KR101811137B1 - Method of Manufacturing Brush-copolymerized Polymer Compound - Google Patents

Abstract

Disclosed is a preparation method of a polymer compound with a brush structure, which is capable of controlling molecular weight, a chemical composition, physical properties and structure of the polymer by designing a polymer at a molecular level, and which is accordingly capable of designing characteristics of each of materials according to requirements of a user. The preparation method of the present invention comprises the steps of: (a) injecting one or more monomers selected from ethylene, olefin, and diene into a reactor; (b) injecting a first catalyst into the reactor to perform a main chain polymerization; (c) additionally injecting the first catalyst into the reactor under different reaction conditions to perform a branched chain polymerization; and (d), after completing the branched chain polymerization, injecting a second catalyst into the reactor and polymerizing an unreacted olefin to recover a polymerized olefin.

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 of producing a polymer compound having a brush structure, and more particularly, to a method of manufacturing a polymer compound having a brush structure by controlling a molecular weight, a chemical composition, a physical property and a 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 capable of designing characteristics to be provided by a user.

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 materials developed and commercialized so far have poor flexibility (softening at room temperature or below) and mechanical properties equivalent to those of soft PVC, and molding is difficult especially for the molding 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.

More specifically, by using such a "tailor-made polymer manufacturing technology", low-cost general-purpose monomers such as styrene and ethylene are introduced into a polymerization process as a main raw material to produce a high-price thermoplastic elastomer (TPE) It is possible to substitute low cost general-purpose soft PVC and EVA resin as eco-friendly materials. That is, by using a precisely coordinated polymerization process and a catalyst, the main chain structure of the polymer is generated between the two-dimensional monomers, and then an optimal two-dimensional structure and molecular weight / molecular weight distribution are controlled, and precisely radical polymerization or anionic polymerization , It is possible to achieve differentiation in terms of function and cost by using a brush-type three-dimensional structure control by generating side chains having tailored-made additional functions.

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.

Accordingly, it is an object of the present invention to solve the above-mentioned problems, and it is an object of the present invention to provide a polymer composition which can control the molecular weight, chemical composition, physical property and structure of a polymer by designing the polymer at a molecular level, And to provide a method for producing a polymer compound having a brush structure capable of being designed in accordance with needs.

(A) introducing at least one monomer selected from ethylene, olefins and dienes into a reactor; (b) introducing a first catalyst into the reactor to perform main chain polymerization; (c) carrying out a side chain polymerization by additionally introducing a first catalyst into a reactor having different reaction conditions; And (d) after the side chain polymerization is completed, introducing a second catalyst to polymerize and recover unreacted olefin, thereby producing a polymer compound having a brush structure.

And the olefin is a C2 to C20 alpha-olefin, a C3 to C20 cycloolefin, a C3 to C20 cyclodiolefin, a substituted styrene or an unsubstituted styrene.

The olefins may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, cyclopentene, Cyclohexene, Cyclopentadiene, Cyclohexadiene, Norbonene, Methyl-2-Norbonene, Styrene, Benzene ring of styrene, Substituted or unsubstituted styrene having a carbon number of 1 to 10, an alkoxy group, a halogen group, an amine group, a silyl group, a haloalkyl group, or the like, or a mixture thereof. .

And the olefin is styrene. The present invention also provides a process for producing a polymer.

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 an ansa-metallocene catalyst.

Also, the present invention provides a process for producing a high molecular compound, wherein the anisometallocene catalyst has a general structure represented by the following general formula (1)

(Formula 1)

(A and B each independently represent a group selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group

Y has a bond with A and B and the other group contains hydrogen or a group containing a hydrocarbon having 1 to 20 carbon atoms which group may contain 1 to 5 nitrogen, boron, silicon, phosphorus, selenium, oxygen, fluorine, chlorine or sulfur atom ) As a substituent, an ethylene group, and a boron residue. Substituents may be different or the same. Y may have a cyclic structure such as a cyclohexylidene group or a cyclopentylidene group

X is independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, Or an amide group having a hydrocarbon substituent having 1 to 22 carbon atoms.

n is an integer of 0, 1 or 2;

M is zirconium, hafnium, or titanium.)

And an equivalence ratio of the diene to ethylene and the olefin is 1: 0.1 to 1:10.

Wherein the equivalence ratio of the diene to ethylene and the olefin 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 promoter 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 monomer is supplied in a slurry, a liquid phase, a gaseous 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 side chain polymerization in step (c) is performed at a temperature of 50 to 200 ° C.

The polymer compound produced by the side chain polymerization in the step (c) has a weight average molecular weight of 500 to 500,000.

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

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 step (d) is performed at a temperature of 10 to 150 ° C.

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 an eco-friendly material which does not require other harmful additives can be provided.

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 relates to a process for the preparation of a copolymer comprising: (a) introducing at least one monomer selected from ethylene, olefins and dienes into a reactor; (b) introducing a first catalyst into the reactor to perform main chain polymerization; (c) carrying out a side chain polymerization by additionally introducing a first catalyst into a reactor having different reaction conditions; And (d) after the side chain polymerization is completed, introducing a second catalyst to polymerize and recover the unreacted olefin, and then to a method for producing the polymer compound having a brush structure.

In the present invention, the olefin is selected from the group consisting of a (C2-C20) alpha-olefin, a (C3-C20) cycloolefin, a (C3-C20) cyclodiolefin substituted styrene Or unsubstituted styrene may be used.

Preferably, the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, cyclopentene, Cyclohexene, Cyclopentadiene, Cyclohexadiene, Norbonene, Methyl-2-Norbonene, Styrene, Benzene rings of styrene substituted styrene 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 or the like is bonded to a phenyl ring, or a mixture thereof, .

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 an ansa-metallocene catalyst, more preferably a general structure of the general formula (1).

 (Formula 1)

(A and B each independently represent a group selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group.

Y has a bond with A and B and the other group contains hydrogen or a group containing a hydrocarbon having 1 to 20 carbon atoms which group may contain 1 to 5 nitrogen, boron, silicon, phosphorus, selenium, oxygen, fluorine, chlorine or sulfur atom ) As a substituent, an ethylene group, and a boron residue. Substituents may be different or the same. Y may have a cyclic structure such as a cyclohexylidene group or a cyclopentylidene group

X is independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, Or an amide group having a hydrocarbon substituent having 1 to 22 carbon atoms.

n is an integer of 0, 1 or 2;

M is zirconium, hafnium, or titanium.)

In the present invention, the content ratio of the diene monomer to ethylene and propylene may be 1: 0.1 to 1:10, preferably 1: 0.1 to 1: 5, more preferably 1: 0.1 to 1: have.

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 monomer may be supplied in a slurry, a liquid phase, a gaseous phase or a 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 of 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 as described above and a side chain polymerization which makes a grafting reaction with polystyrene in which a growth chain, Reaction step. In this method for producing a polystyrene side chain, the unreacted gas (ethylene) is simply removed by vortexing in the polymer, and then the first catalyst of the formula (1) is introduced again after leaving the styrene monomer to polymerize the polystyrene side chain And then polymerizing.

In the present invention, the side chain polymerization in step (c) can be determined 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 50 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 (c) 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.

Due to the two-step reaction, a compound having an additional side chain bonded to the main chain is generated, but unreacted monomers must be removed because unreacted monomers are included together. Since ethylene is present in the gaseous phase at room temperature, it is mostly removed by simple venting, but olefin is present in a liquid state at room temperature and is not easily removed. Therefore, in order to remove the olefin-based monomer, it is preferable to polymerize the residual polyolefin with polyolefin by performing anionic polymerization.

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 step (d) may be carried out in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the kind of the reactor. However, the polymerization temperature may be 10 to 150 ° C, preferably 25 to 100 ° C .

In the present invention, the polyolefin may have a weight average molecular weight (Mw) of 100 to 100,000, preferably 500 to 5,000, and more preferably 1,000 to 2,000.

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

Example 1

≪ First polymerization step - Preparation of polyolefin main chain copolymer by solution process >

After replacing the inside of the high-pressure reactor (internal capacity: 2.8 L, stainless steel) with nitrogen at room temperature, 1 L of cyclohexane and 2.0 mmol of triisobutylaluminum were added, and then 70 mL of styrene purified on alumina and divinylbenzene 2.0 mL. Ethylene gas was then continuously fed into the reactor at a rate of 20 bar. The reactor was preheated to 140 ° C., and ethylene bis (indenyl) zirconium dichloride (7.5 μmol) and triisobutylaluminum (187.5 μmol) Was mixed with a solution of dimethylanilinium tetrakis (pentabluorophenyl) borate promoter (45.0 μmol), and the mixture was injected into the reactor, followed by polymerization for 20 minutes.

≪ Second polymerization step - Preparation and copolymerization of side chain of styrene by solution process >

After the polymerization, the temperature was lowered to 50 캜, and the venting valve was opened to remove residual ethylene gas. After all of the ethylene gas was removed, the temperature was elevated to 100 占 폚, and 2.5 占 퐉 ol of ethylene bis (indenyl) zirconium dichloride was added and the polymerization reaction was carried out for 10 minutes.

≪ Third polymerization step - residual styrene polymerization by solution process >

After the above-mentioned polymerization step, the temperature was maintained, 0.5 mmol of catalyst n-BuLi was injected for anionic polymerization

Polymerization was carried out for 30 minutes. After the polymerization reaction was carried out, the temperature was lowered to room temperature, the residual gas was discharged, and the copolymer dispersed in the solvent was dried at 80 DEG C in a vacuum oven.

Example 2

The procedure of Example 1 was repeated except that the polymerization temperature was set at 80 占 폚 lower in the <second polymerization step>.

Example 3

In the < Second polymerization step &gt;, the same procedure as in Example 1 was carried out, except that the polymerization temperature was set to 120 ° C lower.

Example 4

The procedure of Example 1 was repeated except that the polymerization time was shortened to 5 minutes in < Third polymerization step &gt;.

Example 5

The procedure of Example 1 was repeated except that the polymerization time was shortened to 15 minutes in the &quot; third polymerization step &quot;.

Example 6

In the < Third Polymerization Step &gt;, the same procedure as in Example 1 was carried out, except that the polymerization temperature was set to 120 DEG C higher.

Comparative Example 1

&Lt; Second polymerization step > and < Third polymerization step > were not carried out.

Comparative Example 2

&Lt; Third polymerization step > was not carried out.

Comparative Example 3

&Lt; Second polymerization step > was not carried out.

Polymerization conditions according to the respective steps of the above Examples and Comparative Examples are shown in Table 1 below, and the results of physical properties analysis of the polymers prepared by the Examples and Comparative Examples are shown in Table 2 below.

Polymerization conditions division The first polymerization step
(Main chain polymerization step) The second polymerization step
(Side chain polymerization step) Third polymerization step
(Unreacted styrene
Removal process) Ethylene
(bar) DVB
(mL) styrene (mL) polymerization
Temperature
(° C) polymerization
Time (minutes) polymerization
Temperature
(° C) polymerization
Time (minutes) polymerization
Temperature
(° C) polymerization
Time (minutes) Example One 20 2 70 140 20 100 10 80 30 2 20 2 70 140 20 80 10 80 30 3 20 2 70 140 20 120 10 80 30 4 20 2 70 140 20 100 10 80 5 5 20 2 70 140 20 100 10 80 15 6 20 2 70 140 20 100 10 120 30 Comparative Example One 20 2 70 140 20 - - - - 2 20 2 70 140 20 100 10 - - 3 20 2 70 140 20 - - 80 30

division Yield In the main chain
Styrene
Contents all
Styrene
Contents Mw MWD Unresolved
Styrene
content MFR density (g) (%) (%) % g / 10 min g / cm3 Example One 126 32.3 41.1 248,555 3.5 0.01 2.0 0.947 2 123 29.3 40.4 255,010 3.8 0.01 1.5 0.935 3 130 29.9 42.1 242,839 3.3 0.01 2.6 0.948 4 118 32.1 38.5 275,025 3.3 0.23 1.0 0.922 5 123 32.3 40.1 248,577 3.5 0.03 1.9 0.935 6 125 32.5 40.3 240,010 3.6 0.01 2.5 0.949 Comparative Example One 98 28.4 28.5 324,555 2.8 11.7 0.5 0.905 2 102 32.5 32.5 302,675 3.1 8.9 0.7 0.921 3 131 30.2 42.2 197,008 4.1 0.01 3.8 0.950

As shown in Table 2, the polymeric compound prepared by the method of the Example showed a high melt flow index (MFR) and could replace the existing thermoplastic elastomer. In Comparative Example 3, However, since the second polymerization process is not carried out, the linear polymer is formed. Therefore, it is considered that the polymer can not be used at a high temperature because the durability is lower than that of the present invention and the molecular weight is small.

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 foregoing 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 (38)

A method for producing a polymer compound having a brush structure, comprising the steps of:
(a) introducing at least one monomer selected from ethylene, olefins and dienes into a reactor;
(b) introducing a first catalyst into the reactor to perform main chain polymerization;
(c) carrying out a side chain polymerization by additionally introducing a first catalyst into a reactor having different reaction conditions; And
(d) after the side chain polymerization is completed, introducing a second catalyst to polymerize and recover unreacted olefin,
Wherein the first catalyst is a transition metal catalyst compound,
Wherein the second catalyst is a compound represented by the following general formula (4).
(Formula 4)
[P-Li]
(P is (C1-C20) alkyl)
The method according to claim 1,
Wherein the olefin is a C2 to C20 alpha olefin, a C3 to C20 cycloolefin, a C3 to C20 cyclodiolefin, a substituted styrene or an unsubstituted styrene.
3. The method of claim 2,
The olefin may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, cyclopentene, ), Cyclopentadiene, cyclohexadiene, norbonene, methyl-2-norbornene, styrene, benzene ring of styrene, A substituted or unsubstituted styrene having one or more groups selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a halogen group, an amine group, a silyl group and a haloalkyl group, or a mixture thereof. Gt;
The method of claim 3,
Wherein the olefin is styrene. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
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 an ansa-metallocene catalyst.
9. The method of claim 8,
Wherein the anisometallocene catalyst has a general structure represented by the following general formula (1).

(Formula 1)

(A and B each independently represent a group selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group
Y has a bond with A and B and the other group contains hydrogen or a group containing a hydrocarbon having 1 to 20 carbon atoms which group may contain 1 to 5 nitrogen, boron, silicon, phosphorus, selenium, oxygen, fluorine, chlorine or sulfur atom ) As a substituent, an ethylene group, and a boron residue. Substituents may be different or the same. Y may have a cyclic structure.
X is independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, Or an amide group having a hydrocarbon substituent having 1 to 22 carbon atoms.
n is an integer of 0, 1 or 2;
M is zirconium, hafnium, or titanium.)
The method according to claim 1,
Wherein the equivalence ratio of the diene to ethylene and the olefin is 1: 0.1 to 1:10.
11. The method of claim 10,
Wherein the equivalence ratio of the diene to ethylene and the olefin 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.
13. The method of claim 12,
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. [
15. The method of claim 14,
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.
17. The method of claim 16,
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)
18. The method of claim 17,
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 17, wherein the promoter compound represented by Formula 2 is at least one 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, 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-tetrafluorophenyl) borate, tripropylammonium tetrakis tetrafluorophcnyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate ), Dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N , N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate (N, N-dimethylanilinium tetrakis Anilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate (N, N-diethylanilinium tetraki s (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl 2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) (2, 3, 4, 6-tetrafluorophenyl) borate) and dialkylammonium.
18. The method of claim 17,
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 &Lt; / RTI &gt;
18. The method of claim 17,
Wherein the promoter compound represented by Formula 3 is at least one selected from the group consisting of trialkylphosphonium, dialkyloxonium, dialkylsulfonium, and carbonium salts.
22. The method of claim 21,
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.
22. The method of claim 21,
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.
22. The method of claim 21,
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.
22. The method of claim 21,
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.
18. The method of claim 17,
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 monomer is supplied in a slurry, a liquid phase, a gaseous phase, or a bulk phase.
28. The method of claim 27,
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.
29. The method of claim 28,
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.
29. The method of claim 28,
The aromatic hydrocarbon solvent may be at least one selected from the group consisting of benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, and chlorobenzene. &Lt; / RTI &gt;
29. The method of claim 28,
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). &Lt; / RTI &gt;
The method according to claim 1,
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 first catalyst per unit volume (L) of the monomer. Gt;
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 side chain polymerization in step (c) is performed at a temperature of 50 to 200 ° C.
The method according to claim 1,
Wherein the polymer compound produced by the side chain polymerization in the step (c) 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 (c) is 1 to 10. [
delete The method according to claim 1,
Wherein the step (d) is performed at a temperature of 10 to 150 ° C.