KR101878047B1 - Method of Manufacturing Brush-copolymerized Polymer Compound - Google Patents

Abstract

In the method of producing a polymer compound having a brush structure, the molecular weight, chemical composition, physical property, and structure of the polymer can be controlled by designing the polymer at the molecular level. Accordingly, A method for producing a polymer compound having a brush structure capable of being designed in accordance with the present invention. (A) introducing at least one monomer selected from ethylene, olefins and dienes into a first reactor; (b) introducing a first catalyst into the reactor to perform main chain polymerization; (c) introducing an olefin monomer and a second catalyst into a second reactor to perform polymerization; And (d) introducing a main chain polymerized polymer of step (b) and a polymerized olefin polymer of step (c) into a third reactor, thereby polymerizing the polymer. Wherein the molecular weight of the olefin polymer produced by the following formula (1) is controlled during the polymerization reaction, and then supplied to the third reactor of the step (d).
(Equation 1)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a polymer compound having a brush structure,

The present invention relates to a method for producing a polymer compound having a brush structure, and more particularly, to a method for manufacturing a polymer compound having a brush structure by controlling the molecular weight, chemical composition, physical properties and structure of the polymer by designing the polymer at a molecular level, The present invention relates to a method for producing a polymer compound having a brush structure that can be synthesized in a continuous reactor as a reaction is carried out in different reactors and a post-treatment step after graft polymerization is unnecessary.

Recently, polymer resins have been widely demanded in industrial fields of specialized and sophisticated materials such as electronic information field, energy related field, high performance structural material field, environment friendliness and biomedical field. In addition, social interest in plastic products used in everyday life is rising due to waste and environmental hormone problems and volatile organic compound (VOC) generation. In the case of soft PVC, dioxin is generated during incineration, It is urgent to find new environmentally friendly, soft, high-molecular-weight polymers that can solve serious problems such as environmental hormones caused by plasticizer dissolution.

In particular, in the medical field, development of a non-PVC polyolefin IV set without the concern of the safety threat of fetus and intensive care, the release of environmental hormones and the adsorption of drugs by the elution of PVC sap tube, DEHP (environmental hormone), the dissolution of environmental hormones and the adsorption problem of drugs Serious, new material development is urgent

However, the polyolefin-based material products developed and commercialized so far have a lack of flexibility (softening at room temperature or below) comparable to soft PVC and mechanical properties, and it is difficult to form the polyolefin-based material under the processing conditions of conventional molding machines. In addition, while achieving unique scratch resistance and abrasion resistance unique to soft PVC, it is a global challenge to find materials with cost competitiveness that can cope with low-priced soft PVC.

In order to precisely control the flexibility, the manufacturing technology of the flexible polymer material that meets these needs is to design the molecular structure of the polymer material itself more precisely, Polymerization control technology is required.

Particularly, "Tailor-made polymer production technology" for producing a polymer which can not be synthesized by conventional techniques can utilize a low-priced general-purpose monomer and an existing process in consideration of economical aspects, The molecular structure in the polymer is precisely designed from the micro to the macro structure so that the material requirement performance of the customer can be immediately reflected in the design of the polymer molecular structure and the so-called step growth polymerization can be obtained.

This "Tailor-made polymer manufacturing technology" is the first step of polymer primary structure. That is, through fine coordination polymerization, which is one of the fastest and most precise control methods for the contents, selectivity and sequence distribution of comonomers in the control of monomer content and stereoregularity, A main chain having a structure of a bidentate copolymer of a "pseudo-blocky" structure is formed, and in the second step, a side chain composed of a functional molecule is formed through a precursor radical or anionic polymerization, etc., chain, it is known as a technology capable of inducing differentiation by innovatively improving additional functions such as heat resistance, high strength and adhesiveness.

However, according to the prior art, it is necessary to carry out a step of preparing a polyolefin copolymer including a diene, then grafting the polystyrene by adjusting the conditions for anion polymerization, but it is difficult to apply it to a continuous process due to different reaction conditions This batch process or semi-batch process is required and is not applied to commercial process. Therefore, it is still required to develop a continuous polymerization process suitable for mass production of the polyolefin graft copolymer.

Japanese Patent Laid-Open No. 2610904 discloses a method of polymerizing an alpha-olefin with a Ziegler-Natta catalyst and then using an anionic polymerization initiator to cocycle a monomer. However, since a Ziegler-Natta catalyst is used, It is difficult to control the length of the polymerization initiator. The use of an anionic polymerization initiator restricts the kinds of side chains that can be used, has a very complicated polymerization condition, requires a large scale of equipment, and has a limitation in production cost.

EP-A-1170313 discloses a method for producing a cross-polymer by cross-linking an ethylene / olefin / diene with a norbornene catalyst using a metelocene catalyst followed by a nBuLi catalyst. The present invention has a disadvantage in that it is difficult to control the length and nature of the side chain by the nBuLi catalyst although the cross-polymer is produced through the second polymerization.

U.S. Patent No. 6,265, 493 discloses a polyolefin graft copolymer composition having a narrow molecular weight distribution derived from a linear copolymer of alpha olefins and divinylzhenes. In the present invention, a linear copolymer is prepared from an alpha olefin and a divinylbenzene, and then a cross-polymer is polymerized through a graft copolymer. However, since the polymerization temperature is low, it is difficult to apply to a solution process. It is difficult to apply it to the continuous process because the post-treatment step is required to perform the process.

U.S. Pat. No. 6,804,342 discloses cross-polymerized olefin / aromatic vinyl compounds / diene copolymers and their preparation. However, this patent also has a disadvantage in that grafting to the first reactant requires post-treatment, which is difficult to apply to continuous process.

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a process for separating a main chain synthesis reaction (first reaction) and a side chain synthesis reaction (second reaction) And to provide a production method capable of synthesizing a polymer composition having a brush structure in a continuous reactor.

(A) introducing at least one monomer selected from ethylene, olefins and dienes into a first reactor; (b) introducing a first catalyst into the reactor to perform main chain polymerization; (c) introducing an olefin monomer and a second catalyst into a second reactor to perform polymerization; And (d) introducing a main chain polymerized polymer of step (b) and a polymerized olefin polymer of step (c) into a third reactor, thereby polymerizing the polymer. Wherein the molecular weight of the olefin polymer produced by the following formula (1) is controlled during the polymerization reaction, and then supplied to the third reactor of the step (d).

(Equation 1)

(M is the molecular weight of the olefin polymer, Mo is the molecular weight of the olefin monomer, [M] is the concentration of the olefin monomer, and [I]

Also, the olefin of the step (a) and the step (c) may be selected from the group consisting of a C2 to C20 alpha olefin, a C3 to C20 cycloolefin, a C3 to C20 cyclodiolefin, a substituted styrene or an unsubstituted styrene And a manufacturing method thereof.

The olefins of steps (a) and (c) may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, , 1-octene, cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbonene, methyl-2-norbornene, Substituted styrene in which an alkyl group of 1 to 10 carbon atoms, an alkoxy group, a halogen group, an amine group, a silyl group, a haloalkyl group, etc. are bonded to a benzene ring of styrene Styrene) or a mixture thereof. The present invention also provides a method for producing a polymer compound.

The olefin of step (a) is 1-octene and the olefin of step (c) is styrene.

Further, the diene may be at least one selected from the group consisting of 1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, ethylidene, norbornene, dicyclopentadiene norbornene 1-cyclohexene, 1-vinyl-1-cyclohexene, o-divinylbenzene, p-divinylbenzene, 2-vinyl-1-cyclohexene, Divinylbenzene, and m-divinylbenzene. The present invention also provides a process for producing a high molecular compound.

And wherein the diene is divinylbenzene.

And the first catalyst is a transition metal catalyst compound.

And the transition metal catalyst compound is a metallocene catalyst. The present invention also provides a method for preparing the same.

And the metallocene catalyst has a general structure represented by the following general formula (1).

(Formula 1)

(M is titanium (Ti), zirconium (Zr) or hafnium (Hf);

Q1 and Q2 are each independently halogen or (C1-C4) alkyl;

R 1 to R 13 are each independently hydrogen or; (C1-C20) alkyl, with or without an acetal, ketal or ether group, wherein at least one of R3 and R4 is (C1-C20) alkyl.

And Q1 and Q2 are each independently methyl or chlorine; R 1, R 2, R 3, R 4 and R 5 are each independently hydrogen or methyl; Wherein R6, R7, R8, R9, R10, R11, R12 and R13 are each hydrogen.

And at least one of R 3 and R 4 is methyl, and R 5 is methyl.

And an equivalence ratio of diene to ethylene and olefin in step (a) is 1: 0.1 to 1:10.

Wherein the equivalence ratio of the diene to the ethylene and the olefin in the step (a) is 1: 0.1 to 1: 5.

And the weight average molecular weight (Mw) of the polymer produced by the main chain polymerization in the step (b) is 10,000 to 1,000,000.

And the weight average molecular weight (Mw) of the polymer produced by the main chain polymerization in the step (b) is 50,000 to 800,000.

And the molecular weight distribution (Mw / Mn) of the polymer produced by the main chain polymerization in the step (b) is 1 to 10. The present invention also provides a method for producing a polymer.

And a molecular weight distribution (Mw / Mn) of the polymer produced by the main chain polymerization in the step (b) is 1.5 to 8. The present invention also provides a method for producing a polymer.

In addition, the step (b) may further include adding a cocatalyst in addition to the first catalyst.

Wherein the cocatalyst is a compound represented by the following general formula (2) or (3).

(2)

[LH] ⁺ [Z (A) ₄ ] ^-

(C6-C20) aryl or (C1-C20) alkyl, wherein L is a neutral or cationic Lewis acid, Z is a Group 13 element, A is (C6-C20) aryl or Alkyl substituted or unsubstituted with halogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, or (C6-C20)

(Formula 3)

[L] ⁺ [Z (A) ₄ ] ^-

(C6-C20) aryl or (C1-C20) alkyl, wherein L is a neutral or cationic Lewis acid, Z is a Group 13 element, A is (C6-C20) aryl or Alkyl substituted or unsubstituted with halogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, or (C6-C20)

Cocatalyst compounds also represented by the general formula (2) [LH] ⁺ is dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - the polymeric compound, characterized in that Of the present invention.

Also, the promoter compound represented by the above formula (2) may be prepared by reacting trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate ), Tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate (Ttri (n-butyl) ammonium tetrakis ) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t- butyl Dimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate (N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6- Dimethylanilinium tetrakis (4- (t-triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate (N, N-dimethylanilinium tetrakis (4- , 6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate (N, N-dimethylanilinium pentafluorophenoxytris N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate (N, N-diethylanilinium tetrakis (pentafluorophenyl) dimethyl-2 , 4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (2,3,5,6-tetrafluorophenyl) borate, N, N-diethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophcnyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetra (N-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) ) Ammonium borate, ammonium tertiary amines such as dimethyl t-butyl ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate), N, N-di Anilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate (N, N-diethylanilinium tetrakis), N, N-dimethyl 2,4,6 (N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate) and trimethyl anilinium tetrakis A dialkylammonium compound, and a dialkylammonium compound. The present invention also provides a method for producing a polymer compound.

Further co-catalyst compound represented by the formula 3 is [L] ⁺ is _{[(C 6 H 5) 3} C] + , and wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - And a method for producing the polymer compound.

Also, the promoter compound represented by Formula 3 is at least one selected from the group consisting of trialkylphosphonium, dialkyloxonium, dialkylsulfonium, and carbonium salts, and provides a method for preparing the polymer compound .

The trialkylphosphonium may be at least one selected from the group consisting of triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolylphosphonium tetrakis (pentafluorophenyl) borate (tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate) or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) The present invention also provides a method for producing a polymer compound.

Also, the dialkyloxonium is preferably selected from the group consisting of diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, or di (2,6-dimethylphenyloxonium tetrakis (pentafluorophenyl) borate) By weight based on the total weight of the composition.

Also, the dialkylsulfonium may be used in combination with diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate) or bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) And a method for producing the polymer compound.

The carbonium salt may be selected from the group consisting of tropylium tetrakis (pentafluorophenyl) borate, triphenylmethylcarbenium tetrakis (pentafluorophenyl) borate, or triphenylmethylcarbenium tetrakis Benzene (diazonium) tetrakis (pentafluorophenyl) borate. The present invention also provides a method for producing a polymer compound.

And the ratio of the co-catalyst compound: the first catalyst is 1: 1 to 1: 100,000.

Also, the monomers of (a) and (c) may be supplied in a slurry, a liquid phase, a gas phase or a bulk phase.

Also, the liquid or slurry monomer is mixed with an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, or a mixed solvent thereof.

The aliphatic hydrocarbon solvent may be selected from the group consisting of butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, The present invention provides a process for preparing a polymer compound characterized in that the polymer is a polymer selected from the group consisting of Undecane, Dodecane, Cyclopentane, Methylcyclopentane, and Cyclohexane.

The aromatic hydrocarbon solvent may be at least one selected from the group consisting of benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, and chlorobenzene. And a method for producing the polymer compound.

The halogenated aliphatic hydrocarbon solvent may be at least one selected from the group consisting of dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, and 1,2-dichloroethane (1, 2-dichloroethane). ≪ / RTI >

The amount of the first catalyst added in step (b) is 1 × 10 ^-8 to 1 mol / L based on the concentration of the central metal (M) in the main catalyst compound per unit volume L of the monomer. Of the present invention.

The main chain polymerization in the step (b) is carried out at a temperature of 50 to 200 ° C and a pressure of 1 to 3000 atm.

And the polymerization in step (c) is carried out at a temperature of 20 to 100 ° C.

And the second catalyst is a compound represented by the following general formula (4).

(Formula 4)

[P-Li]

(P is (C1-C20) alkyl)

And the side chain polymerization in step (d) is performed at a temperature of 20 to 200 ° C.

And the weight average molecular weight of the polymer compound produced by the side chain polymerization in the step (d) is 500 to 500,000.

And the molecular weight distribution of the polymer compound produced by the side chain polymerization in the step (d) is 1 to 10. The present invention also provides a method for producing the polymer compound.

And the steps (a) to (d) are performed in a continuous manner.

The monomer feed rate in steps (a) and (c) is 0.01 to 100 kg / hr.

And the feed rate of the first catalyst and the second catalyst is 0.001 to 100 mmol / hr.

(E) recovering the reaction solution after step (d), and (f) recovering unreacted monomers. The present invention also provides a method for preparing a polymeric compound.

And the molecular weight (Mn) of the olefin polymer fed to the step (d) is 500 to 15,000.

According to the present invention, the raw material component of the present invention is a non-halogen and non-polar material, and as a polymer, a harmful remnant component is not included in polymerization, and the structure of the polymer itself is controlled to impart softness and other performance, And other environmentally friendly materials that do not require harmful additives.

In addition, the polymers synthesized with anions have unique characteristics of "living" polymerization in which the molecular weight can be well controlled, the molecular weight distribution is narrow, and the anion growth chain does not easily disappear. Therefore, the polymer to be grafted to the main chain is controlled by initiator and monomer And it can be applied to a continuous process by a method of reacting with a polyolefin copolymer including a diene. It is possible to synthesize a polymer composition having a more uniform composition according to the above method.

1 is a schematic view of a method for producing a polymer composition according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The inventors of the present invention have observed that the use thereof is limited due to the waste of conventional thermoplastic elastomers, the problem of environmental hormones, the generation of VOCs, and so on. As a result of intensive studies, it has been found that ethylene, styrene monomer, When a polymer compound having a bristle structure is prepared by crosslinking after copolymerization, a polarizing element and a halogen element are not used while having a physical property similar to that of a conventional thermoplastic elastomer, and a plasticizer that leaves a harmful residue at the time of polymerization is not used It is possible to minimize the influence on the environment during use, leading to the present invention.

Accordingly, the present invention provides a process for the production of a copolymer comprising: (a) introducing at least one monomer selected from ethylene, olefins and dienes into a first reactor; (b) introducing a first catalyst into the reactor to perform main chain polymerization; (c) introducing an olefin monomer and a second catalyst into a second reactor to perform polymerization; And (d) introducing a main chain polymerized polymer of step (b) and a polymerized olefin polymer of step (c) into a third reactor, thereby polymerizing the polymer; and (c) , The molecular weight of the olefin polymer formed by the following formula (1) is controlled and supplied to the third reactor of the step (d).

(Equation 1)

(M is the molecular weight of the olefin polymer, Mo is the molecular weight of the olefin monomer, [M] is the concentration of the olefin monomer, and [I]

In the present invention, the olefins of steps (a) and (c) may be selected from the group consisting of (C 2 -C 20) α-olefin, (C 3 -C 20) cycloolefin, Cyclohexane-substituted styrenes, cyclodiolefin substituted styrenes and unsubstituted styrenes.

Preferably, the olefins of steps (a) and (c) are selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, Hexene, 1-octene, cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbonene, methyl-2-norbornene, A substituted or unsubstituted benzyl ring in which an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a halogen group, an amine group, a silyl group, a haloalkyl group and the like is bonded to a benzene ring of methylene-2-norbornene, styrene, The olefin of step (a) may be 1-octene, and the olefin of step (c) may be styrene.

In the present invention, the diene is preferably a diene selected from the group consisting of 1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, ethylidene, 1-cyclohexene, 1-vinyl-1-cyclohexene, o-divinylbenzene, p-vinyl-1-cyclohexene, - divinylbenzene, and m-divinylbenzene, and may be preferably divinylbenzene.

In the present invention, the first catalyst may be a transition metal catalyst compound. Preferably a metallocene catalyst, more preferably a general structure of formula (1).

 (Formula 1)

(M is titanium (Ti), zirconium (Zr) or hafnium (Hf);

Q1 and Q2 are each independently halogen or (C1-C4) alkyl;

R 1 to R 13 are each independently hydrogen or; (C1-C20) alkyl, with or without an acetal, ketal or ether group, wherein at least one of R3 and R4 is (C1-C20) alkyl.

Also preferably, each of Q1 and Q2 is independently methyl or chlorine; R 1, R 2, R 3, R 4 and R 5 are each independently hydrogen or methyl; R6, R7, R8, R9, R10, R11, R12 and R13 may each be hydrogen, and most preferably at least one of R3 and R4 is methyl, and R5 may be methyl.

In the present invention, the content ratio of the diene monomer to ethylene and olefin in the step (a) is 1: 0.1 to 1:10, preferably 1: 0.1 to 1: 5, more preferably 1: 1: 1 < / RTI >

In the present invention, the weight average molecular weight (Mw) of the polymer produced by the main chain polymerization in the step (b) may be 10,000 to 1,000,000, preferably 50,000 to 800,000, and more preferably 50,000 to 500,000.

In the present invention, the molecular weight distribution (Mw / Mn) of the polymer produced by the main chain polymerization in the step (b) may be 1 to 10, preferably 1.5 to 8, more preferably 1.5 to 6

In the present invention, the density of the polymer produced by the main chain polymerization in the step (b) may be 0.850 to 0.920 g / ml.

In the step (b) of the present invention, a cocatalyst may be added in addition to the first catalyst, and the cocatalyst may be a compound represented by the following general formula (2) or (3).

 (2)

[LH] ⁺ [Z (A) ₄ ] ^-

(C6-C20) aryl or (C1-C20) alkyl, wherein L is a neutral or cationic Lewis acid, Z is a Group 13 element, A is (C6-C20) aryl or Alkyl substituted or unsubstituted with halogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, or (C6-C20)

(Formula 3)

[L] ⁺ [Z (A) ₄ ] ^-

(C6-C20) aryl or (C1-C20) alkyl, wherein L is a neutral or cationic Lewis acid, Z is a Group 13 element, A is (C6-C20) aryl or Alkyl substituted or unsubstituted with halogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, or (C6-C20)

Further co-catalyst compound represented by the above formula (II) [LH] ⁺ is dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - can be and preferably trimethyl (Pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (Pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, Ttri (n-butyl) ammonium tetrakis N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate, ), N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) (N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate), N, N-dimethylanilinium tetrakis (4- (t- butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate , N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis , 5,6-tetrafluorophenyl) borate (N, N-dimethylanilinium tetrakis (4- (triisopropysilyl) -2,3,5,6-tetrafluorophenyl) borate), N, N-dimethylanilinium pentafluorophenoxy N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate), N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) N, N-dimethylammonium tetrakis (2,3,5,6-tetrafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) (2,3,4,6-tetrafluorophenyl) borate), tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophonyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophcnyl) borate, tri (n-butyl) ammonium tetrakis tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) , 3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate (N, N-dimethylanilinium tetrakis) , 4,6-tetrafluorophenyl) borate (N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate), N, N-dimethyl 2,4,6-trimethylanilinium tetrakis , 3,4,6-tetrafluorophenyl) borate (N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate) and dialkylammonium Or more.

Further co-catalyst compound represented by the formula 3 is [L] ⁺ is _{[(C 6 H 5) 3} C] + , and wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - And preferably at least one selected from the group consisting of trialkylphosphonium, dialkyloxonium, dialkylsulfonium and carbonium salts.

The trialkylphosphonium may be at least one selected from the group consisting of triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolylphosphonium tetrakis (pentafluorophenyl) borate (tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) The dialkyl oxonium is preferably selected from the group consisting of diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) (pentafluorophenyl) borate), or di (2,6-dimethylphenyloxonium tetrakis (pentafluorophenyl) borate). The dialkylsulfonium , Diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate (di (o-tolyl) sulfonium tetrakis pentafluorophenyl) borate or bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the carbonium salt (Pentafluorophenyl) borate, triphenylmethylcarbenium tetrakis (pentafluorophenyl) borate, or benzene (diazonium) borate, Tetrakis (pentafluorophenyl) borate). ≪ / RTI >

In the present invention, the addition amount of the co-catalyst compound may be determined in consideration of the amount of the main catalyst compound to be added, the amount required for sufficiently activating the co-catalyst compound, and the like. Accordingly, the co-catalyst compound may be contained in a molar ratio of 1: 1 to 100,000, preferably 1: 1 to 10,000, more preferably 1: 1 to 5,000, relative to the main catalyst compound. More specifically, the promotor compound represented by Formula 2 or 3 may be used in an amount of 1: 1 to 100, preferably 1: 1 to 10, more preferably 1: 1 to 1, 4. ≪ / RTI >

In the present invention, the monomers of steps (a) and (c) may be supplied in slurry, liquid phase, gas phase or bulk phase. When the monomer is supplied in the form of a liquid or slurry, it is preferably mixed with an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent or a mixed solvent thereof, more preferably the aliphatic hydrocarbon solvent Butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, Wherein the aromatic hydrocarbon solvent is selected from the group consisting of Benzene, Monochlorobenzene, Dichlorobenzene, Dicyclohexane, Dodecane, Cyclopentane, Methylcyclopentane and Cyclohexane. Trichlorobenzene, toluene, xylene, or chlorobenzene, and the halogenated aliphatic hydrocarbon solvent may be dichloromethane, toluene, xylene, Dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, or 1,2-dichloroethane.

In the present invention, the addition amount of the first catalyst may be determined within a range in which the polymerization reaction of the monomers can sufficiently take place in the slurry, liquid phase, gas phase or massive process, and thus the amount is not particularly limited. ) relative to the concentration of the central metal (M) in the main catalyst compound per 1X10 ^-8 ~ 1mol / L, preferably from ^{1X10 -7 ~ 1X10 -1 mol / L} , more preferably 1X10 ^-7 ~ 1X10 ^-2 mol / L may be added.

In the present invention, the temperature and pressure conditions of the polymerization reaction in step (b) can be determined in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the kind of the reaction, And the pressure may be 1 to 3000 atm, preferably 1 to 1000 atm.

The method for producing a polymer compound having a brush structure according to the present invention is characterized in that a main chain polymerization reaction comprising an ethylene-olefin-diene copolymer is carried out in a first reactor as described above and a polystyrene And a side chain polymerization reaction step in which the main chain polymer produced in the first reactor and the polystyrene produced in the second reactor are subjected to a grafting reaction in a third reactor. Such a method for producing a polystyrene side chain chain can be carried out in a continuous reactor since a post-treatment step for separating unreacted styrene after the graft polymerization is not necessary.

In the present invention, the polymerization in the step (c) can be carried out in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the type of the reaction. However, the reaction temperature is preferably 20 to 100 ° C, Deg.] C, more preferably 40 [deg.] C.

In the present invention, the second catalyst may be a compound represented by the following formula (4), more preferably an ethyl group, a methyl group, a propyl group, a n-propyl group, an isopropyl group, a n- Lt; / RTI >

 (Formula 4)

[P-Li]

(P is (C1-C20) alkyl)

In the present invention, the side-chain polymerization in the step (d) can be carried out in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the type of the reaction. However, the reaction temperature is preferably 20 to 200 ° C, Lt; 0 > C.

In the present invention, the weight average molecular weight (Mw) of the polymer compound produced by the side chain polymerization in the step (d) may be 500 to 500,000, preferably 1,000 to 250,000, more preferably 1,000 to 100,000. The molecular weight distribution (Mw / Mn) of the polymer compound produced by the side chain polymerization may be 1 to 10, preferably 1.5 to 8, more preferably 1.5 to 6.

In the present invention, the steps (a) to (d) may be carried out continuously. The steps (a) to (d) may be carried out using a batch type reactor, but in the case of the present invention, it is preferable to continuously perform the reaction through the continuous type reactor because it is more efficient. In this case, the monomer feed rate in steps (a) and (c) may be 0.01 to 100 kg / hr, and the feed rate of the first catalyst and the second catalyst is preferably 0.001 to 100 mmol / hr.

In the present invention, step (d) may be further followed by step (e) of recovering the reaction solution and step (f) of recovering unreacted monomers. It is not necessary to recover by olefin polymerization by continuous reaction, but when the reaction solution and the unreacted base are separated, it is possible to produce the produced polymer compound in a pellet state. Therefore, it is preferable that the reaction solution is recovered using the high-temperature and high-pressure recovery process, and the unreacted monomers are recovered through the high-temperature and low-pressure recovery process.

In the present invention, the molecular weight (Mn) of the olefin polymer fed to the step (d) may be 500 to 15,000, preferably 1,000 to 10,000, more preferably 1,000 to 8,000. When the molecular weight of the olefin polymer is less than 500 or more than 15,000, the olefin polymer having a molecular weight of 500 to 15,000 is preferably supplied to the third reactor because tensile strength and elongation are lowered.

Hereinafter, a specific embodiment of the present invention will be described.

Polymer composition synthesis method

≪ First polymerization step &

After replacing the inside of the high-pressure reactor (first reactor, inner capacity: 2.8 L, stainless steel) with nitrogen at room temperature, 1 L of cyclohexane and 2 mmol of triisobutylaluminum were added, mL, and 10.0 mL of DVB. Next, 135 g of ethylene gas was introduced, and then the reactor temperature was preheated to 140 ° C. To the mixed solution of the catalyst compound (7.5 μmol) and triisobutylaluminum (187.5 μmol) having the structure of the following formula 5 was added dimethylanilinium tetra (45.0 μmol) solution of kiss (penta-blueorophenyl) borate were mixed and injected into the reactor, followed by polymerization for 5 minutes.

(Formula 5)

≪ Preparation of Polystyrene Polymer &

Styrene was dispersed in cyclohexane in a separate flask (second reactor) and then an n-butyllithium (n-BuLi) anion catalyst compound was added to prepare a polystyrene polymer. At this time, the molecular weight of the polystyrene was controlled by controlling the amount of the styrene and the anion catalyst, and was calculated through the following equation (1) to produce a polymer having a desired molecular weight.

Where Mo means the molecular weight of the monomer, i.e., styrene; [M] is the concentration of styrene; [I] means the concentration of the anionic catalyst.

≪ Second polymerization step &

After the first polymerization step, a part of the previously prepared polystyrene polymer was added in a state where no additional temperature and pressure change were given (third reactor), and the polymerization reaction was carried out for 10 minutes.

After the completion of the second polymerization, the temperature was lowered to room temperature, excess ethylene was discharged, and the copolymer dispersed in the solvent was dried at 80 DEG C in a vacuum oven to prepare a polyolefin-based copolymer.

Example 1

Among the synthesis methods described above, the polystyrene polymer was grown so as to have a molecular weight Mn of 8,00 and then charged into the main chain to prepare a final polyolefin graft copolymer.

Example 2

The procedure of Example 1 was repeated except that the polystyrene polymer was grown so that the molecular weight of the polystyrene polymer was Mn 4,000.

Example 3

The procedure of Example 1 was repeated except that the polystyrene polymer was grown so that the molecular weight of the polystyrene polymer was Mn 2,000.

Example 4

The same procedure as in Example 1 was carried out except that the polystyrene polymer was grown so as to have a molecular weight of Mn 1,000.

Comparative Example 1

The procedure of Example 1 was repeated except that the polystyrene polymer was grown so that the molecular weight of the polystyrene polymer was Mn 15,000.

Comparative Example 2

The same procedure as in Example 1 was carried out except that the polystyrene polymer was grown so as to have a molecular weight Mn of 500 in the synthesis method described above.

The results of polymerization according to each step of the above Examples and Comparative Examples are shown in Table 1 below.

division PS
Mn value Yield
(g) Activity
(kg / mmol Cat. hr) Mw
(x 10 ⁴ ) Mwd Tm-1
(° C) Tm-2
(° C) Tg
(° C) TS
(kgf / cm ² ) EL
(%) Shorea Density Example One 8,000 96.3 154.1 32 7.0 53.8 113.6 -57 68 700 83 0.890 2 4,000 109.9 175.9 28 7.0 59.8 104.7 -54 53 760 65 0.873 3 2,000 101.6 162.6 28 7.2 61.1 104.8 -54 73 930 67 0.872 4 1,000 94.9 151.9 27 6.5 58.8 105.1 -57 70 890 62 0.876 Comparative Example One 15,000 75.4 120.6 24 7.6 55.4 110.6 -56 46 540 87 0.882 2 500 89.2 142.7 26 7.4 57.9 106.7 -52 51 370 52 0.879

As shown in Table 1, when the molecular weight of the polystyrene supplied to the third reactor was 500 (Comparative Example 2) or 15,000 (Comparative Example 1), the tensile strength (TS) and elongation (EL) were significantly lowered. Therefore, by controlling the molecular weight of the polystyrene bound to the side chain, the properties of the entire polyolefin graft copolymer can be controlled and a polymer composition having excellent elongation and tensile strength can be prepared by preparing polystyrene having an appropriate range of molecular weight .

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (45)

(a) introducing at least one monomer selected from ethylene, olefins and dienes into a first reactor;
(b) introducing a first catalyst into the reactor to perform main chain polymerization;
(c) introducing an olefin monomer and a second catalyst into a second reactor to perform polymerization; And
(d) introducing a main chain polymerized polymer of step (b) and a polymerized olefin polymer of step (c) into a third reactor to perform side chain polymerization;
In a process for producing a polymeric compound,
Wherein the first catalyst is a transition metal catalyst compound,
Wherein the second catalyst is a compound represented by the following formula (4)
(Formula 4)
[P-Li]
(P is (C1-C20) alkyl)
The steps (a) to (d) are carried out continuously,
Wherein the molecular weight of the olefin polymer formed by the following formula (1) is controlled during the polymerization in the step (c), and then supplied to the third reactor of the step (d) .
(Equation 1)

(M is the molecular weight of the olefin polymer, Mo is the molecular weight of the olefin monomer, [M] is the concentration of the olefin monomer, and [I]
The method according to claim 1,
Wherein the olefin in the steps (a) and (c) is a C2 to C20 alpha-olefin, a C3 to C20 cycloolefin, a C3 to C20 cyclodiolefin, a substituted styrene or an unsubstituted styrene Way.
3. The method of claim 2,
The olefins of steps (a) and (c) may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-Octene, Cyclopentene, Cyclohexene, Cyclopentadiene, Cyclohexadiene, Norbonene, Methyl-2-norbornene, 2-norbornene, styrene, benzene ring of styrene, substituted styrenes having 1 to 10 carbon atoms, an alkoxy group, a halogen group, an amine group, a silyl group, ) Or a mixture thereof.
The method of claim 3,
Wherein the olefin of step (a) is 1 octene, and the olefin of step (c) is styrene.
The method according to claim 1,
The diene may be selected from the group consisting of 1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, ethylidene, norbornene, dicyclopentadiene norbornadi Vinyl-1-cyclohexene, 1-vinyl-1-cyclohexene, o-divinylbenzene, p-divinylbenzene or divinylbenzene, and m-divinylbenzene.
6. The method of claim 5,
Wherein the diene is divinylbenzene.
delete The method according to claim 1,
Wherein the transition metal catalyst compound is a metallocene catalyst.
9. The method of claim 8,
Wherein the metallocene catalyst has a general structure represented by the following general formula (1).
(Formula 1)

(M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
Q1 and Q2 are each independently halogen or (C1-C4) alkyl;
R 1 to R 13 are each independently hydrogen or; (C1-C20) alkyl, with or without an acetal, ketal or ether group, wherein at least one of R3 and R4 is (C1-C20) alkyl.
10. The method of claim 9,
Each of Q1 and Q2 is independently methyl or chlorine;
R 1, R 2, R 3, R 4 and R 5 are each independently hydrogen or methyl;
Wherein R6, R7, R8, R9, R10, R11, R12 and R13 are each hydrogen,
11. The method of claim 10,
Wherein at least one of R 3 and R 4 is methyl and R 5 is methyl.
The method according to claim 1,
Wherein the equivalence ratio of the diene to the ethylene and the olefin in the step (a) is 1: 0.1 to 1:10.
13. The method of claim 12,
Wherein the equivalence ratio of the diene to the ethylene and the olefin in the step (a) is 1: 0.1 to 1: 5.
The method according to claim 1,
Wherein the weight average molecular weight (Mw) of the polymer produced by the main chain polymerization in the step (b) is 10,000 to 1,000,000.
15. The method of claim 14,
Wherein the polymer produced by the main chain polymerization in the step (b) has a weight average molecular weight (Mw) of 50,000 to 800,000.
The method according to claim 1,
Wherein the molecular weight distribution (Mw / Mn) of the polymer produced by the main chain polymerization in the step (b) is 1 to 10. [
17. The method of claim 16,
Wherein a molecular weight distribution (Mw / Mn) of the polymer produced by the main chain polymerization in the step (b) is 1.5 to 8.
The method according to claim 1,
Wherein the step (b) further comprises adding a cocatalyst in addition to the first catalyst.
19. The method of claim 18,
Wherein the co-catalyst is a compound represented by the following formula (2) or (3).
(2)
[LH] ⁺ [Z (A) ₄ ] ^-
(C6-C20) aryl or (C1-C20) alkyl, wherein L is a neutral or cationic Lewis acid, Z is a Group 13 element, A is (C6-C20) aryl or Alkyl substituted or unsubstituted with halogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, or (C6-C20)
(Formula 3)
[L] ⁺ [Z (A) ₄ ] ^-
(C6-C20) aryl or (C1-C20) alkyl, wherein L is a neutral or cationic Lewis acid, Z is a Group 13 element, A is (C6-C20) aryl or Alkyl substituted or unsubstituted with halogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, or (C6-C20)
20. The method of claim 19,
Co-catalyst compound represented by the above formula (II) [LH] ⁺ is dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- the polymeric compound, characterized in that ^- is _{[B (C 6 F 5)} 4] Gt;
The method of claim 19, wherein the co-catalyst compound represented by Formula 2 is selected from the group consisting of trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis N, N-dimethyltris (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t- N-dimethyl anilinium tetrakis (4- (t-triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate (N, N-dimethylanilinium tetrakis (4- , 5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxytris (Pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate (N, N-diethylanilinium tetrakis , N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (2,3,5,6-tetrafluorophenyl) 4,6-tetrafluorophenyl) borate, N, N-diethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis Tripropylammonium tetrakis (2,3,4,6-tetrafluorophcnyl) borate, tri (n-butyl) ammonium tetrakis (2,3 Tetrakis (tetrabutyl) ammonium tetrakis (2,3,4-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis Dimethyl t-butyl ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetra N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate) , N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis - dimethyl 2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate (N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6- 6-tetrafluorophenyl) borate, and dialkylammonium. The method for producing a polymer compound according to claim 1,
20. The method of claim 19,
Co-catalyst compound represented by the formula 3 is [L] ⁺ is _{[(C 6 H 5) 3} C] + , and wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - in ≪ / RTI >
20. The method of claim 19,
Wherein the promoter compound represented by Formula 3 is at least one selected from the group consisting of trialkylphosphonium, dialkyloxonium, dialkylsulfonium, and carbonium salts.
24. The method of claim 23,
The trialkylphosphonium is preferably at least one selected from the group consisting of triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolylphosphonium tetrakis (pentafluorophenyl) borate, (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. A method for producing a polymer compound.
24. The method of claim 23,
The dialkyl oxonium is preferably selected from the group consisting of diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) (2,6-dimethylphenyl oxonium tetrakis (pentafluorophenyl) borate) or di (2,6-dimethylphenyloxonium tetrakis (pentafluorophenyl) borate) Wherein the polymer is a polymer.
24. The method of claim 23,
The dialkylsulfonium is preferably selected from the group consisting of diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate) or bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) Wherein the polymer is a polymer.
24. The method of claim 23,
The carbonium salt may be selected from the group consisting of tropylium tetrakis (pentafluorophenyl) borate, triphenylmethylcarbenium tetrakis (pentafluorophenyl) borate, (Diazonium) tetrakis (pentafluorophenyl) borate). 2. The process for producing a polymer compound according to claim 1, wherein the poly (diazonium) tetrakis (pentafluorophenyl) borate is benzene (diazonium) tetrakis.
20. The method of claim 19,
Wherein the molar ratio of the promoter compound to the first catalyst is 1: 1 to 1: 100,000.
The method according to claim 1,
Wherein the monomers of the steps (a) and (c) are supplied in a slurry, a liquid phase, a gaseous phase, or a bulk phase.
30. The method of claim 29,
Wherein the liquid or slurry monomer is mixed with an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixed solvent thereof.
31. The method of claim 30,
The aliphatic hydrocarbon solvent may be selected from the group consisting of butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, Wherein the polymer is a polymer selected from the group consisting of Undecane, Dodecane, Cyclopentane, Methylcyclopentane, and Cyclohexane.
31. The method of claim 30,
The aromatic hydrocarbon solvent may be at least one selected from the group consisting of benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, and chlorobenzene. ≪ / RTI >
31. The method of claim 30,
The halogenated aliphatic hydrocarbon solvent may be at least one selected from the group consisting of dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, and 1,2-dichloroethane -Dichloroethane). ≪ / RTI >
10. The method of claim 9,
Wherein the metallocene catalyst is added in an amount of 1 × 10 ^-8 to 1 mol / L based on the concentration of the central metal (M) in the compound of Formula 1 per unit volume (L) of the monomer .
The method according to claim 1,
Wherein the main chain polymerization in the step (b) is carried out at a temperature of 50 to 200 DEG C and a pressure of 1 to 3000 atm.
The method according to claim 1,
Wherein the polymerization in step (c) is performed at a temperature of 20 to 100 ° C.
delete The method according to claim 1,
Wherein the side chain polymerization in step (d) is performed at a temperature of 20 to 200 ° C.
The method according to claim 1,
Wherein the polymer compound produced by the side chain polymerization in the step (d) has a weight average molecular weight of 500 to 500,000.
The method according to claim 1,
Wherein the molecular weight distribution of the polymer compound produced by the side chain polymerization in the step (d) is 1 to 10. [
delete The method according to claim 1,
The monomer feed rate in steps (a) and (c) is 0.01 to 100 kg / hr.
The method according to claim 1,
Wherein the feed rate of the first catalyst and the second catalyst is 0.001 to 100 mmol / hr.
The method according to claim 1,
Further comprising a step (e) of recovering the reaction solution after the step (d) and a step (f) of recovering unreacted monomers.
The method according to claim 1,
Wherein the molecular weight (Mn) of the olefin polymer fed to the step (d) is 500 to 15,000.

Images