JPS60226514A - Production of ethylenic copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer with a high ethylene content and narrow molecular weight distribution in the state of suppressed formation of insoluble components in a polymer solution, by reacting ethylene with an alpha-olefin in the presence of a specific vanadium compound and organoaluminum compound as a catalyst. CONSTITUTION:Vanadium trichloride described in ASTM 15-382 is reacted with an alcohol, preferably methyl alcohol in a molar amount of 1-20 times that of the vanadium trichloride to give a vanadium compound expressed by formula I (ROH is alcohol; m is 0-1.5; n is 0.5-3.5), which is then mixed with (B) an aluminum compound expressed by formula II (Y is hydrocarbon; X is halogen or alkoxyl; l is 0-2) at 1:1 molar ratio between the components (A) and (B) to form a polymerization catalyst. Ethylene is reacted with an alpha-olefin, e.g. butene- 1, in the presence of the resultant catalyst preferably at -80-+100 deg.C to give the aimed copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an ethylene copolymer by copolymerizing ethylene and α-olefin in the presence of a novel catalyst system consisting of a vanadium compound and an organoaluminum compound. be.

Conventionally, various catalysts for producing ethylene copolymers have been proposed, and so-called Ziegler-type catalysts are particularly effective. Among Ziegler type catalysts, catalysts consisting of octa- to pentavalent vanadium compounds (e.g., vanadium triacetylacetonate, vanadium tetrachloride oxyvanadium trichloride) and organoaluminum compounds that are soluble in the polymerization solvent are particularly excellent. It is well known that it has a positive effect.

In addition, in the presence of Cholera's catalyst, ethylene and α-olefins (e.g. propylene, butene-1) are copolymerized to produce soft plastics (ethylene content 70-95%), ethylene It is also known that elastomers (ethylene content 120 to 70% by weight) are produced by copolymerizing α-olefins and polyenes (for example, Japanese Patent Publication No. 44-9668, Japanese Patent Publication No. 46-1988).
11028, Japanese Patent Publication No. 47-26186).

However, these catalysts have a narrow molecular weight distribution and a compositionally homogeneous copolymer can be obtained at a polymerization temperature of 20°C or lower; copolymer with a high ethylene content (ethylene content of 5
The problem is that the more one attempts to produce a copolymer (0 weight or more), the broader the molecular weight distribution and composition distribution of the copolymer become, making it difficult to obtain a homogeneous copolymer.

It tends to become insoluble in solvents and precipitate during polymerization, giving a heterogeneous polymer solution, which has the disadvantage of causing operational problems such as clogging of polymer solution extraction lines in industrial-scale polymerization equipment. . In addition, for example, in slurry polymerization of soft plastics, low-molecular members and amorphous components dissolve in the polymerization solvent, resulting in blockages in the extraction line due to increased viscosity of the polymer solution, and separation of the solvent from the slurry using a centrifuge, etc. When doing so, there are manufacturing disadvantages such as a decrease in the yield of the copolymer.

In addition, since the composition of the copolymer is heterogeneous, its strength and
It also has drawbacks such as reduced quality such as transparency.

The present inventors have discovered that a new vanadium compound obtained by reacting vanadium trichloride and alcohol is particularly useful for ethylene and α
- A copolymer useful for copolymerization with olefins, which has even higher polymerization activity than vanadium compounds soluble in the polymerization solvent, and which can be used even at polymerization temperatures higher than 20°C, and furthermore has a high ethylene content. (Ethylene content is 60
Even when producing copolymers with a narrow molecular weight distribution and homogeneous composition, the production of components insoluble in the polymerization solvent during solution polymerization is significantly suppressed. Copolymerization is a method of copolymerization because operational problems can be significantly improved, copolymers with higher ethylene content can be easily produced than conventional copolymers, and the formation of components soluble in the polymerization solvent during slurry polymerization is significantly suppressed. We have discovered that the yield of coalescence is significantly improved, and have arrived at the present invention.

That is, the present invention relates to a vanadium compound obtained by reacting vanadium trichloride and an alcohol and a compound having the general formula Y3-1AI.
Ethylene and α-olefin are mixed in the presence of a catalyst system consisting of an organic aluminum compound represented by X/ (where Y is a hydrocarbon group, The present invention relates to a method for producing an ethylene copolymer characterized by copolymerization.

The vanadium trichloride used in the present invention is ASTM16-8
82, the X-ray powder spectrum (i.e. d
-5,75λ, d=2.67JLd-1, r4X, etc.), and also includes VCl3 which shows the spread of the diffraction line in half value.

Alkoxy groups used in the reaction with vanadium trichloride, e.g., methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol% tert-butyl alcohol, hexyl alcohol, octyl alcohol etc., and methyl alcohol, ethyl alcohol, i-propyl alcohol, etc. having a low boiling point are preferably used.

As a method for obtaining the vanadium compound of the present invention, for example, in the absence of a hydrocarbon solvent, vanadium trichloride and alcohol in an amount of 1 to 20 times its mole, preferably 8 to 10 times its mole, are used, and the alcohol is heated at 0°C. A method of obtaining a tar-like or liquid vanadium compound by carrying out the reaction at a temperature between the boiling point of 9 or vanadium trichloride in the absence of a hydrocarbon solvent and 1 to 40 times the mole of vanadium trichloride, preferably 8 to
A reaction was carried out in the same manner as in Synthesis Method A using 20 times the mole of alcohol, an inert hydrocarbon solvent such as n-hebutane was added, and the mixture was dried under reduced pressure with stirring to obtain the general formula V(OR)mC13-
m・nROH (here ROM is alcohol, m is Ojm
jl, 5, n is a number expressed as 0.55n58.5) A method for obtaining a solid powdery complex compound insoluble in an inert hydrocarbon solvent (hereinafter abbreviated as synthesis method B), or an inert hydrocarbon In the presence of a solvent, vanadium trichloride is catalytically reacted with 1 to 50 times the mole of alcohol, preferably 8 to 80 times the mole of vanadium trichloride. The alcohol is discharged from the system (in this case, an inert hydrocarbon solvent with a boiling point higher than that of the alcohol is used), and the general formula V (
OR)mC#a-Hl@nROH (hereinafter abbreviated as synthesis method C), which is obtained by precipitating a solid powdery complex compound insoluble in an inert hydrocarbon solvent. These synthesis methods are illustrative and not limited to these, but among them, the inert carbon obtained by synthesis method B or C is preferable to the tar-like or liquid vanadium compound obtained by synthesis method A. The solid powder complex compound VCOR) mC113-m@nROH which is insoluble in the hydrogen chloride solvent has higher polymerization activity and is particularly preferred for the present invention.

Further, the vanadium compound of the present invention can also be supported on a carrier such as silica or alumina.

The values of n and n in the general formula v(OR)mC13-m@nROH are 0m-1,5 and 0.5-n! 8.5 is preferred, but 0! m! 1 and i! n! a is more preferred.

In addition, the X-ray powder S,j vector of the solid powder complex compound is completely different from that of vanadium trichloride reported in ASTM15-882, and has a spectrum peculiar to vanadium trichloride (i.e., d-5,75'A, d= Figure 1 shows that the vanadium compound of the present invention and commercially available vanadium trichloride were oxidized to Cu- using high slag VD-〇. This is an X-ray powder spectrum measured with rays. The broken line indicates the vanadium compound VCA obtained with (N) of Examples 1 to 4 of the present invention.
! s・2, lCzHsOH, the solid line is the X-ray powder spectrum of commercially available sodium trichloride. .75λ
, d=2.67, d=1.74X, etc.) are not observed.

The organoaluminum compound used in the present invention has the general formula Y
3-. AlX1 (where Y is a hydrocarbon group, X1.t halogen or alkoxy group, l is a number represented by o'-152), trialkylaluminum, dialkylaluminum monohalide, dialkylaluminum monoalkoxide, alkyl This can be carried out using aluminum sulfuride, alkylaluminum cybaride, etc. These may be used alone or in combination, or
After premixing the sodium compound and the organoaluminium compound, the process can be carried out using the same or a different class of organoaluminium compounds. Among these, particularly preferred are diethylaluminum chloride, ethylaluminum dichloride, and mixtures thereof.

When producing an ethylene copolymer using the vanadium compound and the organoaluminum compound, the molar ratio of the vanadium compound and the organoaluminum compound is normally determined. @l
The mole ratio can be carried out at a ratio of from 1:1 to 1:100, but in the case of a tar-like or liquid vanadium compound obtained by synthesis method A, the above molar ratio is preferably from 1:5 to 1:50, and when using a tar-like or liquid vanadium compound obtained by synthesis method B or C. Solid powder complex compound V(OR)mc
The above molar ratio in the case of zs-m, nROH is 1:2 to 1
vs. B0 is preferred.

Furthermore, it is well known that the activity of vanadium compounds soluble in polymerization solvents can be improved by using various polymerization activators, and polymerization activators can be similarly used in the vanadium compound of the present invention. .

Examples of polymerization activators include alkyl esters of trichloroacetic acid and tribromoacetic acid (Japanese Patent Publication No. 48-150
52), perchlorocrotonic acid esters (Japanese Patent Publication No. 1185B-6), cellosolve esters of trichloroacetic acid or tribromoacetic acid (Japanese Patent Publication No. 1185B-6)
288), halogen compounds such as halogenated ketones, halogenated lactones, and halogen-containing cycloolefins.

In carrying out the present invention, the α-olefin used for copolymerization with ethylene is represented by the general formula CH2-CHR (where R is a hydrocarbon group having 1 to 8 carbon atoms), and specific examples include Propylene, butene-11pentene-
Examples include 11hexene-1,4-methylpentene-1. Among them, propylene and butene-1 can be preferably used.

Further, in order to introduce unsaturated bonds into the molecule, polyene components such as those shown below can be used in copolymerization with ethylene and α-olefin. For example, l,4-hexadiene, 1,6-octadiene, 6-methyl-1,5-
Hebutadiene, 1,9-octadecadiene, cycloheptadiene-1,4, dicyclopentadiene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, 2-methyl 2,5-norbornadiene, 5-
Examples include ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, cyclooctadiene-1,6, methyltetrahydroindene, and 1.4
-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are particularly preferred.

Polymerization can be carried out by solution polymerization or slurry polymerization in the presence of a polymerization solvent. Polymerization solvents include saturated hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogens such as trichloroethylene, tetrachloroethane, l,2-dichloroethane, and methylene chloride. Hydrocarbons, etc. can be used.

Also, in the absence of a hydrocarbon solvent, the catalyst system of the present invention is used in liquid α-oxyfins.

Ethylene can also be copolymerized.

The polymerization temperature can be varied over a wide range, but is usually between -80 and -1
It is carried out at 00°C, particularly preferably in the range of -80 to 80°C.

The polymerization is carried out at atmospheric pressure or under increased pressure and can be either batch or continuous.

In producing a copolymer by the method of the present invention, a commonly used molecule *h moderating agent can be used to obtain a copolymer having an arbitrary molecular weight. That is, diethylzinc, aryl chloride, and pyridine are used as molecular weight regulators.
N-oxide, hydrogen, etc. are often used, and hydrogen is particularly preferred.

Hereinafter, the method of the present invention will be specifically explained using examples, but the present invention is not limited to the same extent by these examples.

In addition, in the examples, the intrinsic viscosity of the copolymer was 185°C,
Measurements were made in tetralin, and propylene or butene-1 content in the copolymer was determined from infrared absorption spectra. In addition, the molecular weight distribution of the copolymer is determined by gelpermeatio
Measured by nchromatography, the broadening of the molecular weight distribution was determined by NB, which is a standard substance of
5-706 (polystyrene) was measured under conditions that give MW/MN=2.1. In addition, the polymerization activity is the polymerization amount (g) of the copolymer per mol of vanadium atoms (
(hereinafter abbreviated as Polymer/V).

Examples 1 to 4 & Formation of captive vanadium compounds 0.021 mol of vanadium trichloride and 0.206 mol of ethyl alcohol were added to a 100 d flask purged with argon, and after reacting at 50°C for 1 hour with stirring, n - Add 80 d of hebutane and dry under reduced pressure at room temperature while stirring,
A pale green solid powdered vanadium compound insoluble in n-hebutane was obtained.

When this vanadium compound was decomposed with pure water and its composition analyzed, it was found that vanadium atoms were 21% by weight and chlorine atoms were 48% by weight.
1%, C2H50H was detected in an amount of 40% by weight. In addition, this vanadium compound is decomposed with DzO (heavy water) to produce G, C
-When analyzed by MS, C2H50D was not detected. Therefore, this vanadium compound is VCl5.2. IC
2HIIOH (general formula v(OR)mC(la-m@nR
It was a compound where m and n of OH are 0 and 2.1).

The X-ray powder spectrum of this vanadium compound is shown in Figure 1, but it is completely different from the vanadium trichloride reported in ASTM 16-882, and the spectrum unique to vanadium trichloride (i.e. d-5, 76, d-2, 6rX,d
Diffraction lines such as −1,74λ) were not observed.

(Bl Copolymerization of ethylene-propylene 21 (D) Attach a stirrer, a thermometer, a dropping funnel, and a reflux condenser to a separable flask, reduce the pressure, and replace with nitrogen. Pour 1 liter of dry n-hexane into the flask. A predetermined amount of the vanadium compound obtained in Example 1 (abbreviated as component A) was added thereto, and a predetermined mixed gas was flowed therein at a flow rate of 1ONl/min for 10 minutes to form a mixed gas. Next, a predetermined amount of ethylaluminum sesquichloride (abbreviated as component B) was added thereto to start copolymerization.The above mixed gas was flowed for 80 minutes while stirring at 80°C. After polymerization, the component dissolved in the polymerization solvent at 80°C (hereinafter, this soluble part is abbreviated as H4F) is extracted from a pipe with a wire mesh, and poured into a large amount of methanol to precipitate a copolymer. The material was washed several times with 50 d of methanol and then dried under reduced pressure.

In addition, components insoluble in the polymerization solvent (hereinafter, this insoluble part is referred to as HI
P) remains in the flask, 50. The insoluble portion was washed several times with / of methanol and then dried under reduced pressure. 1st
Table 2 shows the amounts of components A and B added, mixed gas composition, polymerization rate, and polymerization activity, and Table 2 shows the propylene content, MW/MN, and limiting viscosity of the obtained copolymer.

In Examples 1 to 8, almost no HIP was generated, 98 to 100% was H4F, and the polymer liquid was homogeneous during polymerization. The obtained copolymers were copolymers obtained using vanadium compounds soluble in polymerization solvents (Comparative Examples 1 to 8).
The molecular weight distribution was narrower and the composition was more homogeneous than that of (see). On the other hand, in Example 4, there were fewer H4F-producing mackerels, and 97
% of HIP, and the resulting copolymer had a narrow molecular weight distribution and was homogeneous in composition, similar to Examples 1 to B.

Comparative Examples 1-8 Vanadium oxytrichloride (abbreviated as A' component) soluble in the polymerization solvent was used instead of the vanadium compound used in Example 1-4.
and 0.2 mmol of ethylaluminum sesquichloride (abbreviated as component B)2. Example 1 except that the method used was to use a method in which the B component and the A' component were added after the mixed gas having the composition shown in Table 8 was dissolved at 80° C. using Omi') moles.
Copolymerization was carried out in the same manner as (Bl) of ~4. Polymerization conditions,
The polymerization results and the composition of the copolymer are shown in Tables 8 and 4.

When the ethylene composition of the mixed gas exceeds 50 molar squares, the amount of HIP that is insoluble in the polymerization solvent increases, and during polymerization,
The polymer liquid becomes heterogeneous. The obtained copolymer had a broader molecular weight distribution and was compositionally heterogeneous as compared to Examples 1 to 4.

Example 5 Synthesis of captive vanadium compound In a 10oWl flask purged with argon, 0.088 mol of vanadium trichloride and 26++/n-hebutane were added, the temperature was raised to 50°C, 0.166 mol of methyl alcohol was added, and an argon stream was added. The mixture was reacted for 1 hour at 50° C. with stirring. After the reaction, the supernatant liquid was extracted through a glass filter and
Washed with 5-n-heptane 8 times, dried under reduced pressure,
A dark green solid powdered vanadium compound insoluble in n-hebutane was obtained.

When the composition of this vanadium compound is analyzed in the same manner as in Examples 1 to 4, is it vanadium? 21% by weight of hydrogen atoms, 42% by weight of chlorine atoms, 40% by weight of CH30H, and no CH30D was detected. Therefore, this vanadium compound is ■
Ce3・8. OCH30H (general formula ■ (OR) mC1j
It was a compound represented by m and n of 3-m@nROH (0 and 8.0). Further, in the X-ray powder spectrum of this compound, similar to the vanadium compounds obtained in Examples 1 to 4, no spectrum peculiar to vanadium trichloride was observed.

(B) Copolymerization of ethylene-propylene After purging a 500 flask equipped with a reduction condenser with argon, add dried n-hebutane 2007 and 0.089 E'J mol of the vanadium compound obtained in the above solution, and A stirrer was attached to raise the internal temperature of the flask to 60°C. A mixed gas containing 75 moles of ethylene and 26 moles of propylene was flowed through this at a flow rate of INI/min for 5 minutes to dissolve the mixed gas.

Then ethylaluminum sesquichloride 1.80
mmol was added to start copolymerization. Polymerization was carried out at 60° C. by flowing the mixed residue for 80 minutes while stirring, and the polymer solution was poured into methanol from a large sardine to recover all of the copolymer.

The obtained copolymer has a molecular weight of 2.96F and has a polymerization activity of 1 mmol of vanadium atom.
When expressed as l (hereinafter abbreviated as Polymer/V), P
olymer/V=28. The intrinsic viscosity of this copolymer is 1.87 dll? The propylene content was 8.7% by weight, Mw/MN=2.6.

Comparative Example 4 A compound was prepared in the same manner as in Example 5, except that 0.096E mol of vanadium oxytrichloride soluble in the polymerization solvent and 0.96E mol of ethylaluminum sesquichloride were used instead of the vanadium compound in Example 5. Perform polymerization, 1.7
The 5Polymer/V from which a copolymer of 92 was obtained was 19. The intrinsic viscosity of this copolymer is 2.486.172,
Propylene content is 17.7% by weight, Mw/MN-5,
It was 4.

Example 6 The vanadium compound obtained in Example 5 (at 0,016
mmol, ethylaluminum sesquichloride 0.
Copolymerization was carried out in the same manner as in Example 5 (Bl) except that 22 mmol was used, the mixed gas composition was 5 to 60 mol % of ethylene, and the polymerization temperature was 80°C.

During the polymerization, no HIP was produced and only 2.5 ip of H4F was obtained. Polymer/V was 157. The intrinsic viscosity of this copolymer is s. 4ed1/2, propylene content was 80.7%, MW/MN-2.4.

Example 7 VC#ael. 5CHa
A vanadium compound represented by OH (general formula (OR) mCRs-m@nROH, where m and n are 0 and 1.6) was obtained. Further, in the X-ray powder spectrum of this compound, similarly to the vanadium compounds obtained in Examples 1 to 4 (5), no spectrum peculiar to vanadium trichloride was observed.

Copolymerization was carried out in the same manner as in Example 6, except that 0.019 mmol of this vanadium compound and 0.26 mmol of ethylaluminum sesquichloride were used.

During the polymerization, no HIP was produced and only 1.67y of H4F was obtained. Polymer/V was 8B. The intrinsic viscosity of this copolymer was a, 9ta #/2, the propylene content was 27.1% by weight, and Mw/MN-2.7. Example 8 Synthesis of captive vanadium compound 11 flask equipped with a dropping funnel After replacing with argon,
0.841 mol of vanadium trichloride and 600 mol of n-hebutane
d was added, the temperature was raised to 50°C, and 1.71 mol of ethyl alcohol was added dropwise from the dropping funnel over 10 minutes. Next, the temperature of the oil bath was raised to 120°C, and after reaction for 2 hours with stirring in an argon stream, the supernatant liquid was extracted with a glass filter and heated to 260°C.
Washed with m/n-hebutane 8 times, dried under reduced pressure,
A solid powdered vanadium compound insoluble in n-hebutane was obtained.

When the composition of this vanadium compound was analyzed in the same manner as in (4) of Examples 1 to 4, the vanadium atoms were 19% by weight,
Chlorine atoms are 8111jl, C2H4OH is 86% by weight
, C2H50D was 8 times 1%. Therefore, this vanadium compound is V(OCzHs)o, yc#z, ae
It was a compound represented by 2.0czHsOH. Also,
In the X-ray powder spectrum of this compound, similar to the vanadium compounds obtained in Examples 1 to 4, no spectrum peculiar to vanadium trichloride was observed.

(B) Copolymerization of ethylene-propylene Copolymerization was carried out in the same manner as in Example 6, except that 0.011J lmol of the vanadium compound obtained above and 0.186E lmol of ethylaluminum sesquichloride were used.

During the polymerization, HIP was not generated and only HSP was obtained at 0.87F. Polymer/V was 79. The intrinsic viscosity of this copolymer was 8.56 dll/y, the propylene content was 29.6% by weight, and MW/'MN=2.6.

Examples 9 to 11 Same as Example 6 except that the vanadium compound obtained in Examples 1 to 4 (abbreviated as component A) and ethylaluminum sesquichloride were adjusted to a predetermined molar ratio (abbreviated as AN/V). Copolymerization was carried out. Table 5 shows the amount of component A added, Aβ/
V, polymerization activity, composition of the obtained copolymer, etc. are shown. Note that the copolymer in each case was only H4F.

Example 12 The vanadium compound obtained in Examples 1 to 4 was 0.0
Copolymerization was carried out in the same manner as in Example 6, except that 19 mmol and 0.28 mmol of diethylaluminum chloride were used instead of ethylaluminum sesquichloride, and the composition of the mixed gas was changed to 65 mol 5 of ethylene and 35 mol % of propylene. , CIPol obtained a copolymer of 1.98P
ymer/V was 102.

The intrinsic viscosity of this copolymer is 8.08 dil/p, the propylene content is 17.0% by weight, and the Mw/MN is 3.0.
Met.

Example 1B (Synthesis of A+ vanadium compound 0.0B0 mol of vanadium trichloride and 50w1 of n-heptane were added to a 200-ml flask purged with argon, and
The temperature was raised to 90°C, 080 mol of ethyl alcohol was added, and the temperature of the oil bath was raised to 90°C. After reacting for 1 hour under stirring in an argon stream, the supernatant liquid was extracted with a glass filter and
5. Washed 8 times with n-hebutane and dried under reduced pressure.
A solid powdered vanadium compound insoluble in n-hebutane was obtained.

The composition of this vanadium compound was analyzed in the same manner as in Examples 1 to 4, and found that vanadium atoms were 19% by weight, chlorine atoms were 87% by weight, C2H50H was 48% by weight, and C2H5
00 is 8-fold IL% and is L. Therefore, this vanadium compound is V(OC2H5)0.2C12,8・2.6C
2H! It was a compound represented by IOH. Further, in the X-ray powder spectrum of this compound, similar to the vanadium compounds obtained in Examples 1 to 4, no spectrum peculiar to vanadium trichloride was observed.

(B) Copolymerization of ethylene-butene-1 0.051 mmol of the vanadium compound obtained in above) and 0.6 mmol of ethylaluminum sesquichloride.
Example 6 except that 6 mmol was used and the composition of the mixed residue was ethylene 885 morph 0 and butene 116.5 mol %.
Copolymerization was carried out in the same manner as above to obtain a 2.50F copolymer. Polymer/V was 49.

The intrinsic viscosity of this copolymer is 2.49 dl/1! , butene-1 content was 14.1w, 1%, Mw/MN = 2.8. Comparative Example 5 In place of the vanadium compound of Example 18, vanadium oxytrichloride soluble in the polymerization solvent was used. Copolymerization was carried out in the same manner as in Example 1B except that 0.40 mmol of o4a=remol and ethylaluminum sesquichloride was used, and 2
A copolymerization of ゜02y was obtained. Polymer/V was 47.

The intrinsic viscosity of this copolymer was 6.56 dl/f, the butene content was 9.4% by weight, and the weight ratio was -6.8.

Example 14 0.020 mole of vanadium trichloride and 020 mole of methyl alcohol were added to a 100y flask purged with argon and reacted at 50'C for 1 hour to obtain a dark green liquid vanadium compound.

This liquid vanadium compound has a vanadium atom of 0. IO
E-remol and ethylaluminum sesquichloride 2
．． Copolymerization was carried out in the same manner as in Example 1B except that 10 mmol was used to obtain a 2,90y copolymer. Polym
er/V was 29.

The intrinsic viscosity of this copolymer was 2.61 d(1/y), 12.8% by weight for the buden-1-containing copolymer, and MW/2.5.

Example 15 Ethylene-propylene copolymerization was carried out using 1 butyl ester of perchlorocrotonic acid (abbreviated as C component) as a co-activator. That is, 0.196 l mol of C component and Examples 1 to 4 were copolymerized. The vanadium compound obtained in (5) 0.
Copolymerization was carried out in the same manner as in Examples 1 to 4 (B), except that the mixture with 095 mmol of ethylaluminum sesquichloride and 1.425 mmol of ethylaluminum sesquichloride was used, and the mixed gas composition was changed to 60 moles of ethylene and 11,250 moles of pro. went. During polymerization, HIP was not produced and only H4F was 86.5
0f was obtained. Polymer/V was 384.

The intrinsic viscosity of this copolymer is 2.88 dll/y.

Otori containing pro-robilene is 27.1% by weight, MW/MN; 2
．． It was 9.

Example 16 Using the vanadium compounds obtained in Examples 1 to 4, terpolymerization of ethylene/propylene-15-teridine-2-norbornene was carried out.

That is, in (B) of Examples 1 to 4, 0.171 mmol of the vanadium compound obtained in Examples 1 to 4, 50 mol% of ethylaluminum sesquichlorane, and propylene 6-log gas were added to LONlj for 1 minute, and then hydrogen was added. Ethylene/propylene 15-ethylidene-2-norbornene ternary copolymerization was carried out in the same manner as fBl in Examples 1 to 4, except that a flow rate of 1Nl/min was used. After polymerization, 80wf of methanol was added to stop the reaction, and the mixture was poured into methanol to precipitate a copolymer. This precipitate was washed several times with 50-methanol and then dried under reduced pressure at 12.40F.
A copolymer was obtained.

Polymer/V was 78.

The intrinsic viscosity of this copolymer is 1.79 dtl/f.

The propylene-containing product is 28.7 weights and has an iodine value of 6.5.
MW/MN=2.8.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an X-ray powder spectrum of the vanadium compound of the present invention and commercially available vanadium trichloride. The broken line indicates the vanadium compound VC obtained in (4) of Examples 1 to 4 of the present invention.
#a-2.1C2H5OH, the solid line is the X-ray powder spectrum of commercially available vanadium trichloride. Figure 1 Procedural Amendment (Spontaneous) 6゜July 18, 1985 (1. Manufacturing method of combination 3 Related to the case of the person making the amendment Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Column ``1''. Contents of the amendment) The scope of the patent claims is amended as shown in the attached sheet.) Specification Page 4, lines 11 to 14. ``The present inventors have discovered that a novel vanadium compound obtained by reacting vanadium trichloride and an alcohol is particularly useful for the copolymerization of ethylene and α-olefin.'' [Although Japanese Patent Publication No. 89-18946 does not describe a specific method for synthesizing the catalyst, a hydrocarbon of vanadium trichloride and dialkyl aluminum monochloride complexed with ethanol, which is insoluble in hydrocarbons, A method has been proposed for producing an amorphous ethylene-a-olefin copolymer at a polymerization temperature of θ° to −50° C. in the presence of a catalyst consisting of a soluble reaction product. This process is carried out using an aromatic hydrocarbon as a polymerization solvent that substantially dissolves the catalyst. - ``I'' I polymerization in an aromatic hydrocarbon solvent; has the disadvantage of producing a low molecular weight ethylene copolymer, and is also more toxic than aliphatic hydrocarbons, resulting in less monopolymerization. Aromatic hydrocarbon solvents cannot be said to be excellent as polymerization solvents for industrial use because it is necessary to pay attention to operational operations such as post-treatment and quality aspects such as preventing residues from remaining in the copolymer. . The present inventors have an object to produce an ethylene copolymer which has higher polymerization activity than the above catalyst, is substantially solubilized in aliphatic or alicyclic hydrocarbons, and has a narrow molecular weight distribution and composition distribution. As a result of searching for a catalyst that can (8) Page 5, lines 9 to 17. ``In other words, the present invention uses vanadium trichloride and alcohol...
・e-el・I・…・I Hibiki……Goku■…・−…Number・
Fairy tale…■−−−−…No. 1 Atonement meeting/War everyone…
...Relates to a method for producing an ethylene copolymer. "of. "That is, the present invention provides the general formula V(OR)mCIls-m
-nROH (where ROH is alcohol, m is 0≦m(
1,5,n is a number expressed as 0.5<n≦8.5) and a solid powdery vanadium compound insoluble in an inert hydrocarbon solvent, and a compound having the general formula Y3gAIXI (a hydrocarbon group, x is a halogen, l is a number expressed as 1<l<2)
An ethylene copolymer characterized by copolymerizing ethylene and α-ol/fin in an aliphatic or alicyclic polymerization solvent in the presence of a catalyst system consisting of an aluminum compound represented by The present invention relates to a manufacturing method. ” he corrected. (4) Page 6, line 14 to page 7, line 2. “In the absence of a hydrocarbon solvent, vanadium trichloride and 1 to 20 times the mole of this...
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......, it is convenient to carry out the reaction in a polymerization vessel) or "" should be deleted. (5) Page 7, line 5. "The reaction was carried out in the same manner as in Synthesis Method A," was corrected to "After the reaction was carried out at a temperature between 0° C. and the boiling point of the alcohol, and vanadium trichloride was dissolved in the alcohol." (6) Page 7, lines 11-12. "(hereinafter abbreviated as 1 synthesis method B)" is deleted. (7) Page 7, line 15. Correct "after" to "after dissolving vanadium trichloride in alcohol." (8) Page 8, lines 2 to 8. "(hereinafter abbreviated as 1 synthesis method C)" is deleted. (9) Page 8, lines 5 to 18. ``However, among these, the tar-like substance obtained by synthesis method A
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・・・・・・・・・・・・・・・◆Sha IH11 meeting 1-...Q
■――・−・Fist-1 tatami −ψ−・・−e−・Warming−・−φ−
e...---------Choga-Kai-Kaikai l-Fight Exposure 1 Hayabusa Hayabusa Ryoban Gossip Music Exposure Drop Exposure... Can also be carried. ” to be deleted. (10) Page 9, line 18 to page 10, line 1θ. "l is a number expressed as 0<l<2)"
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.........'... are particularly preferred. "of. [1 is a number represented by 1<n<2], and can be carried out with a mixture of dialkylaluminum di)z-lide, alkylaluminum sesquinolide, etc. Among them, the general formula Yls
Organoaluminum compounds represented by AIjX1s are preferred, and ethylaluminum sesquichloride is particularly preferred. The vanadium compound and the organoaluminum compound are 9
Although copolymerization is usually carried out without premixing, copolymerization can be carried out with or without adding the organoaluminum compound after premixing the two. ” he corrected. (11) Page 10, lines 15 to 20, [Tar-like substance obtained by synthesis method A]
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In the case of ・・・・・・・・・, the above monosi ratio is deleted. (12) Page 1B, lines 1 to 8. [Polymerization takes place in the presence of a polymerization solvent...
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・・・・・・・・・・・・・・・Halogenated hydrocarbons etc. can be used. "Polymerization can be carried out by solution polymerization or slurry polymerization in the presence of a polymerization solvent.As a polymerization solvent, a saturated hydrocarbon9, for example, hexane, heptane,
Aliphatic hydrocarbons like octane, cyclohexane. Preference is given to selecting from alicyclic hydrocarbons such as cycloheptane. ” he corrected. (18) Page 29, line 18 to page 80, line 4. [Example 12 Mw/MN=8.0. "of. [Comparative Example 5 0.02 mmol of the vanadium compound obtained in (A) of Examples 1 to 4 and 0.4 mmol of diethylaluminum chloride instead of ethylaluminum sesquichloride.
Using mmol, the composition of the mixed gas was 65 mol% ethylene,
Copolymerization was carried out in the same manner as in Example 6, except that propylene was changed to 85 mol %, to obtain a 1.2F copolymer. Polymerization in progress. The polymer liquid was heterogeneous. Polymer/V is 6
It was 0. The intrinsic viscosity of this copolymer was 8.01 dl/f. Propylene content is 16.9% by weight, Mw/MN=8.
It was 7. ” he corrected. (14) Page 82, line 1, page 88, line 17, and page 84, line 1. "Example 18" is corrected to "Example 12". (15) p. 88, line 16. "Comparative Example 5" is corrected to "Comparative Example 6". (16) Page 84, line 7 to page 86, line 1. Delete "Example 14 MW/MW=2.5." (17) Page 85, line 2. "Example 15" is corrected to "Example 18J." (18) p. 35, line 18. "Example 16J is corrected as Example 14J. The above (9 complete) Special zero 1,000,000 ratio wind compound and the general formula Ys-IAIXI (where Y is a hydrocarbon group, X
In the presence of a catalyst system consisting of an organoaluminum compound, where is a halogen and l is a number represented by 1 < l minus 2, ethylene and an α-olefin are synthesized in a polymerization solvent consisting of an aliphatic or alicyclic hydrocarbon. A method for producing an ethylene copolymer, comprising copolymerizing with.

Claims (2)

[Claims] (1) A vanadium compound obtained by reacting vanadium trichloride and alcohol with the general formula Y3-4AIXz (where Y is a hydrocarbon group, X is a halogen or alkoxy group, and l is a number represented by o:ni2) 1. A method for producing an ethylene copolymer, comprising copolymerizing ethylene and an α-olefin in the presence of a catalyst system comprising an organoaluminum compound represented by: (2) The vanadium compound has the general formula V(OR)mCl3-
m@nROH (here, ROH is an alkoxy group, m is O-
2. The method according to claim 1, wherein the compound is a solid powder compound insoluble in an inert hydrocarbon solvent having the formula m1.6, n being a number expressed as 0.5n-8.5.