KR101011497B1 - Process for the preparation of very low density polyolefin copolymers - Google Patents

Abstract

The present invention relates to a method for producing an ultra low density polyolefin copolymer using a catalyst composition comprising a transition metal compound. Specifically, the method for producing an ultra low density polyolefin copolymer according to the present invention uses a catalyst composition containing a transition metal compound containing a quinoline group, and a method for producing an ultra low density polyolefin copolymer having a low density value even at a high polymerization temperature. It is about.

Quinoline group, transition metal compound, ultra low density polyolefin copolymer

Description

Production method of ultra low density polyolefin copolymer {PROCESS FOR THE PREPARATION OF VERY LOW DENSITY POLYOLEFIN COPOLYMERS}

1 is a diagram of one continuous hot solution polymerization process to which the present invention may be applied.

The present invention relates to a method for producing an ultra low density polyolefin copolymer.

In general, in the existing production method for producing an ultra low density polyolefin copolymer, it is known that the polymerization temperature is mainly 120 ° C. or less in order to produce an ultra low density polyolefin copolymer having a low density value of 0.860 g / cc.

However, the production method using the polymerization temperature has a problem that the process for producing the ultra low density polyolefin copolymer is complicated and the operating conditions are not easy.

It is an object of the present invention to provide a method for preparing an ultra low density polyolefin copolymer which can be prepared even at a high polymerization temperature using a catalyst composition comprising a transition metal compound.

The present invention provides a method for producing an ultra low density polyolefin copolymer having a polymerization temperature of 160 to 210 ° C. in the method for producing an ultra low density polyolefin copolymer using a catalyst composition containing a transition metal compound.

The present invention also provides an ultra low density polyolefin copolymer prepared by the method for producing an ultra low density polyolefin copolymer.

Hereinafter, the present invention will be described in detail.

The present invention provides a method for producing an ultra low density polyolefin copolymer having a polymerization temperature of 160 to 210 ° C. in the method for producing an ultra low density polyolefin copolymer using a catalyst composition containing a transition metal compound.

Ultralow density polyolefin copolymers generally refer to polyolefin polymers having a density value of 0.860 to 0.900 g / cc.

The method for producing an ultra low density polyolefin copolymer having a polymerization temperature of 160 to 210 ° C. according to the present invention has a capacity of a freezer used to remove the heat of reaction when compared to a method for preparing an ultra low density polyolefin copolymer having a low polymerization temperature. Since the high temperature is required in the product and solvent separation step after the polymerization reaction, the manufacturing method of the ultra low density polyolefin copolymer according to the present invention reduces the energy cost in the entire process of preparing the ultra low density polyolefin copolymer. can do. In addition, since the viscosity of the copolymer produced by the high polymerization temperature is lowered, it is easy to transport the product, and there is an effect of increasing the unit yield of the ultra low density polyolefin copolymer due to the high mixing effect.

In the present invention, the transition metal compound constituting the catalyst composition is preferably a transition metal compound represented by the following formula (1).

In Chemical Formula 1,

R1 and R2 may be the same as or different from each other, and each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; Aryl group; Silyl groups; Alkenyl groups having 2 to 20 carbon atoms; Alkylaryl group; Arylalkyl group; Or a metalloid of a Group 14 metal substituted with hydrocarbyl; R 1 and R 2 may be linked to each other to form an aliphatic or aromatic ring;

R 3 may be the same as or different from each other, and each independently hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; Aryl group; An alkoxy group; Aryloxy group; Or an amido group; Two or more R3 in said R3 may be connected to each other to form an aliphatic or aromatic ring;

CY ₁ is a substituted or unsubstituted aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q ₁ and Q ₂ may be the same as or different from each other, and each independently halogen; An alkyl group having 1 to 20 carbon atoms; Alkyl amido groups; Aryl amido groups; Alkenyl groups having 2 to 20 carbon atoms; Aryl group; Alkylaryl group; Arylalkyl group; Or alkylidene Q ₁ and Q ₂ are linked to each other.

In the present invention, the general formula (1) is preferably represented by the following formula (2).

In Chemical Formula 2,

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

R6 is an alkyl group having 1 to 20 carbon atoms; Aryl group; Alkenyl groups having 2 to 20 carbon atoms; Alkylaryl group; Arylalkyl group; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group; Or an amido group; Two or more R6 in said R6 may be linked to each other to form an aliphatic or aromatic ring;

Q ₃ and Q ₄ may be the same as or different from each other, and each independently halogen; An alkyl group having 1 to 20 carbon atoms; Alkyl amido groups; Or an aryl amido group;

M is a Group 4 transition metal.

In addition, in the present invention, Chemical Formula 1 is preferably represented by one of the following structural formulas.

In the above structural formula,

R7 may be the same as or different from each other, and each independently hydrogen or a methyl group,

Q ₅ and Q ₆ may be the same or different from each other, and are each independently a methyl group, a dimethylamido group or a chloride.

The catalyst composition including the transition metal compound of the present invention may include one or more of the promoter compounds represented by the following Chemical Formula 3, Chemical Formula 4 or Chemical Formula 5.

-[Al (R8) -O] _n-

In Chemical Formula 3,

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;

D (R8) ₃

In Chemical Formula 4,

R8 is as defined in Formula 3 above;

D is aluminum or boron;

_{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} -

In Formula 5,

L is a neutral or cationic Lewis acid;

H is a hydrogen atom;

Z is a Group 13 element;

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

Examples of the compound represented by Formula 3 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.

Examples of the compound represented by Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound of Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, Trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-tripololomethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentaflo Rophenylboron, N, N-diethylamyldium tetraphenylboron, N, N-diethylanilidedium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium Tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium Niumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum , Tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium Tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium Tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, N, N-die It shall not help tetraphenyl boron, triphenyl car I Titanium tetra (p- methylphenyl to triple) and the like boron, triphenyl car I phenyl Titanium tetra-penta flow boron.

Catalyst composition comprising a transition metal compound that can be used in the present invention, as a first method

1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 3 or Formula 4 to obtain a mixture; And

2) adding a compound represented by Chemical Formula 5 to the mixture

It may be prepared by a method comprising a.

In addition, the catalyst composition including the transition metal compound that can be used in the present invention may be prepared by a method of contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 3 as a second method.

In the case of the first method of the method for preparing the catalyst composition, the molar ratio of (transition metal compound represented by Formula 1 / compound represented by Formula 3 or Formula 4) is preferably 1 / 5,000 ~ 1/2 More preferably 1 / 1,000 to 1/10, and most preferably 1/500 to 1/20. When the molar ratio of (transition metal compound represented by Formula 1 / compound represented by Formula 3 or Formula 4) is more than 1/2, the amount of alkylating agent is so small that alkylation of the metal compound does not proceed completely. If the molar ratio is less than 1 / 5,000, the alkylation of the metal compound is made, but there is a problem that the activation of the alkylated metal compound is not fully achieved due to the side reaction between the remaining excess alkylating agent and the activator of the formula (5). . In addition, the molar ratio of the (transition metal compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 5) is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 / 5 to 1. When the molar ratio of (transition metal compound represented by Chemical Formula 1 / compound represented by Chemical Formula 5) is greater than 1, the amount of the activator is relatively small, so that the catalyst composition is not formed due to complete activation of the metal compound. If the molar ratio of less than 1/25, and the molar ratio is less than 1/25, the metal compound is fully activated, but the remaining excess activator does not economically cost the unit of the catalyst composition or the purity of the resulting polymer is poor have.

In the second method of the method for preparing the catalyst composition, the molar ratio of (transition metal compound represented by Formula 1 / compound represented by Formula 3) is preferably 1 / 10,000 to 1/10, more preferably Is 1 / 5,000 to 1/100, most preferably 1 / 2,000 to 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, and thus the activity of the resulting catalyst composition is inferior. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economically low or the purity of the resulting polymer is inferior with the excess activator remaining.

In preparing a catalyst composition including the transition metal compound, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used. In addition, the transition metal compound and the promoter may be used in a form supported on silica or alumina.

The method for preparing an ultra low density polyolefin copolymer of the present invention uses a catalyst composition containing a transition metal, and the ultra low density polyolefin copolymer may be prepared by a general method known in the art, except that the polymerization temperature is 160 to 210 ° C. Can be.

Hereinafter, the present invention will be described based on the continuous high temperature solution polymerization process method shown in FIG. 1. However, the scope of the present invention is not limited thereby.

A) polymerization process

The polymerization process is carried out by introduction of a monomer and a catalyst composition comprising the above transition metal compound and a promoter on a reactor. In the case of copolymers, comonomers are additionally introduced into the reactor. In the case of solution phase and slurry phase polymerization, a solvent is injected onto the reactor. Therefore, in the case of solution polymerization, a mixture of a solvent, a catalyst composition, a monomer and a comonomer is present in the reactor.

In the method for producing an ultra low density polyolefin copolymer of the present invention, examples of the olefin monomer or comonomer which can be used include ethylene, alpha-olefin, cyclic olefin, and the like, and a diene olefin monomer having two or more double bonds. Or a triene olefin monomer can also be used.

Specific examples of the monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, nobonadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, etc., These monomers may be mixed and copolymerized.

More specifically, the monomer constituting the ultra low density polyolefin copolymer of the present invention is ethylene, and the comonomer is selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene It is preferable.

The method for preparing the ultra low density polyolefin copolymer is carried out in the presence of a solvent, and in the case where the monomer is a mixture of two monomers, the first monomer is ethylene, the second monomer is 1-butene, and the solvent is n-hexane. desirable.

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 the (monomer / comonomer) or the (first monomer / second monomer) exceeds 100, the density of the produced polymer is increased, making it difficult to prepare a low density polymer. If it is less than 1/100, the amount of unreacted comonomer or second monomer is increased, and the conversion rate is lowered, resulting in an increase in process recycle.

The molar ratio of monomer to solvent suitable for the present invention 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 / solvent) is 1 / 10,000-10, preferably 1 / 100-5, most preferably 1 / 20-1. If the molar ratio of (monomer / solvent) is greater than 10, the amount of solvent is too small to increase the viscosity of the fluid, which is a problem in the transfer of the resulting polymer, and if the molar ratio is less than 1 / 100,000, the amount of solvent There are many problems, such as the increase in equipment and the increase in energy costs due to the recirculation of the purification of the solvent.

The solvent is introduced into the reactor at a temperature of -40 ~ 150 ℃ using a heater or a freezer, and the polymerization reaction is started with the monomer and the catalyst composition. If the temperature of the solvent is less than -40 ℃, there will be some differences depending on the reaction amount, but the temperature of the solvent is too low, the reaction temperature is also accompanied by a problem that is difficult to control the temperature, the temperature of the solvent 150 ℃ If it exceeds, the solvent temperature is too high, there is a problem that the heat removal of the reaction heat due to the reaction is difficult.

The high capacity pump raises the pressure above 50 bar to supply the feeds (solvent, monomer, catalyst composition, etc.), thereby allowing the mixture of feeds to pass through without additional pumping between the reactor arrangement, pressure dropping device and separator. Can be.

The internal pressure of the reactor suitable for the present invention is 1 to 300 bar, preferably 30 to 200 bar, most preferably about 50 to 100 bar. When the internal pressure is less than 1 bar, the reaction rate is low, productivity is low, and there is a problem due to evaporation of the solvent used.

The polymer produced in the reactor is maintained at a concentration of less than 20 mass% in the solvent and is passed to the primary solvent separation process for solvent removal after a short residence time.

The residence time of the polymers suitable for the present invention in the reactor is 1 minute to 10 hours, preferably 3 minutes to 1 hour, most preferably 5 minutes to 30 minutes. If the residence time is less than 1 minute, there is a problem such as a decrease in productivity and a loss of the catalyst due to a short residence time, such as an increase in the manufacturing cost. It becomes large, and accordingly, there is a problem of an increase in equipment costs.

B) Solvent Separation Process

The solvent separation process is performed by varying the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. The polymer solution transferred from the reactor is heated to about 200 ~ 230 ℃ through a heater and then the pressure is lowered through a pressure drop device to vaporize unreacted raw materials and solvent in the primary separator.

The pressure in the separator suitable for the present invention is suitably 1 to 30 bar, preferably 1 to 10 bar and most preferably 3 to 8 bar. If the pressure in the separator is less than 1bar, the content of the polymer is increased, there is a problem in the transfer, if the pressure in the separator exceeds 30 bar there is a problem that the separation of the solvent used in the polymerization process is difficult.

In addition, the temperature in the separator is suitable for 150 ~ 250 ℃, preferably 170 ~ 230 ℃, most preferably 180 ~ 230 ℃. If the temperature in the separator is less than 150 ℃, the viscosity of the polymer and mixtures thereof is increased, there is a problem in the transfer, if the temperature exceeds 250 ℃, there is a problem of discoloration due to carbonization of the polymer due to the modification according to the high temperature.

The solvent vaporized in the separator can be recycled to the condensed reactor in the overhead system. After the primary solvent separation process to obtain a polymer solution concentrated to 65%, which is transferred to the secondary separator by a transfer pump through a heater, the separation process for the residual solvent in the secondary separator. In order to prevent the deformation of the polymer due to the high temperature while passing through the heater, a heat stabilizer is added and a reaction inhibitor is added to the heater together with the heat stabilizer to suppress the reaction of the polymer due to the residual activity of the activator present in the polymer solution. Inject. The residual solvent in the polymer solution injected into the secondary 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. Solvents and other unreacted monomers vaporized in the secondary separation process can be sent to a recovery process and reused after purification.

C) recovery process

The organic solvent added with the raw material to the polymerization process may be recycled to the polymerization process together with the unreacted raw material in the primary solvent separation process. However, the solvent recovered in the secondary solvent separation process contains a large amount of water that acts as a catalyst poison in the solvent due to contamination due to the incorporation of a reaction inhibitor to stop the catalytic activity and steam supply from the vacuum pump. Should be reused.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these Examples are only for illustrating the present invention, and the scope of the present invention is not limited thereby.

<Ethylene and 1- Butene  Copolymerization>

< Comparative example  1 ~ 2> Ethylene and 1- Butene  Copolymerization

A dimethylsilyl (t-butylamido) (tetramethylcyclopentadienyl) titanium dichloride compound was purchased from Boulder Scientific, USA, and used for ethylene copolymerization after methylation. Copolymerization conditions of ethylene and 1-butene are shown in Table 1 below, and experimental results of the density of the prepared copolymer are shown in Table 2 below.

< Example  1 to 8> Ethylene and 1- by Continuous Solution Process Butene  Copolymerization

In a 1 L continuous stirred reactor preheated to 100-150 ^° C., hexane, 1-butene and ethylene monomers as solvent were fed at a pressure of 89 bar. [(7-methyl-1,2,3,4-tetrahydroquinolin-8-yl) trimethylcyclopentadienyl-eta5, kappa-N] titanium dimethyl treated with triisobutylaluminum compound from catalyst storage tank Octadecylmethylammonium tetrakis (pentafluorophenyl) borate was fed to the reactor as a compound (Al / Ti = 25) and as a cocatalyst to proceed with the copolymerization reaction. The polymerization was carried out at a relatively high temperature of 161 ~ 205 ℃ and the polymer solution formed by the copolymerization reaction was decompressed to 7bar at the rear end of the reactor, and then sent to a solvent separator preheated to 230 ^° C. most of the solvent by a solvent separation process Removed. The copolymer sent to the secondary separator by the pump completely removed the residual solvent by a vacuum pump, and then passed through cooling water and a cutter to obtain granulated polymer. Copolymerization conditions of ethylene and 1-butene according to the present invention are shown in Table 1 below, and the experimental results of the density of the prepared copolymer are shown in Table 2 below.

To the samples treated with a density (Density) is an antioxidant (1,000ppm) of the copolymer prepared in the experimental results shown in Table 2 180 ^o C press mold (Mold Press) to a thickness 3mm, radius 2cm sheet preparation and 10 ^o to the Cool to C / min and measure on a Mettler balance.

Main catalyst: [(7-methyl-1,2,3,4-tetrahydroquinolin-8-yl) trimethylcyclopentadienyl-eta5, kappa-N] titanium dimethyl compound treated with triisobutylaluminum compound (Al / Ti = 25),

Promoter: Octadecylmethylammonium tetrakis (pentafluorophenyl) borate,

B / Ti: Ti of promoter / catalyst

As the copolymer according to the present invention can be seen in the experimental results of Table 2, it can be seen that the copolymer having a wide range of density of 0.860 ~ 0.897 g / cc can be produced according to the polymerization conditions. The density of the copolymer largely depends on the polymerization temperature and the composition ratio of ethylene / butene, and the lower the polymerization temperature in the reactor, the higher the ratio of butene to ethylene in the feed composition is. In particular, for Examples 6-8, the copolymers produced at high temperatures of 184.5 ° C., 195 ° C. and 205 ° C. had low density values of 0.860 g / cc, 0.864 g / cc and 0.861 g / cc, respectively. It can be seen that an ultra low density polyethylene copolymer having

When preparing an ultra low density polyolefin copolymer through the method according to the present invention, it is possible to produce an ultra low density polyolefin copolymer having a low density value even at a high polymerization temperature.

Claims (23)

As a polymerization process for producing an ultra low density polyolefin copolymer using a transition metal compound represented by the formula (1) and a catalyst composition containing at least one of the cocatalyst compound represented by the following formula (3), (4) or (5), Method for producing an ultra low density polyolefin copolymer, characterized in that the polymerization temperature is 160 ~ 210 ℃: [Formula 1]

In Chemical Formula 1, R1 and R2 may be the same as or different from each other, and each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; Aryl group; Silyl groups; Alkenyl groups having 2 to 20 carbon atoms; Alkylaryl group; Arylalkyl group; Or a metalloid of a Group 14 metal substituted with hydrocarbyl; R 1 and R 2 may be linked to each other to form an aliphatic or aromatic ring; R 3 may be the same as or different from each other, and each independently hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; Aryl group; An alkoxy group; Aryloxy group; Or an amido group; Two or more R3 in said R3 may be connected to each other to form an aliphatic or aromatic ring; CY ₁ is a substituted or unsubstituted aliphatic or aromatic ring; M is a Group 4 transition metal; Q ₁ and Q ₂ may be the same as or different from each other, and each independently halogen; An alkyl group having 1 to 20 carbon atoms; Alkyl amido groups; Aryl amido groups; Alkenyl groups having 2 to 20 carbon atoms; Aryl group; Alkylaryl group; Arylalkyl group; Or Q ₁ and Q ₂ are alkylidene linked to each other; (3) -[Al (R8) -O] _n- In Chemical Formula 3, 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; [Formula 4] D (R8) ₃ In Chemical Formula 4, R8 is as defined in Formula 3 above; D is aluminum or boron; [Chemical Formula 5] _{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} - In Formula 5, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A may be the same or different from each other, and each independently is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with one or more hydrogen atoms, halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. . delete The method of claim 1, wherein the transition metal compound is represented by the following Chemical Formula 2. [Formula 2]

In Chemical Formula 2, R4 and R5 may be the same as or different from each other, and each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; Aryl group; Or a silyl group; R6 is an alkyl group having 1 to 20 carbon atoms; Aryl group; Alkenyl groups having 2 to 20 carbon atoms; Alkylaryl group; Arylalkyl group; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group; Or an amido group; Two or more R6 in said R6 may be linked to each other to form an aliphatic or aromatic ring; Q ₃ and Q ₄ may be the same as or different from each other, and each independently halogen; An alkyl group having 1 to 20 carbon atoms; Alkyl amido groups; Or an aryl amido group; M is a Group 4 transition metal. The method of claim 1, wherein the transition metal compound is represented by any one of the following structural formulas:

In the above structural formula, R7 may be the same as or different from each other, and each independently hydrogen or a methyl group, Q ₅ and Q ₆ may be the same or different from each other, and are each independently a methyl group, a dimethylamido group or a chloride. delete The method of claim 1, wherein the compound represented by Chemical Formula 3 is selected from methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane. The method of claim 1, wherein the compound represented by the formula (4) is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tri Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxy Seed, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron, characterized in that the production method of ultra-low density polyolefin copolymer. The compound represented by the formula (5) is triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p -Tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-tripololomethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributyl Ammonium tetrapentafluorophenyl boron, N, N-diethyl amyldium tetraphenyl boron, N, N-diethylanilidedium tetraphenyl boron, N, N-diethylanilinium tetrapentafluorophenyl boron , Diethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl al Aluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p- Dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-di Ethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, Tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluorome Phenyl) boron, N, N-diethylanilinium tetraphenylboron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron and triphenylcarbonium tetrapentafluorophenyl boron A method for producing an ultra low density polyolefin copolymer. The catalyst composition of claim 1, wherein the catalyst composition comprising the transition metal compound 1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 3 or Formula 4 to obtain a mixture; And 2) adding a compound represented by Chemical Formula 5 to the mixture Method for producing an ultra low density polyolefin copolymer, characterized in that it is produced by a method comprising a. The ultra low density polyolefin air according to claim 9, wherein the molar ratio of the transition metal compound represented by Chemical Formula 1 / compound represented by Chemical Formula 3 or Chemical Formula 1 in step 1) is 1 / 5,000 to 1/2. Process for the preparation of coalescing. The method of claim 9, wherein the molar ratio of the transition metal compound represented by the formula (1) / compound represented by the formula (5) in the step 2) is 1/25 to 1. The method of claim 1, wherein the catalyst composition comprising the transition metal compound is prepared by a method of contacting the transition metal compound represented by the formula (1) and the compound represented by the formula (3) of the ultra-low density polyolefin copolymer Way. The method for producing an ultra low density polyolefin copolymer according to claim 12, wherein a molar ratio of the (transition metal compound represented by Chemical Formula 1 / compound represented by Chemical Formula 3) is 1 / 10,000 to 1/10. The method of claim 1, wherein an olefinic monomer, or an olefinic monomer and a comonomer is used for the polymerization of the ultra low density polyolefin copolymer, and the olefinic monomer or the comonomer is ethylene, alpha-olefin, cyclic olefin, diene olefin or tree It is an olefin, The manufacturing method of the ultra low density polyolefin copolymer characterized by the above-mentioned. The method according to claim 14, wherein the olefin monomer or comonomer is ethylene, propylene 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1- Undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1, 4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene or 3-chloromethylstyrene. The method of claim 1, wherein an olefin monomer and a comonomer are used for the polymerization of the ultra low density polyolefin copolymer, and the ultra low density polyolefin air is characterized in that the molar ratio of (olefin monomer / comonomer) is 1/100 to 100. Process for the preparation of coalescing. The method of claim 1, wherein a solvent is added to the reactor at a temperature of −40 to 150 ° C. during the polymerization of the ultra low density polyolefin copolymer. The method for producing an ultra low density polyolefin copolymer according to claim 17, wherein the molar ratio of (monomer / solvent) used for the polymerization of the ultra low density polyolefin copolymer is 1 / 10,000 to 10. The method of claim 1, wherein the polymerization of the ultra low density polyolefin copolymer is carried out by adding a reactant to the reactor, and the internal pressure of the reactor is 1 to 300 bar. The method of claim 19, wherein the residence time of the reactant in the reactor during polymerization of the ultra low density polyolefin copolymer is 1 minute to 10 hours. The method of claim 1, wherein a solvent separation process is performed in a separator after the polymerization process of the ultra low density polyolefin copolymer, and the pressure in the separator is 1 to 30 bar. The method of claim 21, wherein the temperature in the separator during the solvent separation step after the polymerization step of the ultra low density polyolefin copolymer is 150 ~ 250 ℃. delete

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