JPS591411B2 - Polymerization method of olefins - Google Patents

Description

[Detailed description of the invention] The present invention relates to the polymerization of alpha-olefins.

More details: Polymerization of ethylene and ethylene and general formula C
It relates to copolymerization with α-olefins represented by H2=CHR. Conventionally, various catalysts for producing copolymers of amorphous olefins have been proposed, and so-called Ziegler-type catalysts are particularly effective.

Among the Ziegler type catalysts, organoaluminum compounds and vanadium compounds, especially 3, which are soluble in inert organic solvents,
It is well known that a catalyst comprising a pentavalent vanadium compound has extremely excellent effects. However, although many of such vanadium-containing catalyst systems exhibit extremely high activity at the initial stage of the polymerization reaction, the activity rapidly decreases in a relatively short period of time, and the catalyst efficiency is also low. Various activators have been proposed to improve this low catalyst efficiency. halogenated hydrocarbons, organic azo compounds, quinones,
Examples include sulfonyl chloride. Alkyl esters of trichloroacetic acid and tribromoacetic acid are also known. (Japanese Patent Publication No. 43-13052) In the method of the present invention, a conventionally known catalyst consisting of an organoaluminum compound and a trivalent to pentavalent vanadium compound soluble in an inert organic solvent is added to a catalyst having the general formula CX3-C-0. -R' (wherein, X is a halogen, and R' is a group having a chain or cyclic ether bond.

An improvement in catalyst efficiency is achieved by using a catalyst formed by adding a halogen compound represented by ) as a novel activator. That is, by using the novel activator of the present invention, the catalytic activity is greatly improved, making it possible to significantly reduce the amount of vanadium compound used per weight of polymer. According to the method of the present invention, it is possible to efficiently polymerize ethylene, and furthermore, it is possible to polymerize ethylene and α-olefins represented by the general formula CH2═CHR (where R is a straight-chain alkyl group or a branched alkyl group).

), and ternary or multi-component copolymerizations containing one or more linear or cyclic diene or polyene monomers having non-conjugated double bonds can be carried out effectively. The organoaluminum compound used in the present invention has the general formula R″AAtX3-a (where R/′ has 1 carbon number
~20 hydrocarbon groups, X is a halogen or alkoxy group, and a is a positive number satisfying 1≦a≦3.

), and trialkyl aluminum, dialkyl aluminum monohalide, dialkyl aluminum monoalkoxide, alkyl aluminum sesquihalide, and alkyl aluminum dihalide are effective, and these are used alone or in combination. Specific examples of these compounds include triethylaluminum, triisopropylaluminium, triisobutylaluminum, trihexylaluminum, diethylaluminium chloride, diethylaluminum bromide, diethylaluminum ethoxide, diisobutylaluminum chloride, diisobutylaluminum bromide, diisobutylaluminum butoxide. side, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, ethylaluminum dichloride, ethylaluminum dibromide, isobutylaluminum dichloride, isobutylaluminum dibromide, and the like. As the vanadium compound used in the present invention, a trivalent to pentavalent vanadium compound that is soluble in an inert organic solvent is used.

As the vanadium compound, vanadium halides, oxyhalides, chelate complexes with oxygen-containing compounds, vanadate esters, and the like are preferable. Specific examples of these compounds include vanadium tetrachloride, vanadium oxytrichloride, vanadium trisacetylacetonate, vanadate triethoxide, vanadate ethoxy monochloride, vanadate ethoxy dichloride, vanadate tributoxide, and vanadate butoxy monochloride. vanadate butoxydichloride, and the like.

The novel activator used in the present invention has the general formula CX3-C
-0-R' (where X is halogen, preferably chlorine or bromine).

R' is a group having a chain or cyclic ether bond. ) In the case of a chain ether, R' is further R1-R2
(where R is an alkylene oxide group or polyalkylene oxide group represented by -FCHY-CH2-0 or +(CH2-+mα), and R2 is a linear or branched alkyl group, phenyl group, or benzyl group. However, Y is hydrogen or an alkyl group, n is 1 to 5,
m is 1-10, and k is an integer of 1-5. ) Specific compounds of the activator include trichloroacetic acid and tribromoacetic acid methyl cellosolve ester, ethyl cellosolve ester, propyl cellosolve ester isopropyl cellosolve ester butyl cellosolve ester, phenyl cellosolve ester, benzyl cellosolve ester, methyl carbitol ester, ethyl carbitol ester , propyl carbitol ester, butyl carbitol ester, propylene glycol monoethyl ether ester, propylene glycol monobutyl ether ester, propylene glycol monomethyl ether ester 1-butoxy-1-2-propanol ester, ester with glycidol, ester with furfuryl alcohol, Examples include esters with tetrahydrofurfuryl alcohol, and further, esters with polyethylene glycol monoalkyl ether and esters with polypropylene glycol monoalkyl ether can also be used.

The non-conjugated diene or polyene components used in carrying out the ternary copolymerization using the catalyst system according to the invention include 1,4-hexadiene, 1,6-octadiene, 6-methyl-1,5 -heptadiene, 1,9-octadecadiene, cyclopentadiene 1,4, cycloheptadiene 1,4, synclopentadiene, 5-methylene-
2-norbornene, 5-isopropenyl-2-norbornene, 2-methyl-2,5-norbornadiene, 5-ethylidene-2-norbornene, cyclooctadiene 1,
5. Examples include methyltetrahydroindene,
Particularly preferred are 1,4-hexadiene, synchropentadiene, and 5-ethylidene-2-norbornene.

Alkyl esters of trichloroacetic acid and tribromoacetic acid are known (Japanese Patent Publication No. 43-13052) as effective catalyst aids, but their activity decreases markedly in ternary copolymerization containing diene monomers, and they also cause problems during polymerization. This causes problems such as gel formation.

However, by using the novel activator of the present invention, it is possible to achieve extremely high catalytic efficiencies that could not be achieved with alkyl esters of trichloroacetic acid and tribromoacetic acid. - No decrease in activity was observed in the ternary copolymerization of olefin-diene. Furthermore, an excellent effect can be obtained in that no gel formation is observed during polymerization. Polymerizations using the catalyst system according to the invention can be carried out using commonly used hydrocarbon or halogenated hydrocarbon solvents, such as hexane, heptane, kerosene, cyclohexane, benzene, chloroform, trichloroethylene, tetrachloroethane, perchloroethylene, etc. The polymerization is carried out using solution polymerization.

Suspension polymerization can also be carried out using a solvent that does not dissolve the copolymer, such as 1,2 dichloroethane or methylene chloride. Furthermore, polymerization can also be carried out in the presence of only monomers and catalyst components without using a solvent. In the present invention, the activator can be added by any method, but it can be added alone, or it can be mixed with a catalyst component before the start of polymerization. They may be added all at once, or may be added continuously or in portions during the polymerization period.

Polymerization temperature can vary over a wide range, but is typically -50°C
It is carried out at a temperature of -100°C, particularly preferably in the range of -30°C to 80°C. Polymerization is carried out at atmospheric pressure or under pressure.
It is preferable to carry out at ~50k9/Cni, especially 1 to 3
Preferably it is between 0k9/Cd. In carrying out the process of the invention, the amount of activator can be varied within a wide range, but must be kept within a range that does not exceed the number of moles of organoaluminum compound.

That is, the activator is used in an amount of 0.005 to 0.8 mol, preferably 0.01 to 0.8 mol, per 1 mol of the organoaluminum compound.
It is in the range of 5 moles. In addition, the ratio of the activator to the vanadium compound is 0.1 mol to 100 mol to 1 mol of vanadium.
It is preferably between 1 mol and 30 mol, particularly preferably between 1 mol and 30 mol. The ratio of organic aluminum to vanadium compound is 100
Ratios as high as 0:1 can be achieved, but typically 5:1
A ratio between 100:1 and 100:1 is preferred. By producing a copolymer of ethylene and α-olefin using the catalyst system according to the invention, it has become possible to vary the composition of the copolymer over a wide range. When copolymerizing ethylene and α-olefins in a normal solvent in which the copolymer is soluble, the copolymer with an ethylene content of more than 75% will not dissolve in the solvent. gives a non-uniform polymer solution, but
If the catalyst system according to the present invention is used, the ethylene content can be reduced to ゜75%.
Even in the above range, it has become possible to produce a uniform polymer dissolved in a solvent. A copolymer of ethylene and α-olefin having a high ethylene content of 90 mol% can be easily polymerized by solution polymerization. In the present invention, a binary copolymer of ethylene and α-olefin and ethylene, α-olefin
In producing a multicomponent copolymer with an olefin and a polyene compound, a commonly used molecular weight regulator can be used to obtain a copolymer with an arbitrary molecular weight.

That is, diethylanine, aryl chloride, pyridine-N-oxide, hydrogen and the like are often used as molecular weight regulators, with hydrogen being particularly preferred. In addition, the active material used in the present invention
Since the annotating agent also has a molecular weight control effect, is it a normal molecular weight system? It has the advantage that only a small amount of agent can be used. The amount of molecular weight control to be used can be easily selected by those skilled in the art depending on the purpose. EXAMPLES The content of the present invention will be specifically explained below using Examples, but the present invention is not limited thereto in any way.

Comparative example 1 This is an example in which no activator is used.

A 2-t separable flask was equipped with a stirrer, a thermometer, a dropping load, and a reflux condenser, and after reducing the pressure, the flask was purged with nitrogen.

One ton of dry n-hexane is placed in this flask, kept at a constant temperature of 30° C., and a mixed gas of 40 mol % ethylene and 60 mol % propylene is passed through the flask at a rate of 10 Nt/min for 30 minutes to saturate the flask. Next, 4 mm01 of ethylaluminum sesquichloride was added, and further 0.2 mm01 of vanadium oxytrichloride was added to initiate polymerization. Further, a mixed gas of ethylene and propylene was continued to flow for 30 minutes while stirring to carry out polymerization. Next, 30 ml of methanol was added to stop the reaction, and after thorough washing with methanol, the reaction mixture was poured into a large amount of methanol to precipitate a copolymer. The precipitate was dried to obtain 13.87 white amorphous solid copolymer. The intrinsic viscosity of this polymer is 2
, 12dt/7 (in xylene, 70°C), and the propylene content of the copolymer determined from infrared absorption spectrum is 4.
It was 1.8%. Example 1 The same apparatus as in Comparative Example 1 was used.

As an activator, 0.8 mm of ester of tritaloacetic acid and ethyl cellosolve was added to 0.8 mm of vanadium oxytrichloride.
Polymerization was carried out in addition to 2 mm01. Thus 64.17
A white amorphous solid copolymer was obtained. This is 4.65 times more catalytic efficiency than in the absence of activator. The intrinsic viscosity of this polymer was 1.96 dt/7 and the propylene content was 39.4%. Comparative Example 2 This is an example using an alkyl ester of trichloroacetic acid.

It was carried out in the same manner as in Example 1. just ! Then, in place of the ester of trichloroacetic acid and ethylene glycol monoethyl ether, 0.8 mm01 of methyl trichloroacetic acid was used.
used. In this case, only 39.27 g of a white amorphous solid copolymer was obtained. The intrinsic viscosity of this polymer is 1
．． At 99 dt/7, the propylene content was 36.2%. Example 2 The same procedure as in Example 1 was carried out.

However, 8 mm01 of ethylidene norbornene was placed in advance in the polymerization flask. Thus 60.47
A white amorphous solid copolymer was obtained. The intrinsic viscosity of this polymer is 1.89 dt/7, and the propylene content is 37.9%.
, the iodine number was 1.9. Example 3 The same procedure as in Example 2 was carried out.

However, synchropentadiene was used instead of ethylidene norbornene. In this case, a white amorphous solid copolymer of 61.2y was obtained. The intrinsic viscosity of this polymer was 1.93 dt/t1 with a propylene content of 38.6% and an iodine number of 2.1. Examples 4 to 13 The same procedure as in Example 1 was carried out.

However, experiments were carried out by changing the activator, organoaluminium, and vanadium compound. The results are shown in Table 1. Nodochloroethylene was used in place of hexane, and butene-1 was used in place of propylene.

Further, hydrogen was bubbled through the reactor at a rate of 2 Nt/min as a molecular weight control agent. In this way, a white amorphous solid copolymer of 51.4f was obtained. This polymer had an intrinsic viscosity of 1.68 dt/f1 and a butene-1 content of 37.6%. Comparative Example 3 This is an example in which ethylene was polymerized without using an activator.

It was carried out in the same manner as in Comparative Example 1.

However, instead of the mixed gas of ethylene and propylene, ethylene was flowed at a rate of 8 Nt/min. In this way, white powdery polyethylene was obtained, but the yield was only 25 f. Example 15 The same procedure as in Comparative Example 3 was carried out.

However, 0.8 mm01 of methyl cellosolve ester of trichloroacetic acid was added together with the vanadium compound as an activator. In this way, white powdered polyethylene 118f
I got it. Example 16 The same procedure as in Example 2 was carried out.

However, an ester of trichloroacetic acid and isopropyl cellosolve was used as an activator, and 30 mm01 of ethylidene norbornene was placed in advance in the polymerization flask. In this way, a white amorphous solid copolymer of 43.21 was obtained.

The intrinsic viscosity of this polymer was 2.60 dt/y, the propylene content was 31.7%, and the iodine number was 9.4. Example 17 The same procedure as Example 16 was carried out.

Claims (1)

[Claims] 1. Polymerization of ethylene and ethylene with the general formula CH_2=
Copolymerization with α-olefins represented by CHR (where R is a straight-chain alkyl group or a branched alkyl group), or copolymerization with one or more straight-chain or cyclic diene or polyene monomers having non-conjugated double bonds. In order to produce a ternary or multicomponent copolymer containing more than 10% of the above, a) organoaluminum compound, b) vanadium compound, c) general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (here R' is a chain or cyclic a group having an ether bond,
X is halogen. ) A method for polymerizing olefins, characterized by using a catalyst system containing as essential components three components consisting of a novel activator represented by: 2 The organoaluminum compound has the general formula R
A patent for a compound represented by ``_aAlX_3_-_a (where R'' is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen or alkoxy group, and a is a positive number of 1≦a≦3) The method according to claim 1. 3. Claim 2, wherein the organoaluminum compound is a compound selected from the group consisting of diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, ethylaluminum sesquichloride, and isobutylaluminum sesquichloride. the method of. 4 3 to 5 in which the vanadium compound is soluble in an inert organic solvent
2. The method according to claim 1, wherein the vanadium compound is a valent vanadium compound. 5. The method according to claim 4, wherein the vanadium compound is a compound selected from the group consisting of vanadium halides, oxyhalides, chelate complexes with oxygen-containing compounds, and vanadate esters. 6 Vanadium compounds include vanadium tetrachloride, vanadium oxytrichloride, vanadium trisacetylacetonate, vanadate triethoxide, vanadate ethoxy monochloride, vanadate ethoxy dichloride, vanadate tributoxide, vanadate butoxychloride, and vanadate The method according to claim 5, wherein the compound is selected from the group consisting of butoxydichloride. 7 R' of the activator is a chain ether (where R'
is represented by R_1-R_2, R_1 is an alkylene oxide group or a polyalkylene oxide group, and R_2 is a linear or branched alkyl, phenyl or benzyl group. 8. The method according to claim 1, wherein X in the activator is chlorine or bromine. 9 R_1 is represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n is 1.
~5, m is 1 to 10, k is an integer of 1 to 5, and Y is hydrogen or an alkyl group. 10 The activator is trichloroacetic acid and tribromoacetic acid methyl cellosolve ester, ethyl cellosolve ester, propyl cellosolve ester, isopropyl cellosolve ester, butyl cellosolve ester, phenyl cellosolve ester, methyl carbitol ester, ethyl carbitol ester, butyl carbitol ester, propylene glycol monoethyl ether ester,
Propylene glycol monobutyl ether ester, propylene glycol monomethyl ether ester, 1-
The method according to claim 1, wherein the compound is selected from the group consisting of butoxy-2-propanol ester, furfuryl alcohol ester, tetrahydrofurfuryl alcohol ester, and glycidol ester. 11 α-olefins include propylene, 1-butene, 1
2. The method according to claim 1, wherein the compound is a compound selected from the group consisting of -pentene, 1-hexene and 4-methyl-1-pentene. 12. The method according to claim 1, wherein the α-olefin is propylene. 13 The nonconjugated diene monomers include 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-
The method according to claim 1, wherein the compound is selected from the group consisting of norbornene. 14 The molar ratio of activator and vanadium compound is 0.1
:1 to 100:1, the molar ratio of the organoaluminum compound to the activator is 1:0.005 to 1:0.8, and the molar ratio of the organoaluminum compound to the vanadium compound is 10.
The method according to claim 1, wherein the ratio is 00:1 to 3:1. 15 The molar ratio of activator and vanadium compound is 1:1
~30:1, the molar ratio of organoaluminum compound to activator is 1:0.01 to 1:0.5, and the molar ratio of organoaluminum compound to vanadium compound is 5:1 to 100.
:1. 16. The method according to claim 1, wherein a hydrocarbon or halogenated hydrocarbon solvent is used as an inert organic solvent to dissolve the copolymer in producing the copolymer. 17. The method according to claim 16, wherein the inert organic solvent is a compound selected from the group consisting of hexane, heptane, kerosene, cyclohexane, benzene, chloroform, trichloroethylene, tetrachloroethane, and perchlorethylene. 18. The method according to claim 1, in which the copolymer is produced by suspension polymerization using an inert solvent that does not dissolve the copolymer. 19. The method according to claim 18, wherein the inert solvent is 1,2-dichloroethane or methylene chloride.