KR20160062552A

KR20160062552A - Method for preparing polyolefin and polyolefin prepared thereby

Info

Publication number: KR20160062552A
Application number: KR1020140165463A
Authority: KR
Inventors: 김석환; 도상록; 박하나; 박종우; 이시정
Original assignee: 주식회사 엘지화학
Priority date: 2014-11-25
Filing date: 2014-11-25
Publication date: 2016-06-02

Abstract

The present invention relates to a process for producing an olefin polymerization catalyst comprising the steps of polymerizing an ethylene monomer and an ethylenically unsaturated monomer of the following formula (2) in the presence of a catalyst for olefin polymerization comprising a metallocene compound represented by the following formula (1) A polyolefin having a functional group such as an excellent carboxyl group can be efficiently produced, and a polyolefin prepared using the same.
[Chemical Formula 1]

(2)

(Wherein A, R ¹ to R ⁵ , R ^{3 '} , R ^4' , M, X, Y, n and p are as defined in the specification)

Description

METHOD FOR PREPARING POLYOLEFIN AND POLYOLEFIN PREPARED THEREBY BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin,

The present invention relates to a process for preparing a functional polyolefin using a metallocene catalyst and a polyolefin produced by the process.

BACKGROUND ART Polyolefins are widely used for extrusion molded articles, blow molded articles and injection molded articles because of their excellent moldability, heat resistance, mechanical properties, hygienic quality, water vapor permeability and appearance characteristics of molded articles. However, polyolefins, particularly polyethylene, have a problem of low compatibility with polar resins such as nylon because of the absence of polar groups in the molecule, and low adhesiveness to polar resins and metals. As a result, it has been difficult to blend the polyolefin with a polar resin or a metal, or to laminate it with these materials. Further, a molded article of polyolefin has a problem of low surface hydrophilicity and antistatic property.

In order to solve such a problem and to increase the affinity for a polar material, a method of grafting a polar group-containing monomer onto a polyolefin through radical polymerization has been widely used. However, this method has a problem in that cross-linking of the polyolefin and molecular chain breakage occur during the grafting reaction, and the viscosity balance of the graft polymer and the polar resin is poor and the miscibility is low. There is also a problem in that the appearance characteristics of a molded article are low due to a gel component produced by intramolecular crosslinking or a foreign substance generated by cleavage of molecular chains.

In addition, a method of producing an olefin polymer such as an ethylene homopolymer, an ethylene / alpha -olefin copolymer, a propylene homopolymer or a propylene / alpha -olefin copolymer can be carried out by copolymerizing a polar monomer with a metal catalyst such as a titanium catalyst or a vanadium catalyst Was used. However, when a polar monomer is copolymerized using the metal catalyst as described above, there is a problem that the molecular weight distribution or the composition distribution is wide and the polymerization activity is low.

As another method, there is known a method of polymerizing in the presence of a metallocene catalyst comprising a transition metal compound such as zircononocene dichloride and an organoaluminum oxy compound (aluminoxane). When a metallocene catalyst is used, a high molecular weight olefin polymer is obtained with high activity, and the resulting olefin polymer has a narrow molecular weight distribution and a narrow composition distribution.

Alternatively, a metallocene compound having a ligand of a non-crosslinked cyclopentadienyl group, a crosslinked or non-crosslinked bisindenyl group, or an ethylene crosslinked unsubstituted indenyl / fluorenyl group is used as a catalyst to prepare a polyolefin containing a polar group As a method, a method using a metallocene catalyst is also known. However, these methods have a disadvantage in that the polymerization activity is very low. For this reason, although a method of protecting a polar group by a protecting group has been carried out, there is a problem that the process becomes complicated because the protecting group must be removed again after the reaction when a protecting group is introduced.

The ansa-metallocene compound is an organometallic compound containing two ligands connected to each other by a bridge group, in which the rotation of the ligand is prevented by the bridge group, The structure is determined.

These anisometallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, it is known that an anisometallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, thereby controlling the microstructure of the polypropylene have.

It is also known that an anhydride-metallocene compound containing an indenyl ligand can produce a polyolefin having excellent activity and improved stereoregularity.

As described above, various researches have been made on anthra-metallocene compounds capable of controlling the microstructure of olefin-based polymers while having higher activity, but the degree of such anisotropy is still insufficient.

Korean Registered Patent No. 288272 (registered on May 2, 2001)

A first object of the present invention is to provide a process for producing a polyolefin having a functional group introduced therein by using a highly active metallocene catalyst containing bisindene as a ligand .

A second technical object of the present invention is to provide a polyolefin produced by the above process.

According to an embodiment of the present invention, there is provided a process for producing a polymer electrolyte membrane, which comprises polymerizing an ethylene monomer and an ethylenically unsaturated monomer represented by the following formula (2) in the presence of a catalyst for olefin polymerization comprising a metallocene compound represented by the following formula Wherein the polyolefin is a polyolefin.

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

M is selected from the group consisting of a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal, and an ethanide series transition metal;

A is an element of Group 14;

R ¹ is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms;

R ² is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms ;

R ³ , R ^{3 '} , R ⁴ and R ^4' each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms;

R ⁵ is a linear alkanediyl group having 8 to 20 carbon atoms,

Each X is independently halogen;

Y is a carboxyl group or a carboxylic acid ester group,

n is an integer of 1 to 20,

p is an integer of 1 to 3, and when p is 2 or 3, each Y is the same or different)

According to another embodiment of the present invention, there is provided a polyolefin produced by the above production method.

By the process for producing a polyolefin according to the present invention, a polyolefin having a functional group introduced therein can be easily produced with excellent efficiency. As a result, the process is particularly useful for the commercial production of functionalized polyolefins.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments of the invention and, together with the description of the invention, It should not be construed as limited.
FIG. 1 is a graph showing infrared spectroscopy (IR) results of the polyolefin prepared in Example 1. FIG.
2 is a graph showing IR results for the polyolefin prepared in Comparative Example 1. Fig.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

A process for producing a polyolefin according to an embodiment of the present invention comprises the step of polymerizing an ethylenic monomer and an ethylenically unsaturated monomer of the following formula (2) in the presence of a catalyst for olefin polymerization comprising a metallocene compound represented by the following formula .

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

M is a Group 3 transition metal (for example, Sc, Y, or La), a Group 4 transition metal (e.g., Ti, Zr, Hf, Ta, etc.), lanthanide series transition metals (e.g., Ce, Nd, etc.), and ethanide series transition metals (e.g., Th, Pa, etc.);

A is a bridge group connecting an indenyl group, specifically a group 14 element (e.g., Si, Ge, etc.);

R ⁵ is a linear alkanediyl group having 8 to 20 carbon atoms,

Each X is independently a halogen group;

Y is a carboxyl group (-COOH) or a carboxylic acid ester group (-COOR, R is a lower alkyl group having 1 to 4 carbon atoms)

n is an integer of 1 to 20,

p is an integer of 1 to 3, and when p is 2 or 3, each Y is the same or different.

More specifically, in Formula 1, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; R ³ And R ^{3 '} are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms; R ⁴ and R ^{4 '} are each independently selected from the group consisting of an aryl group having 6 to 18 carbon atoms and an alkylaryl group having 7 to 20 carbon atoms; n is an integer from 1 to 6; A may be silicon (Si).

More specifically, in the general formula (2), R ⁵ is preferably an alkylene group having ¹ to 10 carbon atoms such as an undecamethylene group, a dodecamethylene group, a tetradecamethylene group, a pentadecamethylene group, a hexadecamethylene group, an heptadecamethylene group, A methylene group and an eicosamethylene group, Y is a carboxyl group, and p may be an integer of 1.

In the method for producing a polyolefin according to an embodiment of the present invention, the catalyst for olefin polymerization includes the metallocene compound of the above formula (1).

In addition, the metallocene compound includes two indenyl groups as a ligand. In particular, the metallocene compound acts as a Lewis base as an oxygen-donor in a bridge group connecting the ligand. And the activity as a catalyst can be maximized.

More specifically, the metallocene compound may be a compound represented by the following formula (1a).

[Formula 1a]

(Ph in the above formula (1a) is a phenyl group)

The metallocene compound may be used at a concentration of 10 to 50 mu mol / l in the polymerization reaction.

In addition, the metallocene compound described above may be used as a catalyst for olefin polymerization itself, or may be used together with a cocatalyst as a catalyst precursor.

The cocatalyst may be alkylaluminoxane such as methylalumineoxane (hereinafter referred to as "MAO"). When such a cocatalyst is used, it can be used as a catalyst in which a halogen group (X) bonded to a metal element (M) of the metallocene compound is substituted with an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms.

The cocatalyst may be used in an amount such that the molar ratio (Al / M) of metal (Al) in the cocatalyst to the metal (M) in the metallocene compound is 1000 to 5000, more specifically 2000 to 3000.

The catalyst for olefin polymerization may be a catalyst supported on a support.

The carrier can be used without any particular limitation as long as it is used as a carrier in a metallocene catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.

In the case where the support is silica, there are few catalysts liberated from the surface during the olefin polymerization process because the functional groups of the silica carrier and the metallocene compound of Chemical Formula 1 form a chemical bond. As a result, it is possible to prevent fouling of the wall surface of the reactor or the polymer particles entangled with each other during the production process of the polyolefin. In addition, the polyolefin produced in the presence of the catalyst containing the silica carrier has excellent particle shape and apparent density of the polymer.

More specifically, the carrier may be a high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on its surface through a method such as high temperature drying.

The carrier may further comprise an oxide, carbonate, sulphate or nitrate component such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ or Mg (NO ₃ ) ₂ and the like.

Meanwhile, in the process for producing a polyolefin according to an embodiment of the present invention, the ethylene monomer is a compound containing an intramolecular polymerizable unsaturated ethylene group and can be used without particular limitation as long as it is used in the production of a polyolefin.

The ethylene monomer may be used in various states, solid, liquid, or gas phase depending on the polymerization method. Specifically, in the present invention, a gaseous ethylene monomer may be used, and in this case, the gaseous ethylene monomer may be supplied to the polymerization catalyst.

The ethylenically unsaturated monomer represented by the above formula (2) as a comonomer copolymerized with the ethylenic monomer is preferably an ethylenically unsaturated monomer having a functional group of a carboxy group or a carboxylic acid ester group in the molecule and a linear hydrocarbon group having 8 or more carbon atoms It is a monomer.

In the case of a metallocene catalyst in general, the activity of the catalyst is greatly reduced as the amount of the functional group-containing monomer is increased. On the contrary, in the present invention, the activity of the metallocene-based catalyst, particularly the supported catalyst, can be improved by increasing the distance between the functional group and the polymerizable reactive group by including a long chain hydrocarbon group.

More specifically, the ethylenically unsaturated monomer is selected from the group consisting of 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, methyl 9-decenoate, methyl 10-undecenoate, Hexanoate, ethyl 6-heptenoate, ethyl 7-octenoate, ethyl 8-nonenoate, ethyl 9-decenoate, ethyl 10-undecenoate, ethyl 11-dodecenoate, isopropyl Octenoate, isopropyl 10-undecenoate, isopropyl 11-dodecenoate, butyl 5-hexenoate, butyl 6-heptenoate, butyl 7-octenoate, butyl 8- Butyl 9-decenoate, butyl 10-undecenoate, or butyl 11-dodecenoate, and the like, alone or in a mixture of two or more. More specifically, the ethylenically unsaturated monomer may be 10-undecenoic acid.

The ethylenically unsaturated monomer may be used in consideration of the content of the carboxyl group or carboxylate ester group in the finally produced olefin polymer or the content of the repeating unit derived from the ethylenically unsaturated monomer containing the functional group. Specifically, the ethylenically unsaturated monomer may be used at a concentration of 10 to 200 mmol / l, more specifically 20 to 40 mmol / l.

In the method for producing a polyolefin according to an embodiment of the present invention, the polymerization reaction may be a slurry polymerization method, a vapor phase polymerization method or a liquid phase polymerization method. For example, the catalyst may be supported on a solid support In the case of using in a solution state, a liquid phase polymerization method may be used.

Specifically, when a gaseous ethylene monomer is used, the metallocene compound of Formula 1 and the co-catalyst are added as the comonomer to the ethylenically unsaturated monomer of Formula 2 as a comonomer, The polymerization reaction can be carried out by mixing and contacting the resultant mixture with ethylene in the gaseous phase.

As the organic solvent that can be used in the polymerization reaction, a hydrocarbon organic solvent having 3 to 20 carbon atoms can be used. Specifically, examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, cumene or cymene; Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, or octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane or methylcyclopentane; Petroleum oils such as gasoline, kerosene or light oil; And halides (chlorides, bromides, etc.) of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons. Any one or a mixture of two or more of them may be used. As the organic solvent, ethers such as ethyl ether and tetrahydrofuran may also be used.

The polymerization reaction may be carried out at a temperature of 25 to 200 ° C and a pressure of 1 to 100 kgf / cm ² for 10 minutes to 1 hour, more specifically a temperature of 40 to 100 ° C and a pressure of 5 to 40 kgf / cm ² &Lt; / RTI > for 10 minutes to 30 minutes.

Further, the polymerization reaction may be carried out for 10 minutes to 1 hour, more specifically 10 minutes to 30 minutes.

The polymerization reaction may be carried out in the presence of an organoaluminum compound.

In this case, a pretreatment step may be further performed in which the ethylenically unsaturated monomer is mixed with and contacted with the organoaluminum compound prior to the polymerization reaction.

The organoaluminum compound may be used in the form of a pretreatment agent for the ethylenically unsaturated monomer. Specifically, the organoaluminum compound may be a compound of the following formula (3): < EMI ID =

(3)

(R _a) _m AlZ ₃ _-m

In Formula 3,

R _a is selected from the group consisting of a hydrocarbon group of 1 to 12 carbon atoms, specifically an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms,

Z is a halogen atom or a hydrogen atom, and

and m may be an integer of 1 to 3.

In Formula 3, R _a is more specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, Tolyl group, and m may be an integer of 3.

More specifically, examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum or tri-2-ethylhexylaluminum; Alkenyl aluminum such as isoprenyl aluminum; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride or dimethylaluminum bromide; Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride or ethyl aluminum sesquih bromide; Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride or ethylaluminum dibromide; Alkyl aluminum hydride such as diethyl aluminum hydride or diisobutyl aluminum hydride, and any one or a mixture of two or more of them may be used. More specifically, the organoaluminum compound may be triisobutylaluminum.

The organoaluminum compound is mixed with the ethylenically unsaturated monomer described above to increase the reactivity of the ethylenically unsaturated monomer in the subsequent polymerization reaction. The organoaluminum compound is preferably used in an appropriate amount in the polymerization reaction, and more preferably 10 to 400 mol / l. < / RTI >

The mixing of the ethylenically unsaturated monomer and the organoaluminum compound may be carried out according to a conventional method. Specifically, the ethylenic unsaturated monomer may be mixed with an organoaluminum compound in an organic solvent.

The organic solvent may be a hydrocarbon-based organic solvent having 3 to 20 carbon atoms, and more specifically, an aromatic hydrocarbon such as benzene, toluene, xylene, cumene or cymene; Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, or octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane or methylcyclopentane; Petroleum oils such as gasoline, kerosene or light oil; And halides (chlorides, bromides, etc.) of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons. Any one or a mixture of two or more of them may be used. As the organic solvent, ethers such as ethyl ether and tetrahydrofuran may be used. The organic solvent may be used as an organic solvent for polymerization in the subsequent polymerization reaction.

The mixing of the ethylenically unsaturated monomer and the organoaluminum compound may be carried out using a heat resistant / pressure resistant device such as an autoclave. More specifically, the mixing can be performed at a temperature of 20 to 100 DEG C and a pressure of 1 to 40 atm for 10 minutes.

In addition, the molecular weight range of the finally produced polymer product can be controlled according to the hydrogenation or non-addition conditions during the polymerization reaction. Particularly, a polyolefin having a high molecular weight can be produced under hydrogen-free conditions, and a low molecular weight polyolefin can be produced with a small amount of hydrogen under the condition of hydrogenation. At this time, the hydrogen content added to the polymerization reaction may be in the range of 0.07 L to 4 L under 1 atm of the reactor condition, or at a pressure of 1 bar to 40 bar in the reactor, or in a molar amount of hydrogen of 168 ppm to 8,000 ppm.

As described above, the method of producing a polyolefin according to an embodiment of the present invention uses a metallocene catalyst containing bis-indene as a ligand to exhibit a high activity, so that a carboxyl group having excellent adhesiveness and compatibility with a metal or a polar resin Can be produced with excellent efficiency.

Specifically, the polyolefin may be a copolymer comprising a repeating unit represented by the following general formula (4) and a repeating unit represented by the following general formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 4 and 5, R ⁵ , Y and p are the same as defined above,

R is each independently a hydrogen atom or a straight or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, and specific examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, Propyl group, n-pentyl group, n-hexyl group, 1-ethyl-1-methylpropyl group , A 1,1-diethylpropyl group, a 2-ethylhexyl group, an octyl group, a decyl group or a dodecyl group.

Since the polyolefin contains a carboxyl group or a carboxylic acid ester group in the polymer, the polyolefin is excellent in adhesion and compatibility with metals or polar resins (nylon, EVOH, etc.), water dispersibility and oil resistance.

Such an improvement effect can be determined by the content of the carboxyl group or the carboxylic acid ester group contained in the polymer, or the content of the repeating unit derived from the ethylenically unsaturated monomer containing the functional group. Specifically, the olefinic polymer according to one embodiment of the present invention may contain the repeating units of the above formulas (4) and (5) in a molar ratio of 99.999: 0.001 to 10:90.

The olefin-based polymer may contain constitutional units other than the repeating units of the formulas (4) and (5) within the range not impairing the object of the present invention.

Examples of the optionally contained constituent units include cyclic olefins other than the monomer of Formula 2, nonconjugated polyenes, hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenic unsaturated compounds, aromatic vinyl compounds , Unsaturated carboxylic acids and derivatives thereof, vinyl ester compounds, or vinyl chloride. When these constituent units are contained, these amounts are 10 mol% or less based on all the constituent units constituting the polar group-containing olefin copolymer.

The above-mentioned additional structural unit may be added together with the addition of the ethylenically unsaturated monomer during the production of the polyolefin.

The olefin-based polymer can have a higher molecular weight than the olefin-based polymer prepared by using the metallocene compound as a catalyst by using the metallocene compound having excellent catalytic activity of the formula (1). Specifically, when the polymerization process is carried out under the condition that hydrogen is not added, the weight average molecular weight (Mw) of the produced polyolefin may be 100,000 to 600,000 g / mol, more specifically 300,000 to 600,000 g / mol. Further, when the polymerization process is carried out under the condition of adding hydrogen, for example, when the polymerization process is carried out under the condition of adding 0.37 L of hydrogen under 1 atm of the reactor condition, the resulting polyolefin has a weight average molecular weight (Mw) of 10,000 To 300,000 g / mol, more specifically from 10,000 to 100,000 g / mol.

The molecular weight distribution (Mw / Mn) of the polyolefin may be 3.3 or less, more specifically 1.2 to 3. When the molecular weight distribution (Mw / Mn) is 3 or less, the olefin polymer is excellent in the orientation of the carboxyl group or the carboxylic acid ester group in the polymer at the interface between the polymer and the polar material, It is excellent in compatibility with materials.

In the present invention, the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined from the results obtained by measurement in 140 ° C in o-dichlorobenzene solvent using GPC (gel permeation chromatography).

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[ Example 1: Production of olefinic polymer]

In the autoclave, 40 mmol / l of 10-undecenoic acid in 900 ml of toluene was contacted with 80 mmol / l of triisobutylaluminum as an organoaluminum compound for 10 minutes. 10 占 퐉 ol / liter of methylaluminoxane (MAO, Al / Zr = 3000) as a cocatalyst and 10 占 퐉 ol / l of a metallocene catalyst (Cat1) having the following structure were added in sequence. The temperature of the reactor was heated to 60 DEG C and the pressure in the reactor was then filled up to 5 atm with ethylene. The polymerization was carried out for 10 minutes so that ethylene was continuously supplied at a pressure of 5 atm, followed by the addition of 10 ml of ethanol to terminate the polymerization. After the reactor was cooled, the product was recovered and dried in a vacuum oven at 60 DEG C for 8 hours to obtain an olefinic polymer. As a result of infrared spectroscopy (IR) on the polymer, the acid content in the polymer was less than 1 mol%.

(Cat1)

[ Comparative Example 1: Production of olefinic polymer]

As shown in the following Table 1, 20 mmol of pentanoic acid was used instead of 40 mmol / l of 10-undecenoic acid, and 40 mmol / l of trimethylaluminum (TMA) was used instead of 80 mmol / l of triisobutylaluminum (TIBA) , The same procedure as in Example 1 was carried out. However, no polymer was produced.

[ Comparative Example 2: Preparation of olefin-based polymer]

Except that 20 mmol / l of pentanoic acid was used instead of 40 mmol / l of 10-undecenoic acid, and 40 mmol / l of triisobutylaluminum (TIBA) was used as shown in Table 1 below. The procedure of Example 1 was repeated to prepare an olefin polymer.

Catalyst (μmol / l) Co-catalyst Ethylene (bar) Comonomer (mmol / l) Organoaluminum compound (mmol / l) Yield (g) The content of carboxy groups in the polymer
(mol%) Comparative Example 1 Cat 1 (10) MAO
(Al / Zr molar ratio = 3000) 5 The pentanoic acid (20) The TMA (40) - - Comparative Example 2 Cat 1 (10) MAO
(Al / Zr molar ratio = 3000) 5 The pentanoic acid (20) TIBA (40) 4.2 - Example 1 Cat 1 (10) MAO
(Al / Zr molar ratio = 3000) 5 10-undecenoic acid (40) TIBA (80) 13.3 Less than 1 mol%

IR analysis was performed on the polymers prepared in Example 1 and Comparative Example 2, and the results are shown in Figs. 1 and 2, respectively.

As a result, a peak of the carboxyl group derived from the comonomer 10-undecenoic acid was confirmed in the polymer of Example 1, but in the case of Comparative Example 2 in which pentanoic acid was used as the comonomer, the presence or absence of the comonomer in the prepared polymer was confirmed No carboxyl group peak was observed. From these results, it can be seen that the use of a comonomer satisfying the conditions according to the present invention makes it possible to produce a polymer having a carboxyl group.

[ Comparative Example 3 to 7: Preparation of olefin polymer]

The procedure of Example 1 was repeated except that 25 ml of toluene was used and the catalyst, co-catalyst, comonomer and additives for preparing the polymer were varied and varied in the kind and content shown in Table 2 below. 1, to prepare an olefin-based polymer.

The catalyst activity was calculated from the molar ratio of the catalyst to the total amount of the olefin polymer prepared in Comparative Examples 3 to 7, and the results are shown in Table 2 below.

However, as shown in the following Table 2, no olefin polymer was produced in any of Comparative Examples 3 to 7.

catalyst
(μmol / l) Co-catalyst Ethylene (bar) Comonomer (mmol / l) Organoaluminum compound (mmol / l) Activity (kg / mmol · hr) Comparative Example 3 Cat 2 (20) MAO 5 The UDA (48) TIBA (96) - Comparative Example 4 Cat 2 (20) AB
(0.1 mM) 5 The UDA (48) TIBA (96) - Comparative Example 5 Cat 2 (20) AB
(0.1 mM) 5 The UDA (48) TIBA (16) - Comparative Example 6 Cat3 (20) MAO 5 The UDA (48) TIBA (96) - Comparative Example 7 Cat3 (20) MAO 5 The UDA (48) TIBA (16) -

The meanings of abbreviations in Table 2 are as follows:

MAO: Methyl aluminoxane (molar ratio of Al / Zr = 3000)

AB: N, N'-Dimethylanilinium tetra (pentafluorophenyl) borate

UDA: 10-undecenoic acid

TIBA: Triisobutyl aluminum

catalyst:

(Cat2)

(Cat3)

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims

A process for producing a polyolefin comprising the step of polymerizing an ethylenic monomer and an ethylenically unsaturated monomer represented by the following formula (2) in the presence of a catalyst for olefin polymerization comprising a metallocene compound represented by the following formula (1).
[Chemical Formula 1]

(2)

(In the above formulas (1) and (2)
M is selected from the group consisting of a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal, and an ethanide series transition metal;
A is an element of Group 14;
R ¹ is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms;
R ² is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms ;
R ³ , R ^{3 '} , R ⁴ and R ^4' each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms;
R ⁵ is a linear alkanediyl group having 8 to 20 carbon atoms,
Each X is independently halogen;
Y is a carboxyl group or a carboxylic acid ester group,
n is an integer of 1 to 20,
p is an integer of 1 to 3, and when p is 2 or 3, each Y is the same or different)

The method according to claim 1,
Wherein the catalyst for olefin polymerization comprises a metallocene compound represented by the following formula (1a).
[Formula 1a]

(Ph in the above formula (1a) is a phenyl group)

The method according to claim 1,
Wherein the catalyst for olefin polymerization is supported on a support selected from the group consisting of silica, silica-alumina and silica-magnesia.

The method according to claim 1,
Wherein the catalyst for olefin polymerization further comprises a cocatalyst of alkylaluminoxane.

5. The method of claim 4,
Wherein the alkylaluminoxane is methylaluminoxane.

The method according to claim 1,
Wherein the ethylenically unsaturated monomer is 10-undecenoic acid.

The method according to claim 1,
Wherein the ethylenically unsaturated monomer is pretreated with an organoaluminum compound.

8. The method of claim 7,
Wherein the organoaluminum compound is a compound represented by the following general formula (3).
(3)
(R _a) _m AlZ ₃ _-m
(3)
Ra is a hydrocarbon group of 1 to 12 carbon atoms,
Z is a halogen atom or a hydrogen atom, and
and m is an integer of 1 to 3)

8. The method of claim 7,
Wherein the organoaluminum compound is triisobutylaluminum.

A polyolefin produced by the process according to claim 1.