, indenyl, phenanthryl group, fluorenyl group, bicyclo(3,3,0)octa-1,3-! ＞
enyl group, 4.5.6.7-titrahydroindenyl group, bicyclo(S,S,O)deca-8゜11-genyl group, tricyclo(s, t, t, a) deca-2,5 −
Genyl groups and their alkyl, alkylsilyl or alkylgermyl substituted products can be exemplified. Among them, indenyl group, fluorenyl group,
It is a group having a 4,5.6.7-titrahydroindenyl skeleton.

The other substituent has a cyclopentadienyl group, such as a cyclopentadienyl group, an indenyl group, a phenanthryl group, a fluorenyl group, a bicyclo(3,3,0)octa-1,3-genyl group, 4, 5.6.7-titrahydroindenyl group, bicyclo(5,3,0)deca-8,
11-t phenyl group, tricyclo(s, 2.1.6'
°6]Deca-L5-yenyl group and their alkyl A/4< are exemplified by alkylsilyl or alkylgermyl substituted products.

Among them, cyclopentadienyl group, indenyl group, fluorenyl group, 4.5. Ei,? -TeF
It is a tomb with a lahydroindenyl skeleton.

K, which binds the above-mentioned substituent at least one of which has a condensed cyclopentadienyl group and the other of which has a cyclopentadienyl substituent, is a hydrocarbon or a silicon atom. Specifically, examples include an alkylene group having a main chain of 1 to 4 carbon atoms, an alkyl- or aryl-substituted alkylene group having a main chain of 1 to 4 carbon atoms, and a dialkyl-substituted silicon group.

Among these, preferred are methylene group, ethylene group, propylene group, and dimethyl Vlyl group.

Component B is hydrogen having a substituent selected from a hydrogen atom, an alkyl group and an aryl group.

As the alkyl group, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 50 carbon atoms, or an alkyl group (having 1 to 12 carbon atoms)
8) The alkyl group having a substituted silicon group is exemplified by an aryl group having 6 to 18 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms, or an aryl group having an alkyl (1 to 8 carbon atoms) substituted silicon. Ru.

Among these, having a sterically bulky substituent, such as an alkyl group or an ortho-substituted aryl group, preferably having a plurality of alkyl groups having 1 to 50 carbon atoms or alkyl substituted groups having 1 to 50 carbon atoms at the position, Furthermore, those having a structure in which monohydrogen or alkyl elimination is difficult to occur, such as a trialkyl-substituted methyl group, an ortho-substituted aryl group, etc. are preferable.

Preferred examples of such groups include bistrimedelsilylmethyl group and mesityl group.

Component C has a trivalent metal atom selected from metals in the lanthanide series with atomic numbers 57 to 710 in the periodic table. Among these, lanthanum, neodymium, gadolinium, dyspro-Vium, and lutetium are preferred.

A catalyst having components A, B and C described above can be intercalated with components a, b and C below with their respective components.

A component having a component is a divalent substituent bonded via a hydrocarbon or silicon atom, at least one of which is a condensed cyclopentadienyl group and the other is a cyclopentadienyl substituent. It is an alkali metal salt or alkaline earth metal salt of a compound having the following. Among the alkali metals, tsutecum, sodium, etc. are preferably used, and among the alkaline earth metals, magne νcum, etc. are preferably used.

More specifically, component a is a compound represented by the general formula %. Here, Q is an alkylene group having 1 to 4 carbon atoms in the main chain, an alkyl or aryl substituted alkylene group having 1 to 4 carbon atoms in the main chain, or a dialkyl or aryl substituted silicon group; The substituent 1Cp d fused diclopentadienyl At-1M1 and M independently represent an alkali metal, and %L< represents an alkaline earth metal, respectively. In addition, when the pigeon or tow is an alkali earth metal, it is necessary that one halogen or alkyl group is bonded thereto.

Specific examples include ethylenebis(indenyl)dilithium, ethylenebis(indenyl)disodium, ethylenebis(indenyl>p potassium, ethylenebis(indenyl)dimagne V cumchloride, ethylenebis(indenyl)dimagneV cumpromide, methylenebis(indenyl) Sirichiku A, 1.s-propylenebis(indenyl)sili?A, L 2-j Robylenebis(indenyl)dilithium, ethylenebis(4,S,6.7-titrahydroindenyl)dilithium, ethylenebis(fluorenyl) Examples include dilithium, 2,2-propylene (cyclopentadienyl, fluorenyl) dilithium, and the like.

The component with component B is an alkali metal or alkaline earth metal compound having substituents selected from alkyl groups and aryl groups.

Specific examples of the components include methyllithium, methylpotassium, methylsodium, methylmagnesium bromide, methylmagnesium bromide, methylmagne V kumuiodishi, ethyllithium, diethermagnereum, n-
Butyl lithium, K-butyl lithium, t@rt-butyl lithium, isoprenyl lithium, neopentyl lithium, di-tart-butyl methyl 9? um, phenyl9f cum, 0->lylphenyllithium, 2,6-dimethylphenyllithium, methylpotassium, O-ethylphenyllithium, O″″tart″tart butylphenyllithium terv sulfenyllithium, penzyllithium, Examples include neofillithium, trimethylvralmethyltecum, and bistrimethylsilylme?A/9fcum.

Among these, preferred are alkali metal or alkaline earth metal salts of a methyl group (such as bistrimethylsilylmethyllithium) substituted with a realkyl silio group, or an ortho-substituted aryl group (such as methylpotassium).

Component C with component C has an atomic number of 57 to 57 on the periodic table.
It is a trivalent metal halide far from the 710 rank nide series metals.

Preferred specific examples of component C include lanthanum trichloride, neodymium trichloride, gadolicium trichloride, dysprosium trichloride, lutetium trichloride, and the like.

The catalyst used in the present invention can be synthesized by applying known techniques. For example, preferably, the compound of component a is mixed with the compound of component C in the presence of an ether organic solvent such as tetrahydrofuran (THF), diethyl ether, or dimethoxyethane (5 to 1,600 times the weight ratio of the organic solvent to component CK). were contacted at a temperature range of -***-200°C in a ratio (molar ratio) of component i: acid component: O, S: 1 to x, zs: 1, and the resulting contact product was further mixed with components. obtained by reacting The solvent used in this reaction is, for example, an aliphatic hydrocarbon such as pentane, hexano, or heptane, an alicyclic hydrocarbon such as cyclohexane, an aromatic hydrocarbon solvent such as toluene, or the above-mentioned ether organic solvent (component). The amount of component C to be used is 5 to
At a ratio of ~2, the reaction temperature is -■O~200c.

In the production of the above catalyst, when an alkali metal or alkaline earth metal compound having an alkyl group or an aryl group is used as a component, hydrogen gas can be used simultaneously or after the reaction of the component.

The above-mentioned catalyst used in the present invention can be used for polymerization as the reaction product ott alone, but it can also be used when supported on a suitable support. As the support used in this case, inorganic carriers such as silica gel, alumina, zeolite, magnesium chloride, and magnesium oxide, and inorganic carriers such as polyethylene particles and polypropylene particles can be used.

〔polymerization〕

The olefin compound polymerized using the rare earth catalyst of the present invention is an olefin compound having a triple viscosity at the terminal represented by the general formula CB, =α-. Here, or a hydrogen atom or a hydrocarbon residue having 1 to 50 carbon atoms, examples thereof include ethylene, propylene, 1-butene, 3-methylbutene-1゜1-hexene, 4-methylpentene-
1,1-octene, 1-decene, styrene, butadiene, isoptzy, 1,! i-hekif t7:cV,
'l-1fAI4. Examples include '1-octadiene. These seven polymers can be used not only for homopolymerization but also for copolymerization.

Polymerization can be carried out in a gas phase, in a liquid phase, or by any other known method. When using a solvent, it is preferable to use an inert organic solvent, such as aromatic hydrocarbon solvents such as pen, toluene, xylene, a-pentane, n-hextin, n-hexyl, etc.
- aliphatic hydrocarbon solvents such as hebutane, n-paraffin, etc.
One of the features of the present invention, which can use alicyclic hydrocarbon solvents such as ν chlorhequitine and methylcyclopentane, is that it is effective even with aliphatic hydrocarbon solvents.

Polymerization temperature is -20 to 260°C, preferably 40 to 2
It is carried out at 00°C.

A molecular weight regulator can be used during polymerization. Hydrogen is effective as a molecular weight regulator. In addition, since hydrogen brings about the effect of improving catalyst activity, it is preferable that hydrogen be present in the polymerization system.

The polymerization pressure is appropriately selected in the range of normal pressure to 30 (10 kl/al G) according to a known process.

u11 Example-1 (Production of catalyst) 300 sIj flask Fcl with stirring blade material sufficiently purged with nitrogen, diindenyl ethane 8 mmol and purified TH
FI! O+d was added, the mixture was cooled to -18°C, and 1 G of a 1.6M hequinane solution of -1-butylridium and 1 S sea bream were added dropwise. The temperature was raised to room temperature and the reaction was continued for 8 hours.

To this, 2,251 grams of anhydrous lutetium chloride was gradually added at 0°C, and the mixture was refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to 10 CK and the solvent was distilled off under reduced pressure. Purified diethyl ether 1001114m was added thereto, and after stirring, the mixture was cooled to KIO°C and the solvent was distilled off under reduced pressure. This operation was repeated twice.

10 parts of purified toluene was added to the obtained product, and at 0°C, 14.3 parts of a 55 mM diethyl ether solution of bistrimethylsilylmethyllithium was added, and the mixture was allowed to react for 8 hours.

The reaction product was filtered under a nitrogen atmosphere, and the solvent was distilled off from the P solution under reduced pressure at 10°C.

The product was recrystallized.

The rare earth catalyst was diluted with purified toluene to give
6 'ff1m0j -Lm/sd -) At en 0
It was used for polymerization as a catalyst solution.

(Polymerization) 300 wan of butane was introduced into a purification autoclave equipped with a stirring blade that was sufficiently purged with nitrogen, and then the above catalyst solution (z, smBo, Then, ethylene was further introduced, the pressure in the polymerization tank was maintained at s#/ajGK, and polymerization was carried out in SOc for 3 hours.

As a result, 51. ig polyethylene was obtained. The molecular weight of the product is Ma 14sX10, hMw5゜14X
10', Q value was 2.09), and IR revealed that this polyethylene had no terminal double bond.

In addition, the ethylene absorption rate during polymerization is 0,
2111/OJS showed good activity persistence, with an OJS of 0.311/min in the second hour and 17 minutes in the third hour.

Example-2 (Polymerization) Purified toluene 30081 was introduced into a crepe similar to Example-1, which was sufficiently purged with nitrogen, and then the catalyst solution 5-(0.1Bmm5A) used in Example-1 was introduced. Add hydrogen @OO+d, propylene 7, Sg, and then introduce ethylene, and set the polymerization tank pressure to 611/al G.
Polymerization was carried out at 60° C. for 6 hours.

As a result, a polymer of 7B, Of was obtained. The bulk density of the produced polymer is 0.49. The molecular weight of the product is Ma3.13X10', Mwll, 44X10', Q
The value was 8.07.

In addition, the ethylene absorption rate during polymerization is (1
, 161/min, 4th hour is 0. ! ? fi/min was 0.321/min at the 6th hour, indicating good activity persistence9.

Example-3 (Polymerization) In Example-2, propylene was converted into 1-hexene xsv
Polymerization was carried out in the same manner as in Example 2, except that the polymerization time was 3 hours and the earthquake occurred.

That's the result! 8.92 polymers were obtained. The molecular weight of the product is MgI2, 88 x 10', Mn9.8
1X10', Q value is! , Of de Atsuku.

Furthermore, the progress of ethylene absorption during polymerization was 0.0% in the first hour.
15ji/min, 2jM 0.221/fl, 3rd hour 0, 2817 min, showing good activity persistence.

Example-4 (Polymerization) In Example-3, 1-hexene was converted into isoprene IQ
Polymerization was carried out in the same manner as in Example 3 except for mA and 9.

As a result, 24.210 polymer was obtained. The molecular weight of the product is Mn, 3.50 x 1G%Mu8
, 3SX10', Q value is 2.39, 6 times 9.

Nine, the progress of ethylene absorption during polymerization is 0.0 in the first hour.
At 1814/', the second special was 0.19, and the first hour was 0.2! A/* indicates good persistence of activity.

Example 5 (Polymerization) An autoclave equipped with an anchor-type stirring blade and having a capacity of 1.5 mm was thoroughly dried and replaced with nitrogen. After thorough drying, trimethylaluminum treatment, heptane washing, and further
9. Filled with 70 tons of polyethylene powder with an average particle size of 840μ to be dried under reduced pressure, then added 2.51 (0.16 mmojL) of the catalyst solution prepared in Example-1, and added 18,001 tons of hydrogen to this. Then, ethylene was introduced, the pressure in the polymerization tank was maintained at 8-GK, and polymerization was carried out at 60° C. for 3 hours.

As a result, the weight of the polymer increased by 14. Of″′cT.

Nineteen. The molecular weight is M! by subtracting the polyethylene of 9 PET used at the beginning from GPC. 13. It was estimated to be about 1×10'.

Example-6 (Polymerization) 5 oosn of purified toluene was introduced into the autoclave which was used in Example-1 after fully replacing the IC1i, and the mixture was prepared in Example-1.
The catalyst solution sm (0.32 mmoj) used in 9 was added, 600 ml of hydrogen and propylene were introduced, and polymerization was carried out at 60° C. under a pressure of 61 G for 3 hours.

After the polymerization is completed, the solvent is distilled off and 1. A polymer of Of was obtained. IR, GPC, and attack potsupropylene with a molecular weight of about 100 ml.

Example 7 (Manufacture of catalyst) 2-(cyclopentadienyl)-2-fluorenylpropane, s, Osl1ld and purified TI were placed in a flask of stirring blade material soz,i which had been sufficiently purged with nitrogen. (
Add F100 and cool to -78°C, and add n-butyl 9? 1.6M hetinane solution 6. Dropped 1 drop of S tank and it was good. 9. Raise the temperature to room temperature and react for 6 hours.

To this, 1.40 [) anhydrous lutetium chloride was gradually added at 0°C, and the mixture was refluxed for 8 hours.

After the reaction is completed, the solvent is distilled off under reduced pressure at a temperature of 10°C or less.

To this, 100 parts of purified diethyl ether and 1 part of sea bream were added and stirred. After death, the solvent was distilled off under reduced pressure again at a temperature of 10°C or less. This was repeated twice.

Add 100 parts of purified toluene to the obtained product and heat to 0'C.
K, bisF trimethyl ν trimethyl lithium, 11m
9 ml of 5% M diethyl ether solution was added and reacted for 8 hours.

After the solvent of the reaction product was distilled off under reduced pressure at a temperature of 10° C. or lower, the residue was extracted with toluene and subjected to nitrogen atmosphere KF.

The obtained product has O, OX 1mmoA-Lm/mA
- It was a catalyst solution in toluene.

(Polymerization) After sufficiently purging the same IA autoclave as used in Example-1 with nitrogen, purified cyclohexine so 01
Then, under a nitrogen atmosphere, add the catalyst solution obtained above and 5sd (0,0!S5mmo), introduce hydrogen 1800s+s,i, and ethylene, and adjust the polymerization tank pressure to II klAd G. 9. Polymerize at 60°C for 3 hours.

As a result, 4,5t1triboethylene was obtained, and the molecular weight of the product was MmLIIX10', Mn4. i! X10
', the 9 value was 2.07.

Example-8 (Manufacture of catalyst) In the same manner as in Example-7, stirrer 11 and 3 were sufficiently purged with nitrogen.
Put 4.9 mm of bis(indenyl)dimethylsilane and 100 mA of purified THF into a 0 omA flask.
The mixture was cooled to −78° C., and a chitin solution (6.21 μl) was added dropwise to 1.6 M of n-°butyllithium.

The temperature was raised to room temperature and the reaction was carried out for 4 hours.

To this, 1.23 fO anhydrous neodymium chloride was gradually added at room temperature, and the mixture was refluxed for 6 hours.

After the reaction was completed, the solvent was distilled off under reduced pressure at a temperature of 10° C. or lower.

Purified diethyl ether 100 steel 1 was added to the mixture, stirred, and then the solvent was distilled off under reduced pressure again at a temperature of 10° C. or lower. I repeated the twist twice.

80 fins of purified toluene was added to the obtained product and heated to 0°C.
Bistrimethylsiwarmethyllithium 0.56mM
Diethyl ether solution 11. lls+sfi was added and reacted for 6 hours.

After the solvent of the reaction product was distilled off under reduced pressure at a temperature of 10° C. or lower, the residue was extracted with toluene and filtered under a nitrogen atmosphere.

The obtained solution was heated at 20°C at 1#/jG under hydrogen atmosphere.
, and stirred for 2 hours.

The concentration of the obtained catalyst solution was 0.017 mmoj −N
d/electron-toluene.

(Polymerization) In the same manner as in Example 7, 300ml of purified toluene was introduced into an IL autoclave which had been sufficiently purged with nitrogen, and then 5ml of the catalyst solution prepared in Example 7 was added under a nitrogen atmosphere.
Then, ethylene was introduced, the polymerization tank pressure was maintained at 6 kl/dG, and the polymerization was carried out at 40°C for 2 hours.

As a result, 0.5 ft of polyethylene was obtained.

The obtained polymer has M! 11.98X10', Mn4
．． 89X1G, Q value was 2.47.

Example-9 (Production of catalyst) In Example-8, 5 m moj! A catalyst was prepared in the same manner as in Example 8, except that the same amount of 1.2 bisindenyl ethane was used instead of 1.2 bisindenyldimethylsilane.

The concentration of the obtained catalyst solution was 0.036 mmon -Nd
Z network was toluene.

(Polymerization) Example 8 was carried out in the same manner as Example 7 except that the catalyst solution prepared above was used as the catalyst and the polymerization time was 1 hour.

As a result, 8.8 tons of polyethylene was obtained.

The obtained polymer had Mn1.76X1G', Mn8.
0OXIO, Q value is 3.40.

Example-10 (Polymerization) Sufficiently dried stirring blade material 1.51 The atmosphere inside the autoclave was replaced with ethylene.
G+) ffil was introduced and 1. Temperature 150'CG'C
Humidity increased. L of ethylene! Introduced in Mal G t,
Further, the catalyst produced in Example-8 was added with 20-11
Polymerization was carried out at 50° C. for 20 minutes after 1-G ethylene pressure.

As a result, polyethylene of 5.6 f was obtained. The molecular weight of the product is Mfi! , 71X1G”, Mn4jSXIO”
, the Q value was 1.57.

Claims (2)

[Claims] (1) Constituent elements of A, B and C below, A: At least one is a condensed cyclopentadienyl group bonded via a hydrocarbon or silicon atom, and the other has a cyclopentadienyl substituent. B: having a substituent selected from a hydrogen atom, an alkyl group, and an aryl group; C: a trivalent metal atom selected from lanthanide series metals with atomic numbers 57 to 71 in the periodic table. in the presence of a rare earth catalyst consisting of a compound having the general formula C
A method for producing a polyolefin, which comprises polymerizing an olefin represented by H_2=CH-R (where R represents a hydrogen atom or a hydrocarbon residue having 1 to 8 carbon atoms). (2) The following component b is added to the contact product of the following component a and component c.
In the presence of a reaction product obtained by contacting
_2=CH-R (where R is a hydrogen atom or a carbon number of 1
1. A method for producing a polyolefin, which comprises polymerizing an olefin represented by 1 to 50 hydrocarbon residues. Component a: Alkali metal of a compound having a divalent substituent, at least one of which is a condensed cyclopentadienyl group and the other is a cyclopentadienyl substituent, bonded via a hydrocarbon or silicon atom. salt or alkaline earth metal salt, component b: an alkali metal or alkaline earth metal compound having a substituent selected from an alkyl group and an aryl group, component c: from a lanthanide series metal having an atomic number of 57 to 71 in the periodic table. Selected trivalent metal halides.