KR101503004B1 - Polyolefin-based copolymer and method for preparation of the same - Google Patents

Abstract

The present invention relates to a polyolefin-based copolymer having a broad molecular weight distribution and excellent flowability, and a process for producing the same. More specifically, the polyolefin-based copolymer is obtained by polymerizing at least one olefin monomer in the presence of a catalyst composition comprising a specific transition metal compound having at least one lower alkyl substituent group in its ring structure as a catalyst And is provided by a method for producing a copolymer.

Description

[0001] POLYOLEFIN-BASED COPOLYMER AND METHOD FOR PREPARATION OF THE SAME [0002]

The present invention relates to a polyolefin-based copolymer having a broad molecular weight distribution and excellent flowability, and a process for producing the same.

Dow has published [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (CGC) in the early 1990s (US Pat. No. 5,064,802). In the copolymerization of ethylene and alpha olefins, the CGC Compared with the known metallocene catalysts, the excellent aspects of the CGC are summarized as follows: (1) high molecular weight copolymers with high activity at high polymerization temperatures and (2) - It is also excellent for the copolymerization of α-olefins with large steric hindrance such as hexene and 1-octene. In addition, as the various characteristics of CGC are gradually known during the polymerization reaction, efforts to synthesize the derivatives and use them as polymerization catalysts have been actively made in academia and industry.

On the other hand, the copolymer produced by the CGC catalyst has a lower melt-flow rate than the copolymer prepared by the conventional Ziegler-Natta catalyst and thus has a limitation on fluidity. Furthermore, existing polyvinyl chloride copolymers have a limitation in the production of polymers having a high molecular weight and a broad molecular weight distribution.

The present invention provides a polyolefin-based copolymer having a remarkably increased fluidity and exhibiting excellent physical properties and at the same time having a broad molecular weight distribution and a method for producing the same.

The present invention relates to a process for the preparation of a catalyst composition comprising, in the presence of a catalyst composition comprising a transition metal compound represented by the following general formula (1) having at least one lower alkyl substituent in its ring structure,

Polymerizing at least one or more olefin monomers or comonomers, comprising the steps of:

[Chemical Formula 1]

In Formula 1,

R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms;

R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or amido Radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring;

CY1 is an aliphatic or aromatic ring in which one or more lower alkyl groups having 1 to 5 carbon atoms are substituted, wherein the aliphatic or aromatic ring is optionally substituted with a substituent selected from the group consisting of hydrogen, a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the substituent of the aliphatic or aromatic ring is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.

Further, the present invention relates to a polyolefin-based copolymer obtained by copolymerizing at least one olefin monomer or a comonomer and having a density of 0.860 to 0.920 g / cm 3 and a molecular weight distribution (Mw / Mn) of 2.0 to 3.0, By weight of the polyolefin-based copolymer.

The polyolefin-based copolymers preferably have a melt index (MI, 2.16 kg) of 0.1 to 1000 g / 10 min.

According to the present invention, olefinic monomers are polymerized using a novel catalyst comprising a structure in which at least one of the cyclic structures is substituted with a lower alkyl group in the production of the polyolefin-based copolymer, so that the fluidity is improved and the molecular weight distribution To give a polyolefin-based copolymer exhibiting excellent physical properties.

Fig. 1 shows the flowability and processability of Example 2 and Comparative Example 1 of the present invention in comparison.
Fig. 2 shows a comparison of flowability and processability for Example 2 and Comparative Example 2 of the present invention.

Hereinafter, a polyolefin-based terpolymer in accordance with a specific embodiment of the present invention and a method for producing the same will be described.

According to one embodiment of the present invention, at least one olefin monomer or comonomer is polymerized in the presence of a catalyst composition comprising a transition metal compound represented by the following formula (1) having at least one lower alkyl substituent in its ring structure A process for preparing a polyolefin-based copolymer comprising the steps of:

[Chemical Formula 1]

In Formula 1,

R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms;

R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or amido Radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring;

CY1 is an aliphatic or aromatic ring in which one or more lower alkyl groups having 1 to 5 carbon atoms are substituted, wherein the aliphatic or aromatic ring is optionally substituted with a substituent selected from the group consisting of hydrogen, a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the substituent of the aliphatic or aromatic ring is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.

As will be supported by the following examples, the present invention can provide a polyolefin-based polymer having a melt index equal to or lower than that of a conventional polymer and exhibiting a broad molecular weight distribution even in a similar density region by using a transition metal compound having the above- Copolymer can be obtained. Therefore, the polyolefin-based copolymer can exhibit better mechanical properties than the previously known olefin-based copolymer. The polyolefin-based copolymer can be more preferably used in various regions, and in particular, the applicability of the elastomer copolymer can be further improved.

Hereinafter, the polyolefin-based copolymer and the method for producing the same will be described in more detail.

The present invention relates to a process for producing a polyolefin-based copolymer using at least one or more olefin monomers or comonomers, wherein a transition metal compound having a cyclic structure is used as a catalyst and at least one lower alkyl group as an essential substituent in the cyclic structure, The above-mentioned transition metal compound having the alkyl group of 1 to 5 is used. According to the use of the catalyst, the present invention can provide a polyolefin-based copolymer having a broad molecular weight distribution and improved fluidity. In particular, the transition metal complex of Formula 1 exhibits excellent shear-thinning properties and can improve workability.

The transition metal compound represented by the above formula (1), unlike the previously known transition metal compounds, can be stably maintained in a pentagonal ring structure around the metal sites by the quinoline amido group contained in the structure, It structurally facilitates the access of monomers. Further, when the catalyst composition comprising the transition metal compound is used, excellent reactivity is exhibited in the copolymerization between ethylene and monomers with large steric hindrance. Therefore, the transition metal compound has an excellent propylene / diene copolymerization degree relative to other transition metal compounds, and EP and EPDM can be produced with high yield even at a high temperature of 100 ° C or higher.

When a catalyst in which at least one lower alkyl group, preferably a methyl group, is introduced to CY1 in the structure of the above formula (1) is used as a catalyst, a product having a relatively broad molecular weight distribution and fluidity can be provided.

In the above formula (1), "hydrocarbyl" is a monovalent radical group in which hydrogen atoms are removed from hydrocarbons, and includes ethyl or phenyl.

In the above formula (1), "metalloid" is a metalloid metal having an intermediate property between a metal and a nonmetal, and includes arsenic, boron, silicon or tellurium.

The transition metal compound represented by the formula (1) is a transition metal compound represented by the following formula (2) or (3), which is more preferable for controlling the electronic and stereoscopic environment around the metal.

(2)

(3)

In the general formulas (2) and (3)

R4 and R5 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Or a silyl radical;

R6 may be the same or different and are each independently selected from the group consisting of hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more R < 6 > among the R < 6 > may be linked to each other to form an aliphatic or aromatic ring ;

R6 'is substituted with at least one lower alkyl group having 1 to 5 carbon atoms, and the remaining substituents include hydrogen, a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical may be substituted, in which two or more substituents may be connected to each other to form an aliphatic or aromatic ring;

Q3 and Q4 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; Or an arylamido radical having 6 to 20 carbon atoms;

M is a Group 4 transition metal.

Further, in the above formula (1), transition metal compounds having the following structures are more preferable compounds for controlling the electronic stereoscopic environment around the metal.

In the above structural formulas, R7 may be the same or different from each other and is independently selected from hydrogen or a methyl radical, Q5 and Q6 may be the same or different from each other and each independently represents a methyl radical, a dimethylamido radical, or a chloride radical Is selected.

The catalyst composition may further include at least one cocatalyst selected from the group consisting of compounds represented by the following formulas (4), (5) and (6)

[Chemical Formula 4]

- [Al (R &_lt; 8 >) - O] _n -

In Formula 4,

R8 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

n is an integer of 2 or more;

[Chemical Formula 5]

D (R 8) ₃

In Formula 5,

R8 is as defined in Formula 4 above;

D is aluminum or boron;

[Chemical Formula 6]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 6,

L is a neutral or cationic Lewis acid;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

Examples of the compound represented by the general formula (4) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 5 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

The compound represented by the general formula (6) includes a non-coordinating anion which is compatible with a cation which is a Bronsted acid. Preferred anions are relatively large in size and contain a single coordination complex containing a metalloid. Particularly, compounds containing a single boron atom in the anion moiety are widely used. From this viewpoint, the compound represented by the formula (6) is preferably an anion-containing salt containing a coordinating complex containing a single boron atom.

As specific examples of such compounds, there may be mentioned trialkylammonium salts such as trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate (Pentafluorophenyl) borate, tri (2-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4-triisopropylsilyl) -2,3,5,6-tetra Fluorophenyl) borate, N, N-dimethylanilinium N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, (2,3,4,6-tetrafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, Anilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) ) Borey , Pentyldimethylammonium tetrakis (pentafluorophenyl) borate, dodecyldimethylammonium tetrakis (pentafluorophenyl) borate, tetradecyldimethylammonium tetrakis (pentafluorophenyl) borate, hexadecyldimethylammonium tetrakis Octadecyldimethylammonium tetrakis (pentafluorophenyl) borate, eicosyldimethylammonium tetrakis (pentafluorophenyl) borate, methyldecylammonium tetrakis (pentafluorophenyl) borate, methyldido (Pentafluorophenyl) borate, methyldiotetradecylammonium tetrakis (pentafluorophenyl) borate, methyldihexadecylammonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylammonium tetrakis Pentafluorophenyl) borate, methyldiacosylammonium tetrakis (pentafluoro (Pentafluorophenyl) borate, tridecylammonium tetrakis (pentafluorophenyl) borate, tridodecylammonium tetrakis (pentafluorophenyl) borate, trityl tetradecylammonium tetrakis (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, trioctadecylammonium tetrakis (pentafluorophenyl) borate, trieocosyl ammonium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, dodecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, octadecyldi (n-butyl) ammonium tetrakis (Pentafluorophenyl) borate, methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecyl anilinium tetrakis The like are exemplified fluorophenyl) borate.

Examples of dialkylammonium salts include di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate and the like.

Examples of the carbonium salt include tropylium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluorophenyl) .

Particularly preferred compounds include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, di (octadecyl) methylammonium tetrakis (pentafluorophenyl) ) Borate, di (octadecyl) (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, tropylium tetrakis For example.

The catalyst composition can be prepared by the following methods.

First, a transition metal compound represented by Formula 1 is contacted with a compound represented by Formula 4 or 5 to obtain a mixture; And adding the compound represented by Formula 6 to the mixture.

Second, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 4.

Third, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 and the compound represented by Formula 5.

In the first method of the catalyst composition, the molar ratio of the compound represented by Formula 4 or Formula 5 to the transition metal compound represented by Formula 1 is preferably 1: 2 to 1: 5,000, More preferably from 1:10 to 1: 1,000, and most preferably from 1:20 to 1: 500. When the molar ratio of the compound represented by Formula 4 or Formula 5 to the transition metal compound represented by Formula 1 is less than 1: 2, the amount of Formula 4 or Formula 5 that can be used as an alkylating agent is very small, There is a problem in that the alkylation of the alkylated metal compound is not completely progressed. When the alkylation of the metal compound exceeds 1: 5,000, the activation of the alkylated metal compound due to the side reaction between the excess excess alkylating agent and the activating agent of the formula There is a problem that can not be achieved.

In the first method, the molar ratio of the compound represented by Formula 6 to the transition metal compound represented by Formula 1 is preferably 1: 1 to 1:25, more preferably 1: 1 to 1:10, Most preferably from 1: 2 to 1: 5. When the ratio of the compound represented by the formula (6) to the transition metal compound represented by the formula (1) is less than 1: 1, the amount of the activator is relatively small and the activation of the transition metal compound represented by the formula The activity of the resulting catalyst composition is poor. When the ratio is more than 1: 25, the transition metal compound represented by the general formula (1) is completely activated. However, There is a problem that the purity of the produced polymer is inferior or not economical.

In the second method of the present invention, the molar ratio of the compound represented by Formula 4 to the transition metal compound represented by Formula 1 is preferably 1:10 to 1: 10,000, more preferably 1: 100 to 1: 5,000, and most preferably from 1: 500 to 1: 2000. When the molar ratio of the compound represented by the general formula (4) to the transition metal compound represented by the general formula (1) is less than 1:10, the amount of the activator is relatively small, The activity of the compound of formula (1) is completely achieved. However, when the excess amount of the activator is used, the unit cost of the catalyst composition is not economical or the purity of the produced polymer is low .

Meanwhile, in the third method of the catalyst composition manufacturing method, the molar ratio of the compound represented by Formula 6 to the transition metal compound represented by Formula 1 is preferably 1: 1 to 1:25, 1: 1 to 1: 10, and most preferably 1: 2 to 1: 5. If the molar ratio of the compound represented by the formula (6) to the transition metal compound of the formula (1) is less than 1: 1, the activation of the compound of the formula (1) There is a problem in that the activity of the catalyst composition is inferior. When the ratio exceeds 1:25, the transition metal compound is completely activated, but the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is decreased there is a problem.

In the preparation of the catalyst composition, hydrocarbon solvents such as pentane, hexane, heptane and the like, aromatic solvents such as benzene and toluene may be used as a reaction solvent, but not always limited thereto, and all solvents usable in the related art are used .

The transition metal compounds and cocatalysts represented by Formula 1 may also be supported on an inert carrier such as silica or alumina.

In the present invention, the olefin-based monomer or comonomer may include at least one member selected from the group consisting of ethylene, alpha-olefin, cyclic olefin, dienolefin-based monomer and triene olefin-based monomer.

Preferably, the olefin monomer or comonomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Dodecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene, norbornene, norbornadiene, ethylidenenorbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, At least one selected from the group consisting of styrene, butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

More specifically, the monomer constituting the olefin polymer of the present invention is ethylene, and the comonomer is preferably selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene .

It is also preferred that the step of polymerizing the olefin monomer or the comonomer is carried out at a temperature of 100 ° C to 200 ° C for 5 minutes to 10 minutes under a pressure of 10 bar to 100 bar.

In the present invention, the polymerization process of the polyolefin-based copolymer is preferably a batch or continuous solution polymerization process using the catalyst composition. The catalyst composition is also applicable to slurry or gas phase processes when used in combination with an inorganic carrier such as silica.

In this case, in the case of the continuous solution polymerization process, it may be composed of a catalytic process, a polymerization process, a solvent separation process, and a recovery process step. Hereinafter, the continuous solution polymerization process will be described in more detail. However, the scope of the present invention is not limited thereto.

a) catalytic process

The continuous solution polymerization process uses a solvent, and the solvent may include at least one selected from the group consisting of an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, an aromatic hydrocarbon solvent, and a hydrocarbon solvent substituted with a chlorine atom.

Specifically, the catalyst composition used in the production of the polyolefin-based copolymer may be prepared by dissolving or diluting the catalyst composition in an aliphatic or aromatic solvent having 5 to 12 carbon atoms substituted or unsubstituted with halogen suitable for the olefin polymerization process, a hydrocarbon solvent substituted with a chlorine atom, It is possible. For example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof, aromatic hydrocarbon solvents such as toluene, xylene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene, Can be used. The solvent used herein is preferably treated with a small amount of alkylaluminum or the like to remove a small amount of water or air acting as a poison to the catalyst, and it is also possible to use the catalyst in an excessive amount.

b) Polymerization process

The polymerization process is carried out by introducing at least one olefin monomer or comonomer and a catalyst composition containing the transition metal compound and the cocatalyst of the above formula (1) in the reactor. In addition, a scavenger can be introduced as needed. In addition, when polymerization proceeds in a solution phase and a slurry phase, the solvent can be injected onto the reactor. Therefore, in the case of solution polymerization, a mixture of a solvent, a catalyst composition, an olefin monomer or a comonomer may be present in the reactor.

Examples of olefinic monomers or comonomers which can be used in the process for producing a polyolefin-based polymer according to the present invention include ethylene, alpha-olefins, cyclic olefins and the like as described above, and dienes having two or more double bonds An olefin-based monomer or a triene olefin-based monomer may also be used. More specifically, the monomer constituting the olefin polymer of the present invention is ethylene, and the comonomer is preferably selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene .

Also, the process for producing the polyolefin-based copolymer is carried out in the presence of a solvent, and when the monomer is a mixture of two monomers, the first monomer is ethylene, the second monomer is 1-octene, and the solvent is n-hexane Particularly preferred.

The molar ratio of (monomer / comonomer) or (first monomer / second monomer) suitable for the present invention is 1/100 to 100, preferably 1/10 to 10, most preferably 1/5 to 2 . When the molar ratio of (monomer / comonomer) or (first monomer / second monomer) exceeds 100, there is a problem that the density of the resulting polymer is increased and the production of a low-density polymer is difficult. If the ratio is less than 1/100, the amount of the unreacted comonomer or the second monomer is increased to lower the conversion rate, resulting in a problem that recycle is increased in the process.

The molar ratio of the monomer to the solvent suitable for the reaction should be a ratio suitable for dissolving the raw material before the reaction and the polymer produced after the reaction. Specifically, the molar ratio of monomer to solvent is from 10: 1 to 1: 10000, preferably from 5: 1 to 1: 100, and most preferably from 1: 1 to 1:20. When the molar ratio is more than 10: 1, the amount of the solvent is too small to increase the viscosity of the fluid, resulting in a problem of transferring the resulting copolymer. When the molar ratio is less than 1: 10000, Or more, and problems such as an increase in equipment and an increase in energy cost due to the refining and recycling of the solvent may occur.

The solvent is preferably introduced into the reactor at a temperature of -40 DEG C to 150 DEG C by using a heater or a freezer, whereby the polymerization reaction starts with the monomer and the catalyst composition. When the temperature of the solvent is less than -40 ° C, there is a slight difference depending on the amount of the reaction. However, since the temperature of the solvent is generally too low, the reaction temperature is also lowered and the temperature is difficult to control. The temperature of the solvent is too high, so that it is difficult to remove the heat of reaction due to the reaction.

A high capacity pump may be used to pump the mixture of feeds without further pumping between the reactor arrangement, the pressure drop device, and the separator by feeding the feeds (solvent, monomer, catalyst composition, etc.) .

The internal temperature of the reactor suitable for the above production method, that is, the polymerization reaction temperature is -15 캜 to 300 캜, preferably 50 캜 to 200 캜, and most preferably 100 캜 to 200 캜. When the internal temperature is lower than -15 ° C, the reaction rate is low and productivity is lowered. If the internal temperature is higher than 300 ° C, generation of impurities due to side reactions and discoloration such as carbonization of the copolymer may occur.

The internal pressure of the reactor suitable for the above production method is 1 to 300 bar, preferably 30 to 200 bar, and most preferably 50 to 100 bar. If the internal pressure is less than 1 bar, the reaction rate is low and the productivity is low, and there is a problem due to vaporization of the used solvent. If the internal pressure exceeds 300 bar, the equipment cost such as the device cost due to the high pressure may be increased.

The copolymer produced in the reactor is preferably maintained at a concentration of less than 20 wt% in the solvent and is preferably transferred to the first solvent separation process for solvent removal after a short residence time. In the above-mentioned production process, the residence time of the copolymer in the reactor is from 1 minute to 10 hours, preferably from 3 minutes to 1 hour, and most preferably from 5 minutes to 30 minutes. When the residence time is less than 1 minute, problems such as a decrease in productivity due to a short residence time and an increase in manufacturing cost due to a loss of catalyst may occur. If the residence time exceeds 10 hours, , The reactor becomes large, and thus the equipment cost may increase.

The present invention may further include the step of injecting a scavenger in the polymerization process as required. Preferably, in the step of polymerizing the olefin monomer or the comonomer, the step of introducing 0.4 to 5 times of the scavenger into the reactor based on the molar ratio of the total amount of water introduced into the reactor may be included.

The scavenger may include a compound represented by the following general formula (7), but is not limited thereto.

(7)

D (R) ₃

In Formula 7,

R may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

D is aluminum or boron.

Examples of the compound represented by Formula 7 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

The scavenger may be preliminarily mixed with the solvent during the continuous solution polymerization process and then introduced into the reactor separately from the catalyst composition containing the transition metal compound.

c) solvent separation process

The present process is a process for removing the solvent present with the copolymer exiting the reactor, and is performed by changing the solution temperature and pressure. For example, the polymer solution transferred from the reactor is heated from about 200 ° C to 230 ° C through a heater, and then the pressure is lowered through the pressure drop device, and the unreacted raw material and the solvent are vaporized in the first separator.

The pressure in the separator is in this case 1 to 30 bar, preferably 1 to 10 bar, most preferably 3 to 8 bar. The temperature in the separator is suitably 150 deg. C to 250 deg. C, preferably 170 deg. C to 230 deg. C, and most preferably 180 deg. C to 230 deg.

When the pressure in the separator is less than 1 bar, the content of the polymer increases and there is a problem in transferring. When the pressure is more than 30 bar, it is difficult to separate the solvent used in the polymerization process. If the temperature in the separator is lower than 150 ° C, the viscosity of the copolymer and its mixture increases to cause a problem in transportation. When the temperature exceeds 250 ° C, there is a problem of discoloration due to carbonization of the polymer due to denaturation at high temperature.

The solvent vaporized in the separator can be recycled to the condensed reactor in the overhead system. When the first stage solvent separation process is carried out, a concentrated polymer solution of up to 65% can be obtained. This is transferred to the second separator by the transfer pump through the heater, and the separation process for the residual solvent is performed in the second separator. A heat stabilizer is added to prevent the polymer from being deformed due to high temperature while passing through the heater. In addition, the reaction inhibitor is injected into the heater together with the heat stabilizer in order to suppress the reaction of the polymer due to the residual activity of the active substance present in the polymer solution. The residual solvent in the polymer solution injected into the second separator is finally completely removed by a vacuum pump, and the granulated polymer can be obtained by passing through the cooling water and the cutter. In the second separation process, the gaseous solvent and other unreacted monomers can be sent to the recovery process for reuse after purification.

d) Recovery process

The organic solvent introduced into the polymerization step together with the raw material may be recycled to the polymerization step together with the unreacted starting material in the primary solvent separation step. However, the solvent recovered in the secondary solvent separation process contains a large amount of water acting as a catalyst poison in the solvent due to contamination due to incorporation of a reaction inhibitor to stop the catalytic activity and steam supply in the vacuum pump, It is preferable to be reused.

According to another embodiment of the present invention, there is provided a polyolefin-based copolymer produced by the above-described method for producing a polyolefin-based copolymer using a specific catalyst.

Preferably, in the present invention, a polyolefin-based copolymer obtained by copolymerizing at least one olefin monomer or a comonomer and having a density of 0.860 to 0.920 g / cm 3 and a molecular weight distribution (Mw / Mn) of 2.0 to 3.0, A polyolefin-based copolymer is provided.

The polyolefin-based copolymer produced by the above method has a melt index (MI, 2.16 kg) of 0.1 to 1000 g / 10 min when measured according to ASTM D-1238 (condition E, 190 ° C, 2.16 kg load) Preferably from 1 to 1000 g / 10 min, more preferably from 1 to 700 g / 10 min.

The weight average molecular weight of the polyolefin-based copolymer may be 10,000 to 200,000.

Thus, the polyolefin-based copolymer according to this embodiment exhibits the same or a lower melt index as compared with the previously known polyolefin-based copolymer in the similar density region, and the flowability can be increased. Furthermore, the polyolefin-based copolymer exhibits a broad molecular weight distribution and can exhibit more excellent physical properties.

Hereinafter, the present invention will be described in detail with reference to specific examples of the present invention. It is to be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the invention.

The organic reagents and solvents required for the polymerization were purified by standard methods from Aldrich, and ethylene was passed through a water and oxygen filtration system of a high purity product of Applied Gas Technology. At every stage of the olefin polymerization, the contact between air and water was blocked to improve the reproducibility of the experiment.

< Example  1 to 2>

Ethylene and &lt; RTI ID = 0.0 &gt; 1- Octane  Copolymer production

A hexane solvent, 1-octene and ethylene monomer were fed at a pressure of 89 bar to a 1.5 L continuously stirred reactor preheated at a temperature of 100-150 占 폚. From the catalyst storage tank, a transition metal compound represented by the following formula (1a) and octadecylmethylammonium tetrakis (pentafluorophenyl) borate promoter were fed into a reactor to conduct a copolymerization reaction. Polymerization was carried out at a relatively high temperature of 140 to 145 ° C. The polymer solution formed by the copolymerization reaction was reduced to 7 bar at the end of the reactor and then sent to a solvent separator preheated at 230 ° C. to remove most of the solvent Respectively. The copolymer sent to the second separator by the pump completely removed the residual solvent by vacuum pump and then passed the cooling water and the cutter to obtain the granulated polymer. The polymerization conditions of the ethylene and the 1-octene copolymer according to the present invention are shown in Table 1 below.

[Formula 1a]

< Comparative Example  1>

The procedure of Example 1 was repeated except that, in the preparation of the polyolefin copolymer, the compound of the following formula (8) was used as the catalyst instead of the transition metal compound of the above formula (1a).

[Chemical Formula 8]

< Comparative Example  2>

For comparative physical properties, a product of Dow (ELITE 5815, density 0.910, MI 15.6), which is commercialized as a conventional ethylene copolymer, was used as Comparative Example 2.

&Lt; Evaluation of physical properties &

The density of the polymer was measured by treating the polymer samples obtained in Examples and Comparative Examples with a 190 占 폚 press mold to prepare a sheet having a thickness of 3 mm and a radius of 2 cm and then cooling at 10 占 폚 / Were measured on a Mettler balance.

The melt index (MI2) of the polymer was measured by ASTM D-1238 (condition E, 190 DEG C, 2.16 kg load).

The molecular weight and the molecular weight distribution were measured by high-temperature gel permeation chromatography (GPC) and TCB (trichlorobenzene) was flowed at a rate of 1.0 mL / min at 160 ° C.

The flowability and processability of Example 2 and Comparative Example 1 are compared and shown in Fig. In addition, the flowability and rigidity of Example 2 and Comparative Example 2 are compared and shown in Fig.

C6 C2 1-C8 1-C8 / C2 H ₂ Temp. pressure density MI MWD unit kg / h kg / h kg / h Weight ratio L / h ℃ bar g / cm3 g / 10 min Example 1 3.15 0.80 0.379 0.473 0.0 155 89 0.900 4.57 2.41 Example 2 3.15 0.97 0.267 0.275 1.5 160 89 0.912 13.5 2.48 Comparative Example 1 3.15 0.80 0.379 0.473 8.0 158 89 0.907 12.1 2.11 Comparative Example 2 0.909 15.6 2.38 C6 = hexane, C2 = ethylene, 1-C8 = 1-octene

As can be seen from the results of Table 1, the polyolefin-based copolymers of Examples 1 and 2 exhibited the same or lower melt index than Comparative Examples 1 and 2 using the above-mentioned specific transition metal compound of the formula (1) In particular, the molecular weight distribution is widened.

Further, as shown in FIG. 1, the polyolefin-based copolymer of Example 2 of the present invention was found to have an excellent shear thinning effect compared to Comparative Example 1. This can be explained by the somewhat wider molecular weight distribution of the copolymer of Example 2 and the difference in the microstructure of the polymer. Therefore, the polyolefin-based copolymer of the present invention is produced using a new catalyst, so that it is possible to obtain a product having a wider molecular weight distribution and a significantly higher fluidity than that of Comparative Example 1 used as a conventional catalyst.

2, it was confirmed that the polyolefin-based copolymer of Example 2 had an excellent shear-thinning effect even in comparison with Comparative Example 2. On the other hand, the ELITE product of Comparative Example 2 has a broad molecular weight distribution, but it is confirmed that the fluidity is inferior to that of Example 2.

Claims (11)

In the presence of a catalyst composition comprising a transition metal compound represented by the following formula (1) having at least one lower alkyl substituent in the ring structure,
Polymerizing the olefin monomer or the comonomer in a reactor,
The continuous solution polymerization process comprises a catalytic process, a polymerization process, a solvent separation process and a recovery process step,
In the solvent separation step, the polymer solution transferred from the reactor is heated from 200 ° C. to 230 ° C., and the unreacted starting material and the solvent are vaporized in the first separator through the pressure strengthening device. The vaporized solvent in the separator is transferred to the second separator And separating the residual solvent,
Wherein the pressure in the first separator is between 1 and 30 bar and the temperature in the separator is between 150 and 250 ° C.
Method of producing polyolefin-based copolymer:
[Chemical Formula 1]

In Formula 1,
R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms;
R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or amido Radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring;
CY1 is an aliphatic or aromatic ring in which one or more lower alkyl groups having 1 to 5 carbon atoms are substituted, wherein the aliphatic or aromatic ring is optionally substituted with a substituent selected from the group consisting of hydrogen, a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the substituent of the aliphatic or aromatic ring is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;
M is a Group 4 transition metal;
Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.
The method of claim 1, wherein the catalyst composition further comprises at least one cocatalyst selected from the group consisting of compounds represented by Chemical Formulas (4), (5) and (6)
[Chemical Formula 4]
- [Al (R &_lt; 8 &gt;) - O] _n -
In Formula 4,
R8 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n is an integer of 2 or more;
[Chemical Formula 5]
D (R 8) ₃
In Formula 5,
R8 is as defined in Formula 4 above;
D is aluminum or boron;
[Chemical Formula 6]
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 6,
L is a neutral or cationic Lewis acid;
H is a hydrogen atom;
Z is a Group 13 element;
A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .
The olefin monomer or comonomer according to claim 1, wherein the olefin monomer or comonomer is at least one selected from the group consisting of ethylene, alpha-olefin, cyclic olefin, dienolefin monomer and triene olefin monomer Gt;
The process of claim 1 wherein said olefin monomer or comonomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Dodecene, 1-tetradecene, 1-hexadecene, 1-aotocene, norbornene, norbornadiene, ethylidene norbornene, phenyl novodene, vinyl novodene, dicyclopentadiene, 1 A polyolefin-based resin comprising at least one member selected from the group consisting of 4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, &Lt; / RTI &gt;
The method according to claim 1, wherein in the step of polymerizing the olefin monomer or the comonomer,
Further comprising the step of feeding 0.4 to 5 times of a scavenger to the reactor based on the molar ratio of the total amount of water introduced into the reactor.
The method for producing a polyolefin-based polymer according to claim 5, wherein the scavenger comprises a compound represented by the following general formula (7):
(7)
D (R) ₃
In Formula 7,
R may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
D is aluminum or boron.
delete The method according to claim 1, wherein the continuous solution polymerization process uses a solvent, and the solvent is at least one selected from the group consisting of an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, an aromatic hydrocarbon solvent, and a hydrocarbon solvent substituted with a chlorine atom By weight based on the total weight of the polyolefin-based copolymer.
The process for producing a polyolefin-based copolymer according to claim 1, wherein the step of polymerizing the olefin monomer or the comonomer is carried out at a temperature of 100 ° C to 200 ° C for 5 minutes to 10 minutes under a pressure of 10 bar to 100 bar.
A polyolefin-based copolymer obtained by copolymerizing at least one olefin monomer or a comonomer,
A polyolefin-based copolymer produced by the process according to any one of claims 1 to 6 and 8 to 9, having a density of 0.860 to 0.920 g / cm3 and a molecular weight distribution (Mw / Mn) coalescence.
The polyolefin-based copolymer according to claim 10, wherein the melt index (MI, 2.16 kg) is 0.1 to 1000 g / 10 min.

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