KR20080060741A - Olefin block copolymer and preparation method thereof - Google Patents

Abstract

A method for preparing an olefin-based block copolymer is provided to enable easy formation of a polyolefin segment containing a hydroxyl group bonded to the end thereof, and easy control of the ratio and molecular weight of a polyolefin segment and functional segment. A method for preparing an olefin-based block copolymer comprises the steps of: (i) providing a polyolefin(PO-OH) containing a hydroxyl group bonded to the end thereof; (ii) converting the polyolefin(PO-OH) into a radical chain polymerization active species(PO-A); and (iii) carrying out radical chain polymerization of the radical chain polymerization active species(PO-A).

Description

Olefin block copolymers and preparation method thereof {OLEFIN BLOCK COPOLYMER AND PREPARATION METHOD THEREOF}

FIG. 1 is a ¹ H NRM spectrum of polyethylene {PE-OH (III)} having an acid group bonded to an end thereof, prepared in Example 3 of the present invention.

2 is a ¹ H NRM spectrum of a radical chain polymerization active species {PE-Br (III)} prepared in Example 11 of the present invention.

3 is a GPC spectrum of block copolymers {PE-g-PMMA (III)} to {PE-g-PMMA (V)} prepared in Examples 14 to 16 of the present invention.

4 is a ¹ H NRM spectrum of the block copolymer {PE-g-PMMA (I)} prepared in Example 12 of the present invention.

Fig. 5 is the ¹ H NRM spectrum of the block copolymer {PE-g-PMMA (II)} prepared in Example 13 of the present invention.

6 is a ¹ H NRM spectrum of block copolymers {PE-g-PMMA (III)} to {PE-g-PMMA (V)} prepared in Examples 14 to 16 of the present invention.

7 is a TEM photograph of the block copolymers {PE-g-PMMA (III)} to {PE-g-PMMA (V) prepared in Examples 14 to 16, and PE and PMMA blending polymers.

The present invention relates to an olefin block copolymer and a method for producing the same, and more particularly, to an olefin block copolymer represented by Formula 1, in which a polyolefin segment and a functional segment are ester-bonded, and a method for producing the same.

Polyolefins are excellent in processability, chemical resistance, electrical properties, mechanical properties, and the like, and are processed into extrusion molded articles, injection molded articles, blow molded articles, films, sheets, and the like, and are used in various applications.

However, since polyolefin is a so-called nonpolar resin which does not have a polar group in a molecule | numerator, it has affinity with various polar substances, including a metal, and it was difficult to adhere | attach with a polar substance or mixing with a polar resin. In addition, the surface of the molded article made of polyolefin is hydrophobic, and in applications requiring anti-fogging and antistatic properties, it is necessary to mix a low molecular weight surfactant or the like, and the surface of the molded article is contaminated with the surfactant. There was a problem that occurred.

On the other hand, in recent years, the demand for physical properties for polyolefins has been diversified. For example, polyolefins having various properties such as polyolefins having excellent heat resistance, polyolefins having a soft hand such as soft polyvinyl chloride, and the like are also desired.

As a method of improving the physical properties of a polyolefin, there are a method of adjusting the type of monomer, the molar ratio and the like, a method of changing the arrangement of monomers such as random or block, a method of graft copolymerizing a polar monomer into a polyolefin, and the like. Method was tried.

In the case of the method of graft copolymerizing a polar monomer to a polyolefin, the method of reacting a polyolefin and a radically polymerizable monomer in the presence of a radical initiator is generally performed, but the graft copolymer obtained by such a method is a homopolymer of a radically polymerizable monomer. Unreacted polyolefins are often contained, and the graft structure is also nonuniform. In addition, since the crosslinking reaction and the decomposition reaction of the polymer chain are accompanied with the graft polymerization, the physical properties of the polyolefin have largely changed.

Regarding a method for synthesizing a block polymer of a polyolefin and a polar polymer without involving the crosslinking reaction or the decomposition reaction as described above, International Publication No. WO98 / 002472 (published on Jan. 22, 1998) shows boron in a polyolefin having an unsaturated bond at its terminal. After addition of a compound, a method of forming a radical chain polymerization active species (macro initiator) by oxidizing it with oxygen is disclosed.

In addition, WO01 / 053369 (published on July 26, 2001) discloses that in addition to the above method, polyolefins having carbon-aluminum bonds at their ends are oxidized to molecular oxygen to be converted into aluminum oxide to generate active species. And a method of ring-opening polymerization of a ring-opening polymerizable monomer to a polyolefin having a hydroxyl group at a terminal and an organic lithium compound to convert to a polyolefin having a lithium at the terminal, and then polymerizing an anionically polymerizable monomer. .

As a method for producing a specific block copolymer comprising a polyolefin segment and a functional segment, International Publication No. WO98 / 002472 discloses a polymethacrylic acid when preparing a block copolymer composed of a polyolefin segment and a polymethacrylic acid ester segment. A method for preparing ester segments by radical polymerization is disclosed.

Moreover, WO 01/053369 discloses stereoregularity of polymethacrylic acid esters by converting the terminal of a specific polyolefin into a specific group and anionic polymerization of the (meth) acrylic acid ester in the presence of a polyolefin containing a specific group at the terminal. A method capable of controlling copolymerizability is disclosed.

As a result of examining the prior arts described above, the present inventors have found a new method for converting the end of a specific olefin into a hydroxyl group, and by easily adjusting the molecular weight of the polyolefin segment and the functional segment, the olefin block air The physical properties of the coalescence could be easily adjusted.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide an olefin-based block copolymer represented by the formula (1), wherein the polyolefin segment and the functional segment are ester-bonded.

In addition, an object of the present invention is to provide a method for producing an olefin-based block copolymer comprising the step of producing a polyolefin having a hydroxyl group bonded to the terminal.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides an olefin block copolymer represented by the following formula (1).

[Formula 1]

PO-g-B

In Formula 1, PO is a segment consisting of repeating units derived from olefins having 2 to 20 carbon atoms, g is an ester bond, and B is a functional segment containing a hetero atom.

In addition, the present invention is a method for producing an olefin block copolymer represented by the formula (1),

(I) preparing a polyolefin (PO-OH) having a hydroxyl group bonded to the terminal;

(II) converting the prepared polyolefin (PO-OH) into a radical chain polymerization active species (PO-A); And

(III) It provides a method for producing an olefin-based block copolymer comprising the step of radical chain polymerization of the converted radical chain polymerization active species (PO-A).

Hereinafter, the present invention will be described in detail.

As a result of examining the prior arts as described above, the inventors have discovered a new method for converting the terminal of a specific polyolefin into a hydroxyl group only by contact with anhydrous oxygen or air after polymerization without further reaction. By applying the above-described method, in the case of the atomic transfer radical chain polymerization which facilitates the control of polymerization in the presence of a polyolefin containing a specific group at the terminal, the ratio and molecular weight of the polyolefin segment and the functional segment can be easily adjusted to provide an olefinic system. It has been found that the physical properties of the block copolymer can be easily adjusted, and based on this, the present invention has been completed.

The olefin block copolymer of the present invention is a block copolymer in which a polyolefin segment and a functional segment are chemically bonded, and are represented by the following Chemical Formula 1.

[Formula 1]

PO-g-B

In Formula 1, PO is a segment consisting of repeating units derived from olefins having 2 to 20 carbon atoms, g is an ester bond, and B is a functional segment containing a hetero atom.

The segment represented by PO is a polyolefin segment produced by polymerizing one or more monomers selected from the group consisting of linear α-olefins having 2 to 20 carbon atoms.

The polyolefin segment may have stereoregularity, wherein either isotactic polyolefin or syndiotactic polyolefin may be used.

The linear α-olefin having 2 to 20 carbon atoms may be ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- One or more types are selected from the group which consists of hexadecene and 1-octadecene, and a linear alpha-olefin of 2-10 carbon atoms is preferable.

 Although the weight average molecular weight of the said polyolefin segment is not specifically limited, Usually, it is 500-1,000,000, Preferably it is 500-500,000, More preferably, it is 500-50,000.

The bond represented by g is an ester bond, which chemically bonds a polyolefin segment and a segment containing a hetero atom. At this time, the ester bond portion may contain a part of the structure formed by radical chain polymerization.

The segment containing the hetero atom represented by said B is a functional segment which consists of a repeating unit derived from 1 or more types chosen from the group which consists of an unsaturated carboxylic acid and its derivative (s).

The unsaturated carboxylic acid is acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid and bicyclo [2,2,1] hept-2 At least one selected from the group consisting of -ene-5,6-dicarboxylic acid, and derivatives thereof include acid anhydrides, acid halides, acid amides, acid imides or esters; Specific examples include maleyl chloride, maleylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-di Carboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconic acid, diethyl citraconate, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5 , 6-dicarboxylic acid dimethyl, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, amino ethyl methacrylate, aminopropyl methacrylate, and the like. Preferred are oxyethyl (meth) acrylate and glycidyl (meth) acrylate.

Although the weight average molecular weight of the said functional segment is not specifically limited, Usually, it is 500-1,000,000, Preferably it is 500-500,000.

The functional segment is not particularly limited in content, but may be included in the olefinic block copolymer of the present invention in an amount of 0.01 to 99.99% by weight, preferably 1 to 99% by weight, more preferably 1 to 95% by weight. It is included.

Method for producing an olefin block copolymer of the present invention is a method comprising the step of preparing a polyolefin having a hydroxyl group bonded to the terminal.

The method for preparing the olefin block copolymer includes (I) preparing a polyolefin (PO-OH) having a hydroxyl group bonded to the terminal; (II) converting the prepared polyolefin (PO-OH) into a radical chain polymerization active species (PO-A); And (III) radical chain polymerization of the converted radical chain polymerization active species (PO-A).

In addition, the step of preparing a polyolefin (PO-PH) having a hydroxyl group bonded to the terminal (I) comprises the steps of: (i) preparing a polyolefin (PO-Group 13 element) having a group 13 element bonded to the terminal; (Ii) oxidizing the ends of the prepared polyolefin (PO-Group 13 elements) with molecular oxygen to produce polyolefins (PO-O-Group 13 elements) whose ends are converted to oxides; And (iii) subjecting the produced polyolefin (PO-O-Group 13 element) to a polyalcoholization reaction.

The reaction scheme for preparing the olefin block copolymer of the present invention is shown in Scheme 1 below.

As shown in Scheme 1, first, a polyolefin (PO-Group 13 element) having a Group 13 element bonded to one end thereof is prepared, and in the presence thereof, oxidized to molecular oxygen by anhydrous oxygen or anhydrous air, After preparing a polyolefin (PO-O-Group 13 element) converted to an oxide, a polyolefin (PO-PH) having a hydroxyl group bonded to the terminal is prepared through a polyalcoholization reaction. The produced polyolefin (PO-OH) may be reacted with a specific compound to convert into a radical chain polymerization active species (PO-A), and the radical chain polymerizable monomer may be chain polymerized therein to prepare an olefin block copolymer. .

Hereinafter, it will be described in detail by dividing into each manufacturing step.

(I) preparing a polyolefin (PO-PH) having a hydroxyl group bonded to the terminal;

In this step, a polyolefin having a Group 13 element bonded to one end thereof is prepared, and oxidized to molecular oxygen by anhydrous oxygen or anhydrous air to prepare a polyolefin whose terminal is converted to an oxide, and then subjected to an alcoholic reaction. It is a step of preparing a polyolefin having a hydroxyl group bonded to the end.

(Iii) preparing a polyolefin (PO-Group 13 element) having a Group 13 element bonded to the terminal;

A polyolefin having a Group 13 element bonded to the terminal is prepared by coordination polymerization with a transition metal. For example, in the presence of a conventionally known catalyst for olefin polymerization, the linear α-olefins having 2 to 20 carbon atoms can be produced alone or by copolymerization. In this case, the prepared polyolefin becomes a polyolefin segment (PO) of the block copolymer.

The olefin polymerization catalyst is conventionally known, and may use a TiCl ₃ -based catalyst, a MgCl ₂ -supported TiCl ₄ -based catalyst, a metallocene catalyst or a postmetallocene catalyst, and preferably a metallocene catalyst. It is.

As the metallocene catalyst, a conventionally known metallocene catalyst can be used, and as a specific example, a metallocene compound of transition metal such as titanium, vanadium, chromium, zirconium or hafnium can be used. The metallocene compound can also be used in a liquid phase or a solid phase under use conditions. In addition, these do not need to be a single compound, they may be supported on other compounds, may be a mixture homogeneously mixed with other compounds, or may be a complex compound or a complex compound with another compound.

In the production of the polyolefin, among the conventionally known metallocene catalysts, there are two substituted cyclopentadienyl groups, and the two cyclopentadienyl groups are bonded to a bonding group such as (substituted) alkylene and (substituted) silylene. Preference is given to using metallocene compounds which are not present. Specific examples include bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxychloride, bis (dimethylcyclopentadienyl) zirconium Bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methyl Propylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate ), Bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadi Nil) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride or bis (tri methylsilylcyclopentadienyl) zirconium dichloride, etc. can be used. .

One or more organometallic components may be used in combination with the metallocene compound as a cocatalyst and a molecular weight regulator. In particular, the molecular weight modifier in the present invention serves to control the molecular weight of the polyolefin, and at the same time plays an intermediate role to convert the end of the polyolefin to a hydroxyl group. Therefore, the molecular weight of the polyolefin segment can be easily adjusted.

The organometallic component may be one containing an element selected from Group 13 of the Periodic Table, preferably an organoaluminum compound, an organoboron compound, or a complex alkyl compound of an element of Periodic Table 1 and aluminum or boron will be.

The organoaluminum compound may be a compound represented by Formula 2 below.

[Formula 2]

R ¹ _n AlX _3-n

In Formula 2, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, n is an integer of 0 to 3.

R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, which may be an alkyl group, a cycloalkyl group, or an aryl group, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, Cyclohexyl, phenyl or tolyl and the like.

The organoaluminum compound represented by the formula (2) is trialkyl aluminum, such as trimethyl aluminum, tri ethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2-ethylhexyl aluminum; Trialkenyl aluminum, such as triisoprenyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide; Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Alkyl aluminum dihalide such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; Alkyl aluminum hydride, such as diethyl aluminum hydride, diisobutyl aluminum hydride, and ethyl aluminum dihydride, etc. can be used.

Another example of the organoaluminum compound may be a compound represented by Formula 3 below.

[Formula 3]

R ¹ _n AlY _3-n

In Chemical Formula 3, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, the same as in Chemical Formula 2, Y is -OR ² , -OSiR ³ ₃ , -OAlR ⁴ ₂ , -NR ⁵ ₂ , Is a -SiR ⁶ ₃ group or -N (R ⁷ ) AlR ⁸ ₂ group, R ² to R ^4, and R ⁸ are methyl, ethyl, isopropyl, isobutyl, cyclohexyl or phenyl, etc., and R ⁵ is hydrogen Atom, methyl, ethyl, isopropyl, phenyl or trimethylsilyl and the like, R ⁶ and R ⁷ are methyl or ethyl, respectively, and n is an integer of 1 to 2.

Specific examples of the organoaluminum compound represented by Formula 3 include (i) a compound represented by R ¹ _n Al (OR ² ) _3-n when Y is a -OR ² group, such as dimethylaluminum methoxide or diethylaluminum ethoxy Seeds, diisobutylaluminum methoxide and the like; (Ii) when Y is -OSiR ³ ₃ , a compound represented by R ¹ _n Al (OSiR ³ ) _3-n , _wherein Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ ), (iso -Bu) ₂ Al (OSiEt ₃ ) and the like; (Iii) when Y is -OAlR ⁴ ₂ , a compound represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n ; Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc .; (Iii) when Y is -NR ⁵ ₂ , a compound represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n ; Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN (Me ₃ Si) _2, and the like; (Iii) when Y is a -SiR ⁶ ₃ group, a compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n (iso-Bu) ₂ AlSiMe ₃ ; (Iii) when Y is -N (R ⁷ ) AlR ⁸ ₂ , a compound represented by R ¹ _n Al [N (R ⁷ ) -AlR ⁸ ₂ ] _3-n ; Et ₂ AlN (Me) -AlEt ₂ ( iso-Bu) ₂ , AlN (Et) Al (iso-Bu) ₂ , and the like can be used.

In addition, compounds similar to the above compounds, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ which is an organoaluminum compound having two or more aluminums bonded via an oxygen atom or a nitrogen atom AlOAl (C ₄ H ₉ ) ₂ or (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _2, etc. may be used, and methylaluminoxane, ethylaluminoxane, propylaluminoxane or butyl Aluminoxanes, such as aluminoxane, can be used.

Another example of the organoaluminum compound may be a compound represented by the following formula (4).

[Formula 4]

R ¹ _n AlXY

In Formula 4, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is the same as in Formula 2 as halogen or hydrogen, Y is -OR ² group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ Group, —NR ⁵ ₂ group, —SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group are the same as in the above Formula (3).

The organoboron compound may be triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron , Tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, texyl borane, dicyclohexyl borane, dicyamil borane, diisopinocamp phenyl borane, 9-bora Bicyclo [3,3,1] nonane, dimethylborane, dichloroborane, catecholborane, B-bromo-9-borabicyclo [3,3,1] nonane, borane-triethylamine complex, borane-methyl Sulfide complexes and the like can be used. Further, as the ionic boron compound, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl ) Ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, N, N-dimethylanilinium Tetra (phenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and the like can be used.

The complex alkyl compound of the Group 1 element of the periodic table and aluminum may be a compound represented by the following formula (5).

[Formula 5]

M ¹ AlR ⁹ ₄

In Formula 5, M ¹ is Li, Na or K, R ⁹ is a hydrocarbon group having 1 to 15 carbon atoms.

LiAl (C ₂ H ₅ ) ₄ , LiA 1 (C ₇ H ₁₅ ) ₄ or the like may be used as the complex alkyl compound of the Group 1 element of the periodic table represented by Chemical Formula 5 and aluminum.

The organoboron compound and the complex alkyl compound of boron may be a compound of the organoaluminum compound and the complex alkyl compound of the periodic table group 1 element and aluminum with boron.

Among the organometallic components, aluminoxanes such as methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, and butyl aluminoxane are preferable as the cocatalyst, and as the molecular weight regulator, an organoaluminum compound represented by Chemical Formula 2 may be used. , Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum and the like are preferable.

The polymerization for producing the polyolefin can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization, or gas phase polymerization. The reaction temperature is usually in the range of -50 to 200 ° C, preferably 0 to 150 ° C. The polymerization pressure is usually 0.1 to 100 atm, preferably 1 to 50 atm. The polymerization can be carried out by any of batch, semi-continuous or continuous methods, and when the polymerization is carried out in two or more stages, the reaction conditions may be the same or different.

In the olefin polymerization method as described above, a polyolefin having a weight average molecular weight of 500 or more is usually produced. At this time, it is preferable to control so that molecular hydrogen which is a molecular weight regulator generally used does not exist in a polymerization system. In particular, in the present invention, it is preferable to adjust the molecular weight by controlling the reaction conditions of at least one of the type, concentration, polymerization temperature and olefin concentration (polymerization pressure) of the organometallic component as the molecular weight regulator. Do. For example, in the polymerization in which molecular hydrogen is not substantially present, increasing the concentration of the organometallic component can lower the molecular weight of the polyolefin obtained, and increasing the polymerization temperature can lower the molecular weight of the polyolefin obtained.

The amount of the molecular weight modifier is an excess of 1 to 100,000 times, preferably 1 to 10,000 times based on the content of the polymerization catalyst during the polymerization.

In particular, the molecular weight regulator in the present invention serves to control the molecular weight of the polyolefin, and at the same time plays an intermediate role of converting the end of the polyolefin to a hydroxyl group.

In addition, a promoter may be used together with the molecular weight modifier, and the amount of the promoter used is 1 to 100,000 times, preferably 1 to 10,000 times, based on the content of the polymerization catalyst.

The polyolefin produced by the above method is a polyolefin having a Group 13 element bonded to one end.

International Publication No. WO98 / 002472 discloses a method for producing a polyolefin having a hydroxyl group at one end by reacting hydrogen peroxide (H ₂ O ₂ ) dropwise and then refluxing in the presence of methanol.

Tomoaki Matsugi also discloses a method of preparing polyolefins having hydroxyl groups at one end by adding allyl alcohol to the Journal of Polymer Science: Part A: Polymer Chemistry, 2003, 41, 3965-3973. have.

Accordingly, the present inventors have found a method of easily adjusting the molecular weight and easily producing a polyolefin (PO-OH) having only a hydroxyl group without generating an unsaturated bond terminal polyolefin at one end with high yield.

(Ii) converting the ends of the polyolefin to oxides

The bonding portion of the polyolefin having a Group 13 element bonded to the terminal prepared in step (iii) can be easily oxidized to molecular oxygen through contact with anhydrous oxygen or air. As a result, the polyolefin segment ends are converted into oxides (PP-O-Group 13 elements).

(Iii) subjecting the end of the polyolefin to a alcoholic reaction

The polyolefin segment (PO-OH) having a hydroxyl group at one end of the polyolefin can be easily prepared by performing an alcoholic reaction of the oxide (PO-O-Group 13 element) polymer at the end of the polyolefin segment prepared in step (ii). have.

The alcohol used for the alcoholic reaction is preferably an alkyl alcohol, specifically methanol, ethanol, propanol or the like can be used.

(II) conversion to radical chain polymerization active species (PO-A)

This step is a step of converting a polyolefin (PO-OH) having a hydroxyl group bonded to the terminal prepared in step (I) to a radical chain polymerization active species.

By "chain polymerized active species" is meant a macro initiator in radical chain polymerization, which serves as an initiator to initiate polymerization or crosslinking reaction with monomers capable of radical chain polymerization.

As Tomoaki Matsugi discloses in the Journal of Polymer Science: Part A: Polymer Chemistry, 2003, 41, 3965-3973, a polyolefin segment having a hydroxyl group bonded to a terminal is reacted with a compound represented by the following formula (6). Acylating with α-halo prepares the active species (PO-A) for radical chain polymerization, in which the α-halo acyl group (A), which is a functional group containing a halogen atom, is bonded at the terminal.

[Formula 6]

In Formula 6, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen, and n is an integer of 0 to 3.

R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, which may be an alkyl group, a cycloalkyl group, or an aryl group, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, Cyclohexyl, phenyl or tolyl and the like.

X is halogen, and Br is more preferable than Cl in view of radical chain polymerization.

The most preferred compound represented by the formula (6) is 2-bromoisobutyryl bromide.

(II) radical chain polymerization

This step is a step of adding a initiator, a transition metal compound, a ligand, a monomer, a solvent to the radical chain polymerization active species (PO-A) prepared in step (II) and performing radical chain polymerization.

As described in International Publication No. WO96 / 030421 (published on October 3, 1996) and Tomoaki Matsugi in the Journal of Polymer Science: Part A: Polymer Chemistry, 2003, 41, 3965-3973, an atomic transition radical polymerization method Do this.

The transition metal compound is preferably a compound represented by the following formula (7).

[Formula 7]

M ₂ ^{n +} X ′ _n

In Formula 7, M ₂ ^{n +} is Cu ¹⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ³⁺ , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ⁺ , Mn ³⁺ , Mn ⁴⁺ , V ²⁺ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ and Ag ²⁺ ,

X ′ is halogen, alkoxy having 1 to 6 carbon atoms, (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ), triflate, hexafluorophosphate , Methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR ¹⁰ (wherein R ¹⁰ is aryl, or straight or branched C1-20, preferably C1-10 Alkyl groups are substituents which may be substituted 1 to 5, preferably fluorine or chlorine 1 to 3 times with halogen atoms, CN and R ¹¹ CO ₂ , wherein R ¹¹ is a hydrogen atom or a straight or branched carbon number 1 And an alkyl group of 6 to 6, preferably methyl, which is a substituent substituted with 1 to 5, preferably fluorine or chlorine 1 to 3 times with a halogen atom.

n is the formal charge on the metal and is an integer of 0 ≦ n ≦ 7.

The ligand may be coordinated to the transition metal via π-bond, a ligand having at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus and sulfur, which may be coordinated to the transition metal through σ-bonding. Ligands containing at least two carbon atoms, and ligands capable of coordinating to the transition metal via μ-bonds or η-bonds, may be used, and N-, O-, P- represented by the following formulas 8 or 9 And S-containing ligands are preferred.

[Formula 8]

R ¹² -ZR ¹³

[Formula 9]

R ¹² -Z- (R ¹⁴ -Z) _{n ′} -R ¹³

In Chemical Formulas 8 and 9,

R ¹² and R ¹³ are hydrogen atoms; Alkyl having 1 to 20 carbon atoms; Aryl such as phenyl, tolyl and methoxyphenyl; Pyridyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyranyl, indolyl, isoindolinyl, indazolyl, benzofuryl, isobenzofuryl, benzo Thienyl, isobenzothienyl, chromenyl, xanthenyl, furinyl, putridinyl, quinolyl, isoquinolyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, phenoxatiinyl, Carbazolyl, cinnolinyl, phenanthridal, acridinyl, 1,10-phenanthrolinyl, phenazinyl, phenoxazinyl, phenothiazinyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl Heterocyclyl groups (preferably pyridyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyranyl or indolyl, most preferably pyridyl); Alkoxy having 1 to 6 carbon atoms; Dialkylamino having 1 to 4 carbon atoms; Alkyl having 1 to 6 carbon atoms substituted with C (= Y) R ¹⁵ , C (= Y) R ¹⁶ R ¹⁷ and YC (= Y) R ¹⁸ , wherein Y is NR ¹⁸ or an oxygen atom, preferably an oxygen atom R ¹⁵ is alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryloxy or heterocyclyloxy; R ¹⁶ and R ¹⁷ are independently hydrogen atom or alkyl having 1 to 20 carbon atoms, or R ¹⁶ and R ¹⁷ may be linked together to form an alkylene group having 2 to 5 carbon atoms to form a 3 to 6 membered ring; R ¹⁸ is a hydrogen atom, a straight or branched alkyl or aryl group having 1 to 20 carbon atoms Independently selected from the group consisting of or R ¹² and R ¹³ may be linked to form a saturated, unsaturated or heterocyclic ring to a heterocyclyl group,

Z is O, S, NR ¹⁹ or PR ¹⁹ , wherein R ¹⁹ is selected from the same groups as R ¹² and R ¹³ above,

Each R ¹⁴ is an alkylene (alkandi) having from 2 to 4 carbon atoms in which the covalent bond to each Z is at an adjacent position (specifically 1,2-array) or β-position (specifically 1,3-array) 1) or alkenylene having 2 to 4 carbon atoms, and cycloalkanediyl having 3 to 8 carbon atoms, cycloalkenediyl having 3 to 8 carbon atoms, arendyl and heterocyclylene in which a covalent bond to each Z is adjacent to each other; It is bivalent selected from the group which consists of,

n 'is an integer of 1-6.

In addition, each of R ¹² -Z and R ¹³ -Z in the ligand may form a ring together with the R ¹⁴ group to which Z is bonded to form a linking or fused heterocyclic ring system. Or when at least one selected from R ¹² and R ¹³ is heterocyclyl, Z is selected from a covalent bond (single or double bond), CH ₂ , or R ¹² and R ^{13 in} addition to the substituents defined above for Z; 4 to 7 membered ring fused to one or more species. Examples of the ring system in the ligand may include bipyridine, bipyrrole, 1,10-phenanthroline, creeptand, crown ether, and the like.

When Z is PR ¹⁹ , R ¹⁹ may be alkoxy having 1 to 20 carbon atoms.

Ligands used in the present invention include CO (carbon monoxide), porphyrin, porphysene, etc. Among the latter two ligands are 1 to 6, preferably 1 to 4 halogen atoms, alkyl groups of 1 to 6 carbon atoms, It may be substituted with an alkoxy group having 1 to 6 carbon atoms, alkoxycarbonyl having 1 to 6 carbon atoms, an aryl group, a heterocyclyl group, an alkyl group having 1 to 6 carbon atoms further substituted with 1 to 3 halogen atoms, and the like.

Other ligands include compounds represented by the following formula (10).

[Formula 10]

R ²⁰ R ²¹ C (C (= Y) R ¹⁵ ) ₂

In Formula 10, Y and R ¹⁵ are as defined in Formulas 8 and 9, and R ²⁰ and R ²¹ are each independently from the group consisting of a hydrogen atom, halogen, alkyl having 1 to 20 carbon atoms, aryl and heterocyclyl R ²⁰ and R ²¹ may be linked to form a cycloalkyl ring having 3 to 8 carbon atoms, a hydrogenated (reduced non-aromatic, or partially or fully saturated) aromatic, or heterocyclic ring, At least one selected from the group consisting of any one except a hydrogen atom or a halogen, preferably 1 to 5, preferably 1 to 3, an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a halogen atom, and an aryl group. It may be further substituted by. Preferably, one of R ²⁰ and R ²¹ is a hydrogen atom or a negative charge.

Further ligands include, specifically, ethylenediamine and propylenediamine in which an alkyl or carboxymethyl group having 1 to 4 carbon atoms can be substituted 1 to 4 times on an amino nitrogen atom; Aminoethanol and aminopropanol in which an alkyl group having 1 to 4 carbon atoms may be substituted one to three times on oxygen, nitrogen, or a mixed atom thereof; Ethylene glycol and propylene glycol wherein an alkyl group of 1 to 4 carbon atoms may be substituted once or twice on an oxygen atom; Diglyme, triglyme, tetraglyme and the like.

Carbon-based ligands include arene and cyclopentadienyl ligands, and preferred carbon-based ligands include benzene, in which an alkyl group having 1 to 4 carbon atoms (specifically, a methyl group) may be substituted with 1 to 6 carbon atoms; Cyclopentadienyl and the like, which may be substituted with 1 to 5 methyl groups, or may be linked to a second cyclopentadienyl ligand via an ethylene or propylene chain. Among these, when using a cyclopentadienyl ligand, it is not necessary to include a co-ion (X ') in a transition metal compound.

Preferred ligands include unsubstituted and substituted pyridine, and bipyridine, acetonitrile, (R ²² O) ₃ P, PR ²² ₃ , wherein R ²² is alkyl having 1 to 20 carbon atoms and each hydrogen atom in the alkyl group is a halide, preferably And independently substituted by fluoride or chloride.), 1,10-phenanthroline, porphyrin, creeptand (eg K ₂₂₂ ) and crown ether (eg 18-crown-6) There is. Most preferred ligands are bipyridine and (R ²² O) ₃ P.

In radical chain polymerization, the amount of use of the chain-polymerized active species (PO-A), the transition metal compound and the ligand, and the relative ratio, are preferably such that they are effective to carry out the atomic transition radical chain polymerization.

In general, in the chain-polymerized active species (PO-A) / transition metal compound / ligand system, the efficiency of the chain-polymerized active species (PO-A) is at least 50%, preferably at least 80%, more preferably at 90% It is very excellent above. Therefore, the amount of the chain-polymerized active species (PO-A) is 10 ^-4 to 1 M, preferably 10 ^-3 to the concentration. It can be selected in the range of about 10 ^-1 M. Alternatively, the molar ratio of the chain polymerized active species (PO-A) to the monomer may be selected from the range of 10 ⁻⁴ : 1 to 10 ⁻¹ : 1, preferably 10 ⁻³ : 1 to 5 × 10 ⁻² : 1 It may be. Particular preference is given to the preparation of end-functional polymers with a concentration of the chain polymerized active species (PO-A) of 0.1 to 1 M.

The molar ratio of the transition metal compound to the chain polymerized active species (PO-A) is generally a ratio effective for polymerizing the selected monomer (s), and is preferably 0.0001: 1 to 10: 1, preferably 0.1: 1 to 5: 1. More preferably from 0.3: 1 to 2: 1, most preferably from 0.9: 1 to 1.1: 1.

When the polymerization is carried out in a homogeneous system, the concentration of the transition metal compound and the ligand is reduced such that the molar ratio of the transition metal compound and the chain polymerized active species (PO-A) is reduced to 0.001: 1.

Likewise, the molar ratio of the transition metal compound to the ligand is generally a ratio of the degree effective to polymerize the selected monomer, but may depend on the number of coordination sites on the transition metal compound that the selected ligand will occupy. The amount of ligand to be used is (a) the ratio of the coordination site on the transition metal compound to (b) the coordination site to be occupied by the ligand is 0.1: 1 to 100: 1, preferably 0.2: 1 to 10: 1, more preferably 0.5 1: 1 to 3: 1, most preferably 0.8: 1 to 2: 1.

The radical chain polymerization of the present invention may be performed by a bulk polymerization method without using a solvent, or may be performed by a method using a solvent.

Examples of the solvent include ethers, cyclic ethers, alkanes having 5 to 10 carbon atoms, cycloalkanes having 5 to 8 carbon atoms which may be substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, acetonitrile and dimethyl. Formamide, or a mixture thereof, may be used, and a supercritical solvent such as alkane having 1 to 4 carbon atoms in which CO ₂ , any hydrogen atom may be substituted with a fluorine atom, or the like may be used.

In addition, the radical chain polymerization may be carried out according to a known suspension, emulsion, or precipitation polymerization.

Radical chain polymerization can be carried out in bulk or gaseous phase in a sealed vessel or autoclave. In the gas phase, the monomer can be carried out by passing through the chain polymerized active species (PO-A) and the catalyst layer previously contacted with the ligand.

The polymerization temperature is -78 to 200 ° C, preferably 0 to 160 ° C, most preferably 80 to 140 ° C.

The polymerization is carried out for a time sufficient to convert the monomers to at least 10%, preferably at least 50%, more preferably at least 75% and most preferably at least 90% to the polymer. Typically the polymerization time can be from several minutes to five days, preferably from 30 minutes to 3 days, most preferably from 1 to 24 hours.

The polymerization can be carried out at a pressure of 0.1 to 100 atm, preferably 1 to 50 atm, most preferably 1 to 10 atmospheres. At this time, when the polymerization is carried out in a sealed container, the polymerization pressure cannot be measured directly.

As described above, the olefin block copolymer of the present invention prepared according to the present invention has a number average molecular weight of 1,000 to 500,000 g / mol, preferably 2,000 to 250,000 g / mol, and more preferably 3,000 to 150,000 g / mol. . When prepared in bulk, the number average molecular weight will amount to 1,000,000 g / mol. The number average molecular weight can be measured by gel chromatography (GPC) or by NMR spectroscopy when the initiator has a group that can be easily distinguished from the monomers.

It is preferable that the said olefin block copolymer has a molecular weight distribution (weight average molecular weight / number average molecular weight) of less than 2.5.

The olefinic block copolymer can be applied to various applications. Specifically, it may be used as a film and sheet such as a shrink film, a protective film, a selective separator, and the like, a resin modifier, a rubber modifier, a lubricant modifier, a cement modifier, a filler modifier, a viscosity modifier. It can be applied to molding modifiers, aqueous emulsions, paint bases, compatibilizers and the like.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

The organic reagents and solvents required for the polymerization are from Aldrich, which was purified by standard methods. Ethylene was used for polymerization after passing high purity products from Applied Gas Technology through water and oxygen filtration. Used.

The physical properties of the prepared copolymer were evaluated by the following method.

* Polymer structure-Measured using 400 NMR (manufactured by Bruker).

* Melting Point-Measured using DSC Q100 (manufactured by TA Instrument).

* Molecular weight, molecular weight distribution-GPC PL-GPC220 (Gel chromatography, manufactured by Polymer Lab.) Was analyzed. In this case, trichlorobenzene (trichlorobenzene) as a solvent at a temperature of 160 ℃, standardized with polystyrene to measure the number average molecular weight (Mn) and weight average molecular weight (Mw).

<Production of Polyethylene (PE-OH) having a Hydroxyl Group at the End>

Examples 1 to 8

To the content as shown in Table 1 below, to a high purity argon atmosphere pressure glass reactor (Andrew flask) 30 mL of purified toluene and methyl aluminoxane (MAO, toluene solution 5.65 wt% Al, density = 0.722) 0.75 to 3.0 mmol After adding 1.5 μmol bis (pentamethylcyclopentadienyl) zirconium dichloride toluene solution, the reactor was left for 10 minutes in a 50 ° C thermostat, and the reactor temperature was the same as that of the thermostat. , 2.0 M toluene solution) was added 0-12.0 mmol. Thereafter, ethylene pressure was rapidly added to 1.25 atm, and polymerization was performed while stirring for 20 minutes. After 20 minutes of polymerization, ethylene pressure was removed, anhydrous oxygen was bubbled for 2 hours, the contents were poured into 100 ml of methanol / hydrochloric acid solution, stirred for 6 hours, and the filter was dried to obtain a white solid polymer (PE). -OH) was obtained. At this time, the yield and activity are measured and shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 MAO (mmol) 0.75 1.5 1.5 3 3 3 3 3 TMA (mmol) 0 0 0 0 1.5 3 6 12 Yield (g) 0.7 1.1 1.0 1.3 2.0 2.3 2.5 2.0 Activity * 1.2 1.8 1.6 2.1 3.2 3.7 4.0 3.2  * Activity: ton / Zr mole atm · h of PE

The physical properties of the polyethylene (PE-OH) prepared in Examples 1 to 8 are shown in Table 2 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Number average molecular weight 8,600 6,500 4,400 2,900 2,200 1,800 1,500 1,000 Molecular weight distribution 1.9 1.8 1.9 2.0 1.8 1.7 1.7 1.4 denomination - PE-OH (Ⅱ) PE-OH (III) - PE-OH (Ⅰ) - - -

As shown in Table 2, according to the present invention, a polyethylene segment having a hydroxyl group bonded to the terminal may be prepared by contacting anhydrous oxygen after polymerization without additional reaction, wherein the molecular weight of the segment can be easily controlled. I could confirm it.

The ¹ H NRM spectrum of polyethylene {PE-OH (III)} having a hydroxyl group bonded to the terminal prepared in Example 3 is shown in FIG. 1. According to Figure 1, through the a-peak appearing at 3.7 ppm, it was confirmed that the polyethylene with a hydroxyl group bonded to the terminal was produced.

<Preparation of radical chain polymerization active species (PE-Br)>

Examples 9-11

The prepared polyethylene (PE-OH) was placed in a flask containing toluene purified under a high purity argon atmosphere, and excess 2-bromoisobutyryl bromide and triethylamine were added, followed by stirring at 90 ° C for 6 hours. The amine salt produced as a side reaction was removed by filtration and dried in vacuo to give a white solid polymer (PE-Br).

The physical properties of the radical chain polymerization active species (PE-Br) prepared in Examples 9 to 11 are shown in Table 3 below.

division Example 9 Example 10 Example 11 PE-OH type PE-OH (Ⅰ) PE-OH (Ⅱ) PE-OH (III) Yield (g) 1.5 1.0 0.96 Number average molecular weight (GPC) 2,200 6,700 4,500 Number average molecular weight (NMR) 2,100 6,200 4,100 Molecular weight distribution 1.8 1.8 1.9 denomination PE-Br (Ⅰ) PE-Br (Ⅱ) PE-Br (Ⅲ)

The ¹ H NRM spectrum of the radical chain polymerization active species {PE-Br (III)} prepared in Example 11 is shown in FIG. 2. According to Figure 2, through the e-peak and f-peak appearing at 4.2 ppm and 2.0 ppm, respectively, it was confirmed that the radical chain polymerization active species is bonded at the end.

<Block copolymer (PE-g-PMMA) manufacture>

Examples 12-16

The prepared radically polymerized active species (PE-Br) was placed in an appropriate amount of reactor under a high purity argon atmosphere, 1.05 equivalents of ligand BA6-TREN, purified chlorobenzene, and then heated to 95 ° C. to produce a chain-polymerized active species (PE-Br). After dissolving), the temperature was raised to room temperature, and 100 to 200 equivalents of methyl (meth) acrylate (MMA) was added to the chain polymerized active species. The temperature was lowered to low temperature, and 1 equivalent of CuCl and 0.05 equivalent of CuCl ₂ were added to the chain polymerized active species, followed by stirring at 95 ° C. for 1 to 20 hours. At this time, in Example 12, [MMA] / [PE-Br] / [CuBr] / [CuBr ₂ ] / [BA ₆ TREN] = 100/1/1 / 0.05 / 1.05, and in Examples 13 to 16, [MMA] ] / [PE-Br] / [CuBr] / [CuBr ₂ ] / [BA ₆ TREN] = 200/1/1 / 0.05 / 1.05. After the polymerization was completed, the polymer was poured into methanol to precipitate, washed with methanol and filtered. Thereafter, after 24 hours of soxlet extraction with heptane, vacuum drying was performed to obtain a white solid polymer as follows.

division Example 12 Example 13 Example 14 Example 15 Example 16 PE-Br type PE-Br (Ⅰ) PE-Br (Ⅱ) PE-Br (Ⅲ) PE-Br (Ⅲ) PE-Br (Ⅲ) PE-Br (g) 0.75 0.9 0.23 0.23 0.23 Hours (h) 20 4 One 2 15 % Conversion 84.6 42.6 13.3 24.8 63.2 Yield (g) 3.0 1.6 0.24 0.29 0.64 Number average molecular weight 14,200 22,800 16,700 18,200 21,000 Molecular weight distribution 1.37 1.41 1.46 1.45 1.47 denomination PE-g-PMMA (Ⅰ) PE-g-PMMA (II) PE-g-PMMA (Ⅲ) PE-g-PMMA (Ⅳ) PE-g-PMMA (Ⅴ)

The GPC spectra of the block copolymers {PE-g-PMMA (III)} to {PE-g-PMMA (V)} prepared in Examples 14 to 16 are shown in FIG. 3. Referring to FIG. 3, it was confirmed that the block copolymer was formed through the increase in the number average molecular weight of the block copolymer compared to {PE-Br (III)}.

In addition, the ¹ H NRM spectrum of the block copolymer {PE-g-PMMA (I)} prepared in Example 12 is shown in FIG. 4. According to Figure 4, the ratio of the PE block and PMMA block of the block copolymer can be confirmed, the ratio of the PMMA block was 82% by weight.

As a result of DSC analysis, the melting point of polyethylene {PE-OH (I)} was 125 ° C, and the melting point of copolymer {PE-g-PMMA (I)} appeared between 106 ° C and 124 ° C. It was confirmed that the block copolymer was formed.

The ¹ H NRM spectrum of the block copolymer prepared in Example 13 {PE-g-PMMA (II)} is shown in FIG. 5, whereby it was confirmed that the proportion of PMMA blocks was 52% by weight. As a result of DSC analysis, the melting point of polyethylene {PE-OH (II)} was 131 ° C, and the melting point of copolymer {PE-g-PMMA (II)} appeared at 129 ° C.

The ¹ H NRM spectra of the block copolymers {PE-g-PMMA (III)} to {PE-g-PMMA (V)} prepared in Examples 14 to 16 are shown in FIG. 6. 6, it can be seen that the ratio of PMMA blocks in the {PE-g-PMMA (III)} to {PE-g-PMMA (V)} 43, 60, 72% by weight, respectively. As a result of DSC analysis, the melting point of polyethylene {PE-OH (III)} was 129 ° C, and the melting point of copolymer {PE-g-PMMA (III)} was 128 ° C and the copolymer {PE-g-PMMA In the case of (IV), the melting point was 125 ° C., and in the case of the copolymer {PE-g-PMMA (V)}, the melting point was confirmed at 124 ° C.

TEM photographs of block copolymers {PE-g-PMMA (III)} to {PE-g-PMMA (V)} prepared in Examples 14 to 16, and PE and PMMA blending polymers are shown in FIG. 7. According to Figure 7, it was confirmed that the image of the block copolymer and the blending polymer is significantly different. That is, the block copolymer has a uniform distribution of PE and PMMA on the TEM image due to the chemical bonding of PE and PMMA, whereas the blending polymer has a physical distribution of PE and PMMA on the TEM image. Apparently separate.

As described above, according to the present invention, a polyolefin segment having a hydroxyl group bonded to the terminal can be easily produced by the contact of anhydrous oxygen or air after the polymerization without further reaction, and converts it into a radical chain polymerization active species. By this radical polymerization, the ratio and molecular weight of a polyolefin segment and a functional segment can be adjusted easily, and the physical property of an olefin block copolymer can be adjusted easily.

Claims (18)

(I) preparing a polyolefin (PO-OH) having a hydroxyl group bonded to the terminal; (II) converting the prepared polyolefin (PO-OH) into a radical chain polymerization active species (PO-A); And (III) radical chain polymerization of the converted radical chain polymerization active species (PO-A), characterized in that Method for producing an olefin block copolymer. The method of claim 1, To prepare a polyolefin (PO-OH) having a hydroxyl group bonded to the terminal of (I), (Iii) preparing a polyolefin (PO-Group 13 element) having a Group 13 element bonded to the terminal; (Ii) oxidizing the terminal of the prepared polyolefin (PO-Group 13 element) to produce a polyolefin (PO-O-Group 13 element) whose end is converted to oxide; And (Iii) subjecting the produced polyolefin (PO-O-Group 13 element) to a alcoholic reaction. Method for producing an olefin block copolymer. The method of claim 2, The step (iii) is a step of solely or copolymerizing a linear α-olefin having 2 to 20 carbon atoms in the presence of a metallocene catalyst, an organic metal component as a promoter and a molecular weight regulator. Method for producing an olefin block copolymer. The method of claim 3, wherein The linear α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 At least one member selected from the group consisting of hexadecene and 1-octadecene. Method for producing an olefin block copolymer. The method of claim 3, wherein The organometallic component is characterized in that represented by the following formula (2) Method for producing an olefin block copolymer. [Formula 2] R ¹ _n AlX _3-n In Formula 2, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, n is an integer of 0 to 3. The method of claim 1, Step (II) is a step of converting the prepared polyolefin (PO-OH) with a compound represented by the following formula (6) to convert the terminal of the polyolefin to an α-halo acyl group (A) which is a functional group containing a halogen atom Characterized by Method for producing an olefin block copolymer. [Formula 6]

In Formula 6, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen, and n is an integer of 0 to 3. The method of claim 1, The step (III) is a step of adding a transition metal compound, a ligand, a monomer and a solvent to the prepared radical chain polymerization active species (PO-A) and performing radical chain polymerization. Method for producing an olefin block copolymer. The method of claim 7, wherein The transition metal compound is selected from compounds represented by the following formula (7) Method for producing an olefin block copolymer. [Formula 7] M ₂ ^{n +} X ′ _n In Formula 7, M ₂ ^{n +} is Cu ¹⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ³⁺ , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ⁺ , Mn ³⁺ , Mn ⁴⁺ , V ²⁺ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ and Ag ²⁺ , X ′ is halogen, alkoxy having 1 to 6 carbon atoms, (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ), triflate, hexafluorophosphate , Methanesulfonate, arylsulfonate, SeR ¹⁰ (wherein R ¹⁰ is aryl or a linear or branched alkyl group having 1 to 20 carbon atoms, which is a substituent which may be substituted 1 to 5 times with a halogen atom), CN and R ¹¹ CO ₂ (wherein R ¹¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms and is a substituent which may be substituted 1 to 5 times with a halogen atom), n is the formal charge on the metal and is an integer of 0 ≦ n ≦ 7. The method of claim 7, wherein The ligand is a ligand having at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus and sulfur, which can be coordinated to the transition metal via σ-bonding, to be coordinated to the transition metal via π-bonding. A ligand containing at least two carbon atoms, and a ligand capable of coordinating to the transition metal via a μ-bond or η-bond. Method for producing an olefin block copolymer. The method of claim 7, wherein The monomer is at least one member selected from the group consisting of unsaturated carboxylic acids and derivatives thereof. Method for producing an olefin block copolymer. The method of claim 1, The olefin block copolymer is represented by the following formula (1) Method for producing an olefin block copolymer. [Formula 1] PO-g-B In Formula 1, PO is a polyolefin segment consisting of repeating units derived from olefins having 2 to 20 carbon atoms, g is an ester bond, and B is a functional segment containing a hetero atom. The method of claim 11, The polyolefin segment has a weight average molecular weight of 500 to 1,000,000 Method for producing an olefin block copolymer. The method of claim 11, The functional segment has a weight average molecular weight of 500 to 1,000,000 Method for producing an olefin block copolymer. Claim 1 to 13 prepared by the method of any one of claims, characterized in that represented by the formula Olefin block copolymers. [Formula 1] PO-g-B In Formula 1, PO is a polyolefin segment consisting of repeating units derived from olefins having 2 to 20 carbon atoms, g is an ester bond, and B is a functional segment containing a hetero atom. The method of claim 14, The polyolefin segment has a weight average molecular weight of 500 to 1,000,000 Olefin block copolymers. The method of claim 14, The functional segment has a weight average molecular weight of 500 to 1,000,000 Olefin block copolymers. The method of claim 14, The weight ratio of the polyolefin segment and the functional segment is 0.01: 99.99 to 99.99: 0.01, characterized in that Olefin block copolymers. The method of claim 14, The olefin block copolymer has a molecular weight distribution of less than 2.5, characterized in that Olefin block copolymers.

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