KR20240077275A - Polyolefin copolymer composition and method for preparing the same - Google Patents

Abstract

In a polymer comprising a polyolefin copolymer polymerized in the presence of a metallocene catalyst, a method for producing a polyolefin copolymer comprising the step of deactivating the metallocene catalyst by mixing a catalyst deactivator, further comprising: A polyolefin copolymer composition prepared by a manufacturing method is provided.

Description

Polyolefin copolymer composition and method for producing the same {POLYOLEFIN COPOLYMER COMPOSITION AND METHOD FOR PREPARING THE SAME}

The present invention relates to a method for producing a polyolefin copolymer and a polyolefin copolymer produced thereby.

Typically, polyolefin is manufactured using a transition metal catalyst, which causes a small amount of catalyst residue to remain in the polymer polymerization solution after the polymerization reaction.

These catalyst residues cause undesirable polymerization reactions when the polymerization products are introduced at higher temperatures, resulting in the formation of low molecular weight oligomers, waxes and greases, or changes in the properties of the polymer. In addition, polymerization reaction outside the reactor may cause excessive heat generation in the reaction product recovery line, etc., and may also cause precipitation of a polymer with a relatively low molecular weight.

To solve this problem, conventional additives such as anti-oxidants, steam, alcohols, and ethers and hydrotalcite-like compounds were used at the rear of the polymerization reactor. The activity of catalyst residues is deactivated by adding deactivators such as acid acceptors such as fatty acids salts and metal oxides.

Recently, the production process has been simplified by omitting the separate recovery and removal process for the remaining transition metal catalyst compound due to the highly activated catalyst and the development of catalyst deactivator. However, color change due to the transition metal catalyst remaining in the polymer polymerization solution. And the deterioration of physical properties has not been completely solved.

Therefore, there is a need for a technology that can suppress adverse reactions between remaining unreacted monomers and metal catalyst compounds by effectively deactivating the remaining transition metal catalyst even in a very small amount, and minimize decomposition and discoloration of the produced polymer.

Korean Patent Publication No. 10-1998-0075880

The present invention is intended to solve the problems of the prior art as described above. By effectively deactivating the remaining transition metal catalyst even in a very small amount, adverse reactions between the remaining unreacted monomers and the metal catalyst compound are suppressed, and the polymers produced are decomposed. and a catalyst deactivator capable of minimizing discoloration and a method for producing a polyolefin copolymer by deactivating a metal catalyst compound using the catalyst deactivator.

In addition, the present invention seeks to provide a polyolefin copolymer with low yellow index and high transmittance through effective catalyst deactivation.

In one aspect, the present invention provides a method for producing a polyolefin copolymer, comprising the step of deactivating the metallocene catalyst by mixing a catalyst deactivator in a polymer comprising a polyolefin copolymer polymerized in the presence of a metallocene catalyst. provides.

From another aspect, the present invention provides a polyolefin copolymer composition prepared by the above production method.

The catalyst deactivator provided in the present invention effectively deactivates the remaining transition metal catalyst even in a very small amount after completion of the polymerization reaction, preventing adverse reactions between the remaining unreacted monomers and the metal catalyst compound from occurring, thereby promoting the production of low molecular weight polyolefin polymer. It is possible to obtain a polymer with improved physical properties and thereby minimize the decomposition and discoloration of the produced polymer.

Therefore, polyolefin copolymers can be produced with high catalytic activity in the same post-treatment process, and are suitable for use in large closed systems. Polyolefin copolymers can be produced with high catalytic activity in the same post-treatment process.

Figure 1 schematically shows the polymerization process for producing an ethylene-alpha-olefin copolymer by the polyolefin copolymer composition production method of the present invention and the location where the catalyst deactivator is added in the production method.

In the present invention, in the production of polyolefin copolymers using a metallocene catalyst, deactivation of the transition metal catalyst is used to prevent phenomena such as catalyst decomposition that may occur at the rear of the reaction and the production of low molecular weight polymers that may be produced within the transfer line. We would like to provide a method.

The method according to the present invention includes the step of mixing a catalyst deactivator capable of deactivating the transition metal catalyst remaining in the effluent containing the polyolefin copolymer produced by polymerization in a polymerization reactor in the presence of the transition metal catalyst. do.

The effluent includes a transition metal catalyst, olefin monomers, along with the polyolefin copolymer produced by the polymerization reaction, and may also include a solvent. When this effluent is introduced into an environment with higher temperature conditions, the remaining transition metal catalyst causes discoloration of the polymer and causes additional polymerization of the monomer to produce low molecular weight polyolefin, thereby changing the properties of the polymer. This may cause deterioration in product quality, so it is desirable to deactivate the remaining transition metal catalyst.

Examples of the olefin monomer include ethylene and alpha-olefin comonomers that can copolymerize with ethylene. The alpha-olefin comonomer may be an alpha-olefin of (C ₃ ~C ₂₀ ), for example, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene. It may be at least one species selected from the group consisting of More preferably, the alpha-olefin comonomer may be 1-octene.

The solvent may be an aromatic hydrocarbon such as benzene, toluene, xylene, or cumene, an aliphatic hydrocarbon such as butane, isobutane, pentane, n-hexane, octane, decane, dodecane, hexadecane, or octadecane, or cyclo It may be an alicyclic hydrocarbon such as decane, cyclododecane, or cyclooctane, and may further be a petroleum fraction such as gasoline, kerosene, or diesel oil. Among these, n-hexane may be more preferable.

The transition metal catalyst remaining in the effluent is not particularly limited as long as it is a catalyst used in olefin copolymerization, but the transition metal catalyst in the present invention may be a transition metal catalyst represented by the following formula (1).

[Formula 1]

In Formula 1, M is selected from the group consisting of elements of groups 3 to 10 on the periodic table, preferably an element of group 4 on the periodic table, and more preferably zirconium (Zr), titanium (Ti), or hafnium (Hf). ) can be,

_{Wherein ​ ​ ​ ​ ​ ​ ​ 6} ~C ₂₀ )aryl group, (C ₆ ~C ₂₀ )aryl(C ₁ ~C ₂₀ )alkyl group, (C ₁ ~C ₂₀ )alkyl(C ₆ ~C ₂₀ )aryl group, (C ₆ ~C ₂₀ ) Selected from the group consisting of arylsilyl group, silyl (C ₆ ~ C ₂₀ )aryl group, (C ₁ ~ C ₂₀ )alkoxy group, (C ₁ ~C ₂₀ )alkylsiloxy group, and (C ₆ ~C ₂₀ )aryloxy group become,

n is an integer from 1 to 5,

Ar ¹ to Ar ² are the same or different from each other, and are each independently a ligand having a cyclopentadienyl skeleton, and the ligand is halogen, (C ₁ to C ₂₀ )alkyl group, (C ₃ to C ₂₀ )cycloalkyl group, ( C ₁ ~ C ₂₀ )alkylsilyl group, silyl (C ₁ ~C ₂₀ )alkyl group, halo (C ₁ ~C ₂₀ )alkyl group, (C ₆ ~C ₂₀ )aryl group, (C ₆ ~C ₂₀ )aryl (C ₁ ~C ₂₀ )alkyl group, (C ₁ ~C ₂₀ )alkyl(C ₆ ~C ₂₀ )aryl group, (C ₆ ~C ₂₀ )arylsilyl group, and silyl(C ₆ ~C ₂₀ )aryl group. It may be substituted or unsubstituted with one or more selected substituents, or the substituent may be combined with another adjacent substituent to form a ring.

The effluent may include a cocatalyst along with the transition metal catalyst as described above. The cocatalyst is added to activate the transition metal catalyst, and the type of cocatalyst is not particularly limited, and any one known in the art may be selected and used without particular limitation. For example, it may be an aluminoxane compound, an organoaluminum compound, or a bulky compound that activates the metallocene catalyst compound. Specifically, in order for the metallocene compound to become an active catalyst component used in olefin copolymerization, the Sike cocatalyst extracts a ligand from the metallocene compound to cationize the central metal (M) and generate a counterion with a weak binding force. That is, one that can act as an anion can be used. For example, it may be at least one kind of compound selected from the group consisting of a compound represented by the following formula (2), a compound represented by the formula (3), and a compound represented by the formula (4).

[Formula 2]

In Formula 2, Y ¹ is a (C ₁ to C ₁₀ )alkyl group, and q is an integer from 1 to 70.

Specifically, the compound represented by Formula 2 is Methylaluminoxane, Ethylaluminoxane, Butylaluminoxane, Hexylaluminoxane, Octylaluminoxane, or Decylaluminoxane. (Decylaluminoxane), and any one of these can be used alone or in a mixture of two or more.

[Formula 3]

In Formula 3, Y ² to Y ⁴ are each independently selected from the group consisting of halogen, (C ₁ to C ₁₀ )alkyl group, and (C ₁ to C ₁₀ )alkoxy group, and at least one of Y ² to Y ⁴ is (C ₁ to C ₁₀ ) It is preferable that it is an alkyl group.

Specifically, the compounds represented by Formula 3 include Trimethylaluminum, Triethylaluminum, Tributylaluminum, Trihexylaluminum, Trioctylaluminum, and Tridecyl Aluminum ( Tridecylaluminum, Dimethylaluminum methoxide, Diethylaluminum methoxide, Dibutylaluminum methoxide, Dimethylaluminum chloride, Diethylaluminum chloride, D Dibutylaluminum chloride, Methylaluminum dimethoxide, Ethylaluminum dimethoxide, Butylaluminum dimethoxide, Methylaluminum dichloride, Ethylaluminum dimethoxide It may be chloride (Ethylaluminum dichloride) or butylaluminum dichloride, and any one of these may be used alone, or two or more types may be used in combination.

[Formula 4]

[L] ⁺ [Z(A) ₄ ] ^-

In Formula 4, L is a neutral or cationic Lewis acid, Z is a Group 13 element, A is the same as or different from each other, and each independently halogen, (C ₁ -C ₂₀ )hydrocarbyl group, (C ₁ -C ₂₀ ) A (C ₆ -C ₂₀ )aryl group substituted with one or two or more substituents selected from the group consisting of an alkoxy group and a phenoxy group; It is a (C ₁ -C ₂₀ )alkyl group substituted with one or two or more substituents selected from the group consisting of halogen, (C ₁ -C ₂₀ )hydrocarbyl group, (C ₁ -C ₂₀ )alkoxy group, and phenoxy group.

Considering the activity of the metallocene compound, the compound represented by Formula 4 is a dimethylanilinium cation when [L] ⁺ is a cationic Lewis acid to which a hydrogen atom is bonded, and when [L] ⁺ is a cationic Lewis acid, [(C ₆ H ₅ ) ₃ C] ⁺ , and [Z(A) ₄ ] ^- may be preferably used as [B(C ₆ F ₅ ) ₄ ]-.

The compound represented by Formula 4 is not particularly limited, but non-limiting examples of the case where [L] ⁺ is a cationic Lewis acid to which a hydrogen atom is bonded include triphenylcarbenium borate, trimethylammonium tetraphenylborate, and methyldioctadecylammonium tetra. Phenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate , N,N-diethylanilium tetraphenyl borate, N,N-dimethyl(2,4,6-trimethylaninium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium Tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate (n-Butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaninium tetrakis(pentafluorophenyl)borate , N,N-diethylanilium tetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6-trimethylaninium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis( 2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6- Tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6- Tetrafluorophenyl)borate, N,N-dimethylaninium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanylnium tetrakis(2,3,4,6 -Tetrafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylaninium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, dioctadecylammonium tetrakis (pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, Methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate Phenyl)borate, methyldi(tetradecyl)-ammonium tetrakis(pentafluorophenyl)borate, triityl tetrakis(pentafluorophenyl)borate, etc.

In the present invention, although not particularly limited, a polymer polymerization solution containing the olefin monomer, a metal catalyst compound, and a solvent is continuously placed inside a reactor containing triisobutylaluminum to remove polar impurities such as moisture inside the reactor. A polyolefin copolymer can be prepared by injecting and stirring at a speed of 100 to 1,000 rpm at 40 to 160°C.

At this time, after polymerization, unreacted olefin monomers and solvents are included along with the polyolefin copolymer product, and the transition metal catalyst or transition metal catalyst and cocatalyst remain. Since these transition metal catalysts and/or cocatalysts remain active, additional reactions may occur when placed under conditions where additional polymerization reactions may occur, for example, high temperature conditions, and low molecular weight polyolefin may be produced. there is. Additionally, a small amount of catalyst residue remaining after the reaction may cause discoloration of the polymer during the high temperature solvent-polymer separation process performed at the rear of the reaction.

Therefore, in the present invention, a catalyst deactivator is added to the reaction effluent to prevent additional polymerization reaction from occurring by deactivating the transition metal catalyst or transition metal catalyst and cocatalyst contained in the reaction effluent as described above. The catalyst deactivator of the present invention can inhibit further polymerization reaction by terminating the reaction by reducing the activity of the catalyst by acting on the active site of the transition metal catalyst and cocatalyst.

Therefore, in the present invention, the deactivator may include alcohol, and the alcohol very effectively inhibits the adverse reaction between the unreacted monomer remaining in the polymer polymerization solution and the metal catalyst compound, thereby suppressing the production of low molecular weight polyolefin, Accordingly, it is possible to obtain a polymer with improved safety properties and minimize decomposition and discoloration of the manufactured polymer.

More specifically, the alcohol included in the deactivator may be at least one selected from the group consisting of monohydric alcohols containing a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 2- It may be ethylhexanol (2-Ethylhexanol), but is not limited thereto.

The alcohol may be included in an amount of 2 mmol to 20 mmol, and more specifically, may be included in an amount of 10 to 20 mmol.

In addition, the alcohol may be added so that the molar ratio of alcohol molecules:transition metal atoms contained in the transition metal catalyst is 1:1 to 20:1, and more specifically, alcohol molecules:transition metal atoms contained in the transition metal catalyst. The molar ratio may be 2:1 to 10:1, and more specifically, the molar ratio of alcohol molecules:transition metal atoms contained in the transition metal catalyst may be 2:1 to 5:1.

If the molar ratio of the alcohol molecule to the transition metal atom contained in the transition metal catalyst is less than 1:1, the deactivation efficiency of the metal catalyst compound remaining in the polymer solution may be reduced, which may result in additional polymerization reaction by the non-deactivated catalyst compound. This may occur, and if the molar ratio of the alcohol molecule to the transition metal atom contained in the transition metal catalyst exceeds 20:1, the residual alcohol during polymer production may cause a decrease in activity and abnormal reactions, thereby reducing the transparency of the polymer of the polyolefin copolymer. This may result in a decrease in physical properties, such as an increase in the cloudiness of the product.

In addition, the alcohol may be added in an amount of 1 to 50 ppm, more specifically, 10 to 30 ppm, based on the total amount of polyolefin copolymer.

The catalyst deactivator may be a mixture of the alcohol and a non-polar solvent. The non-polar solvent is not particularly limited, but at least one of toluene, chloroform, normal hexane, and (C ₄ to C ₁₀ ) hydrocarbon solvents can be used.

At this time, the mixing ratio of the alcohol and non-polar solvent included in the catalyst deactivator is not particularly limited.

By adding the above catalyst deactivator to the reaction effluent containing the polyolefin copolymer, olefin monomer, and transition metal catalyst, the transition metal catalyst or transition metal catalyst and cocatalyst remaining in the reaction effluent can be deactivated.

Figure 1 schematically shows the polymerization process for producing an ethylene-alpha-olefin copolymer by the polyolefin copolymer composition production method of the present invention and the location where the catalyst deactivator is added in the production method.

Referring to FIG. 1, a catalyst deactivator containing alcohol in the polymer polymerization solution is added to the reaction effluent discharged from the polymerization reactor. Typically, after the reaction effluent is discharged from the polymerization reactor, it is fed into the liquefaction system through a high-temperature transfer line to maintain the flowability of the reaction effluent. At this time, side reactions due to residual catalyst occur, so the catalyst deactivator is used to prevent the polymerization. It is preferred that it be introduced downstream of the reactor array and upstream of the liquefaction (devolatilization) system after discharge from the reactor.

According to the method of the present invention, the metal catalyst compound can be deactivated by adding a catalyst deactivator containing alcohol into a solution of the effluent containing the polyolefin copolymer produced by the polymerization reaction, and the polymer polymer obtained by the method There may be a small amount of deactivated transition metal catalyst compound in the solution, but since the content of the deactivated transition metal catalyst compound is usually less than 5 ppm, there is no need to perform a separate removal process to remove the transition metal catalyst.

In the polyolefin copolymer obtained by the method of the present invention, the activity of the residual transition metal catalyst is reduced by the catalyst deactivator, so additional polymerization reaction may not proceed at the rear end of the polymerization reactor, and as a result, low molecular weight polymer within the polyolefin polymer The content may decrease.

Specifically, based on the entire polyolefin, the content of low molecular weight polymer with a weight average molecular weight of 10,000 or less may be 1.0% by weight or less, and more specifically, the content of low molecular weight polymer with a weight average molecular weight of 10,000 or less may be 0.8% by weight or less. , more specifically, the content of low molecular weight polymer with a weight average molecular weight of 10,000 or less may be 0.7% by weight or less.

Accordingly, the polyolefin copolymer obtained by the method of the invention has a minimized low molecular weight polymer and residual catalyst compound content, and thus can have a low yellow index and high transmittance.

Example

Hereinafter, the present invention will be described in more detail through examples. However, the following examples specifically show one embodiment of the present invention and are not intended to limit the present invention thereby.

Examples 1, 2 and Comparative Examples 1 to 4

Solvent, comonomer, and catalyst were added in the amounts shown in Table 1 below, and polyolefin copolymer polymerization was performed under the conditions of a temperature of 140°C and a pressure of 60kg/cm2. The catalyst is a transition metal catalyst, dimethylsilyl(t-butyl amino)(tetramethyl cyclopentadienyl)titanium dimethyl, hereinafter referred to as 'LMC-1'. used.

menstruum Comonomer 1 Comonomer 2 catalyst ingredient hexane ethylene 1-octene LMC-1 input 2200kg/h 580 kg/h 550kg/h 2.5 g/h

The components and contents of the catalyst deactivator added to deactivate the metal catalyst compound after the polymerization reaction are shown in Table 2 below. In Table 2, “alcohol: molar ratio of transition metal atoms” refers to the molar ratio between alcohol molecules and transition metal atoms contained in the transition metal catalyst.

Example 1 Example 2 Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 catalyst deactivator 2-Ethylhexanol Ethylalcohol Not entered hydro
Talsite calcium
stearate Antistatic agent
Atmer163 Appearance Liquid Liquid - Powder Powder Liquid Boiling point (℃) 185 78 - - - - Input amount (g) 16.4 16.4 0 625 625 625 Alcohol: molar ratio of transition metal atoms 5:1 3:1 - 133:1 185:1 95:1 Compared to polymers
Input cost (ppm) 16 16 0 500 500 500

The obtained polyolefin copolymer was evaluated for catalyst activity, weight average molecular weight, molecular weight distribution, content of polyolefin copolymer with a molecular weight of 10,000 or less, yellow index, and transmittance using the following methods, and the results are shown in Table 3. indicated.

- Catalytic activity (kg POE/g cat)-

It was calculated as the ratio of the weight (kg) of the polyolefin copolymer produced per the mass (g) of the catalyst used.

- Weight average molecular weight, molecular weight distribution (Mw, MWD) and low molecular weight polymer content-

It was measured at 160°C using a 1,2,4-trichlorobenzene solvent using GPC (Gel Permeation Chromatography, device name: PL-GPC220, manufactured by Agilent).

- Yellow Index (YI) -

It was measured at Observer 2 degrees using a C light source according to ASTM D1925 using a color meter (ColorFlex).

- Transmissivity-

After molding the specimen to a thickness of 3 mm, the total light transmittance for light with a wavelength of 550 nm was measured using a hazemeter. A specimen of solar cell encapsulation material was placed in a specimen holder, the total light transmittance was measured three times, and the average value was obtained, and the measurements were made under the standard conditions of JIS K 7105.

polymer properties Example 1 Example 2 Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 catalytic activity
(kg/g-cat) 255 231 200 198 192 211 Mw 212K 210K 192K 200K 198K 195K MWD 2.1 2.3 3.4 2.2 2.3 2.4 Low molecular weight polymer content (Mw 10K or less, unit: weight%) 0.65 0.66 2.74 0.88 0.89 1.31 Y.I. 2.5 2.6 19.5 4.3 4.5 5.5 Transmittance (3mm specimen, unit: %) 90.5 90.2 87.5 86.9 85.5 87.0

As presented in the present invention, in the case of Examples 1 and 2 using alcohol, hydrotalcite, calcium stearate, and antistatic agent (Atmer163) were used as catalyst deactivators, as well as Comparative Example 1 in which no catalyst deactivator was used. Compared to Comparative Examples 2 to 4, it showed a very low yellowness value and a transparency of 90 or more, and it was confirmed that the production rate of low molecular weight polymer was also significantly reduced. On the other hand, in the case of Comparative Example 1 in which no catalyst deactivator was used, a high yellowness value was shown due to yellowing caused by residual catalyst, and the content of low molecular weight polymer was also confirmed to be the highest.

In Comparative Examples 2 to 4, in which hydrotalcite, calcium stearate, and antistatic agent (Atmer163) were added to the rear end of the reactor, the remaining catalyst was deactivated, resulting in lower yellowness than when no deactivator was used. However, it was confirmed that the yellowness value was still higher than that of the example of the present invention and the transparency was less than 90%.

More specifically, in Comparative Examples 2 and 3, the appropriate dosage of catalyst deactivator to deactivate the catalyst compound was very high, and as a result, the catalyst deactivator was impregnated into the polymer, so that the polyolefin copolymers of Comparative Examples 2 and 3 had low transmittance. I was able to confirm that I had it.

In addition, Comparative Examples 2 to 4 contained 0.8% by weight or more of a low molecular weight polymer, and it was confirmed that significantly more additional polymerization reactions of monomers due to residual catalyst compounds occurred compared to the present invention using alcohol.

In particular, in Comparative Example 4, although the catalyst deactivator added was liquid, its viscosity was high, so the effect of deactivating the catalyst in the polymer was reduced. As a result, it was confirmed that the polyolefin copolymer of Comparative Example 4 contained a low molecular weight polymer of 1.3% by weight or more.

From the above results, when using the catalyst deactivator containing alcohol provided in the present invention, the quality of the polymer product can be improved by suppressing the formation of low molecular weight polymers by effectively deactivating the catalyst, and achieving low yellowness and It was found that a polyolefin copolymer with high transparency could be produced.

Claims (6)

A method for producing a polyolefin copolymer, comprising the step of deactivating the metallocene catalyst by mixing a catalyst deactivator in a polymer comprising a polyolefin copolymer polymerized in the presence of a metallocene catalyst. The method of claim 1, wherein the catalyst deactivator is at least one selected from the group consisting of monohydric alcohols containing a linear or branched alkyl group having 1 to 10 carbon atoms. The method of claim 2, wherein the alcohol is 2-Ethylhexanol. A polyolefin copolymer composition prepared by the polyolefin copolymer production method of any one of claims 1 to 3. The polyolefin copolymer composition according to claim 4, wherein the content of the copolymer having a weight average molecular weight of 10,000 or less is 1.0% by weight or less. 6. The polyolefin copolymer composition of claim 5, wherein the polyolefin copolymer comprises ethylene structural units and 1-octene structural units.