JP4263136B2 - Olefin-based block copolymer and production method - Google Patents

Description

  The present invention relates to an olefinic block copolymer, and more particularly to an olefinic block copolymer having a specific structure comprising a polyolefin segment having a functional site (functional group) and a method for producing the same.

  Polyolefins are excellent in processability, chemical resistance, electrical properties, mechanical properties, etc., so they are processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, etc., and used in various applications. Yes. However, since polyolefin is a so-called nonpolar resin that does not have a polar group in the molecule, it has poor affinity with various polar substances including metals, and adhesion with polar substances or blending with polar resins is difficult. It was. In addition, the surface of the molded body made of polyolefin is hydrophobic, and in applications that require anti-fogging properties and antistatic properties, it is necessary to add a low molecular weight surfactant, etc. In some cases, problems such as contamination occurred.

  In recent years, demands for physical properties of polyolefins have been diversified. For example, polyolefins having various properties such as polyolefins having excellent heat resistance and polyolefins having soft feel such as soft polyvinyl chloride are desired.

  There are various methods for improving the physical properties of polyolefins, such as a method for adjusting the type and molar ratio of monomers, a method for changing the monomer sequence such as random and block, and a method for graft copolymerization of polar monomers to polyolefin. The method has been tried.

  When graft copolymerizing a polar monomer (polar olefin) with a polyolefin, a method of reacting a polyolefin with a radical polymerizable monomer in the presence of a radical initiator is generally performed. The graft copolymer often contains a homopolymer of a radical polymerizable monomer or unreacted polyolefin, and the graft structure is also non-uniform. Furthermore, since the polymer chain is accompanied by a cross-linking reaction or a decomposition reaction of the polymer chain, the physical properties of the polyolefin often change greatly. Regarding a method for synthesizing a block polymer of a polyolefin and a polar polymer without the crosslinking / decomposition reaction as described above, International Publication WO 98/02472 describes a method in which a boron compound is added to a polyolefin having an unsaturated bond at a terminal. A method is described in which radical polymerization active species are formed by oxidation with oxygen, followed by radical polymerization.

  In addition, as a method for producing a block (co) polymer composed of two different polymer segments, JP-A-60-252614, JP-A-60-252623, JP-A-5-503546, JP-A-8-92338, JP-A-9-87343, and the like disclose methods utilizing living polymerization. Among them, JP-A-60-252614 discloses a method for producing a block copolymer comprising a polyolefin segment and a polymethacrylic acid ester segment by living polymerization. However, in this method using living polymerization, only one polymer can be obtained from one catalyst active point, and it is preferable that the number of polymers obtained from one catalyst active point is larger in view of cost.

Such a block (co) polymer is an excellent material having the characteristics of combining two different polymer segments, but in order to meet various physical property requirements for polymer materials from the industrial world in recent years, Development of a block (co) polymer having a reactive functional group in the main chain segment is desired in order to impart functionality suitable for the above applications.
WO98 / 02472 JP-A-60-252614 JP 60-252623 A Japanese National Patent Publication No. 5-503546 JP-A-8-92338 JP-A-9-87343

  As a result of investigations based on such conventional techniques, the present inventors have found a novel olefin block copolymer having a structure comprising a polyolefin segment having a specific functional site (functional group) and a production method thereof. It was.

The olefin block copolymer of the present invention has at least one reactive unsaturated bond in the main chain (A) having crystallinity composed of an olefin chain having a repeating unit derived from ethylene as a main structural unit. An olefin block copolymer having at least one side chain (B) comprising a polymer of a compound having a moiety, wherein the compound having a reactive unsaturated bond is an aromatic ring-containing vinyl compound and (meta ) A polymer selected from acrylic ester compounds, wherein the main chain (A) has a weight average molecular weight (Mw) of 1,000 to 10,000,000 measured by gel permeation chromatography (GPC) (A '), And the main chain of the olefin block copolymer has at least one group selected from a carboxyl group and an acid anhydride group. This is an olefin block copolymer.

The present invention also relates to a crystalline polymer (A ′) comprising an olefin chain having a repeating unit derived from ethylene as a main structural unit and having at least one group selected from a carboxyl group and an acid anhydride group. And a polymer (B ′) having an active site activated by at least one metal selected from alkali metals and alkaline earth metals, and a method for producing an olefin block copolymer It is.

  The olefin block copolymer according to the present invention is a block copolymer in which a polyolefin segment constituting a main chain and a compound segment having a reactive unsaturated bond portion constituting a side chain are chemically bonded to each other. It has a carboxyl group and / or an acid anhydride group in it, is a polymer that combines the physical properties and characteristics of both segments and has a reactive group, mechanical properties such as heat resistance and flexibility, electrical properties, and adhesion Excellent in coating properties and coating properties.

Hereinafter, the olefin block copolymer according to the present invention will be specifically described. The olefin block copolymer according to the present invention comprises at least one type of reactive unsaturation in the main chain (A) having crystallinity composed of an olefin chain having a repeating unit derived from ethylene as a main structural unit. An olefin block copolymer having one or more side chains (B) made of a polymer of a compound having a bond part, wherein the compound having a reactive unsaturated bond part is an aromatic ring-containing vinyl compound and ( A polymer having a weight average molecular weight (Mw) of 1,000 to 10,000,000 as measured by gel permeation chromatography (GPC). A ′), and at least one group selected from a carboxyl group and an acid anhydride group is present in the main chain of the olefin block copolymer. It is an olefin block copolymer characterized by having the above. Hereinafter, the main chain (A) and the main chain (B) forming the olefin block copolymer of the present invention will be described in detail.

Main chain (A)
The main chain (A) is composed of an olefin chain having a repeating unit derived from ethylene as a main structural unit. The olefin chain may have the following olefins in addition to ethylene.

  Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and nonconjugated polyenes.

  Specific examples of the linear or branched α-olefin include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 A linear α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as hexadecene, 1-octadecene, 1-eicosene, etc .; for example, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1- Preferably branched α-olefins such as hexene and 3-ethyl-1-hexene are preferably 5 to 20, more preferably 5 to 10.

  Examples of the cyclic olefin include those having 3 to 20, preferably 5 to 15 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylcyclohexane and the like.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Mono or polyalkyl styrenes such as ethyl styrene are mentioned.

  Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene. , 1,3-octadiene and the like having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms.

  Non-conjugated polyenes include, for example, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2 -Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1 , 4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene -2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2 -5 carbon atoms such as norbornadiene 20, preferably include the 5 to 10.

  Examples of functionalized vinyl compounds include hydroxyl group-containing olefins, halogenated olefins, acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid and 8-nonenoic acid. , Unsaturated carboxylic acids such as 9-decenoic acid, unsaturated amines such as allylamine, 5-hexeneamine, 6-hepteneamine, (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride and the above In the examples of compounds in the saturated carboxylic acids, unsaturated acid anhydrides such as compounds in which the carboxylic acid group is replaced with a carboxylic anhydride group, in the examples of compounds in the unsaturated carboxylic acids, the carboxylic acid group is converted to a carboxylic acid Unsaturated carboxylic acid halides such as compounds substituted with halide groups, 4-epoxy-1-butene, -Epoxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy Examples thereof include unsaturated epoxy compounds such as -1-undecene.

  The hydroxyl group-containing olefin is not particularly limited as long as it is a hydroxyl group-containing olefin compound, and examples thereof include terminal hydroxylated olefin compounds.

  Specific examples of the terminal hydroxylated olefin compound include vinyl alcohol, allyl alcohol, hydroxyl-1-butene, hydroxyl-1-pentene, hydroxyl-1-hexene, hydroxyl-1-octene, hydroxyl-1 -Decene, hydroxyl-1-dodecene, hydroxyl-1-tetradecene, hydroxyl-1-hexadecene, hydroxyl-1-octadecene, hydroxyl-1-octadecene, hydroxyl-1-eicosene, etc. 2-20, preferably 2 10 linear hydroxylated α-olefins; for example, hydroxylated 3-methyl-1-butene, hydroxylated 4-methyl-1-pentene, hydroxylated 3-methyl-1-pentene, hydroxylated-3 -Ethyl-1-pentene, hydroxyl-4,4-dimethyl-1-pentene, hydroxyl-4-methyl-1-hexene, hydroxyl-4,4-dimethyl-1-hexene, hydroxyl-4-ethyl hydroxide -1-hexene, hydroxide-3-ethyl-1-hexene Preferably, a branched hydroxylated α-olefin having 5 to 20 and more preferably 5 to 10 is used.

  Specific examples of the halogenated olefin include, for example, vinyl halide, halogenated-1-butene, halogenated-1-pentene, halogenated-1 having a group 17 atom in the periodic table of chlorine, bromine, iodine, etc. -Hexene, halogenated-1-octene, halogenated-1-decene, halogenated-1-dodecene, halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated-1- Straight chain halogenated α-olefins having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as eicosene; for example, halogenated-3-methyl-1-butene, halogenated-4-methyl-1-pentene, halogen -3-methyl-1-pentene, halogenated-3-ethyl-1-pentene, halogenated-4,4-dimethyl-1-pentene, halogenated-4-methyl-1-hexene Halogenated-4,4-dimethyl-1-hexene, halogenated-4-ethyl-1-hexene, halogenated-3-ethyl-1-hexene, etc., preferably 5-20, more preferably 5-10 Examples include branched halogenated α-olefins.

Backbone consisting of the olefin chain (A) is homopolymer of good Mashiku is ethylene emissions, ethylene and at least one copolymer derived from an olefin selected from olefins having 3 to 20 carbon atoms, with propylene is a segment derived from a copolymer obtained from at least one olefin selected from olefins of ethylene and carbon atom number 4 to 20.

The main chain (A) comprising the olefin chain has crystallinity, and the crystallinity of the segment constituting the main chain (A) is 20% or more, preferably 25% or more, more preferably 30% or more. is there. When the segment constituting the main chain (A) is a segment derived from a copolymer obtained using at least one olefin selected from olefins having 3 to 20 carbon atoms, measurement using, for example, NMR The stereoregularity clarified by the formula (1) may be any polyolefin having an isotacticity of 50% or more, or a syndiotacticity of 50% or more. Since the main chain (A) composed of an olefin chain has crystallinity, it not only exhibits olefin-derived physical properties, but also has excellent mechanical properties such as rigidity of the copolymer.

Side chain (B)
Next, the side chain (B) composed of a polymer of at least one compound having a reactive unsaturated bond part, which forms the olefin block copolymer of the present invention will be described. The side chain (B) is a polymer of a compound having a reactive unsaturated bond portion or a copolymer comprising a compound having two or more types of reactive unsaturated bond portions.

Examples of the compound having a reactive unsaturated bond portion, is needed use the replacement vinyl compound.

The substituted vinyl compound is a compound selected from ( meth) acrylic acid esters and aromatic ring-containing vinyl compounds .

  Examples of the (meth) acrylate used in the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and vinyl acrylate. , 2-methoxyethyl methacrylate, 2- (N, N-diethylamino) ethyl methacrylate and the like. These (meth) acrylic acid esters can be used singly or in combination of two or more.

  As an aromatic ring containing vinyl compound used for this invention, the compound represented by a following formula is mentioned, for example.

上記式において、Ｒ³およびＲ⁴は、互いに同一でも異なっていてもよく、水素原子または炭素原子数が１〜３のアルキル基を示し、具体的には、メチル基、エチル基、プロピル基およびイソプロピル基を挙げることができる。また、Ｒ⁵は炭素原子数１〜３の炭化水素基またはハロゲン原子を示し、具体的には、メチル基、エチル基、プロピル基およびイソプロピル基並びに塩素原子、臭素原子およびヨウ素原子などを挙げることができる。また、ｎは通常は０〜５、好ましくは１〜５の整数を表す。

In the above formula, R ³ and R ⁴ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, and Mention may be made of the isopropyl group. R ⁵ represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a chlorine atom, a bromine atom, and an iodine atom. Can do. N represents an integer of usually 0 to 5, preferably 1 to 5.

  Specific examples of the aromatic ring-containing vinyl compound represented by the above formula include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, Examples thereof include mono- or polyalkyl styrene such as o-ethyl styrene, m-ethyl styrene, and p-ethyl styrene, p-chlorostyrene, m-chlorostyrene, and p-chloromethylstyrene.

  Examples of the aromatic ring-containing vinyl compound include a heterocyclic compound residue-containing vinyl compound containing a hetero atom. Specific examples of the heterocyclic compound-containing vinyl compound include 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, and 2-isopropenylpyridine. 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, N-vinylpyrrolidone and the like.

  Among these, two or more aromatic ring-containing vinyl compounds can be copolymerized to produce a polyaromatic ring-containing vinyl compound segment.

  The side chain (B) according to the present invention may be used as a copolymer segment by using an aromatic ring-containing vinyl compound and / or (meth) acrylic acid and / or (meth) acrylic acid ester in combination.

  Examples of the olefin having 2 to 20 carbon atoms used for the side chain (B) include linear or branched α-olefins and cyclic olefins shown in the description of the main chain (A) composed of the olefin chain described above. Conjugated dienes and non-conjugated polyenes.

  The side chain (B) comprising a polymer of the above substituted vinyl compound is a segment comprising these aromatic ring-containing vinyl compounds, and / or (meth) acrylic acid, and / or (meth) acrylic ester and / or olefin. Preferably, an aromatic ring-containing vinyl compound or a (meth) acrylic acid ester homopolymer, or an olefin homopolymer, a copolymer comprising two or more aromatic ring-containing vinyl compounds, two types A copolymer comprising the above (meth) acrylic acid ester, a copolymer of an aromatic ring-containing vinyl compound and (meth) acrylic acid ester, an aromatic ring-containing vinyl compound and an olefin having 2 to 20 carbon atoms. A copolymer obtained from at least one olefin selected from (meth) acrylic acid esters and olefins having 2 to 20 carbon atoms A copolymer obtained from at least one olefin, and a copolymer obtained from at least one olefin selected from an aromatic ring-containing vinyl compound and a (meth) acrylic acid ester and / or an olefin having 2 to 20 carbon atoms Is mentioned.

Next, the manufacturing method of the olefin type block copolymer of this invention is demonstrated. The olefin block copolymer of the present invention comprises an olefin chain having a repeating unit derived from ethylene as a main structural unit, and has at least one group selected from a carboxyl group and an acid anhydride group. A side chain (B) having an active site activated by at least one kind of metal selected from alkali metals and alkaline earth metals and a polymer (A ′) having crystallinity to form It is produced by reacting the polymer (B ′). In the present invention, the number of groups selected from carboxyl groups and acid anhydride groups present in the main chain and the number of side chains (B) are the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). It can be calculated from the value of. [1] Production method of polymer (A ′), [2] Production method of polymer (B ′), and [3] Olefin by reaction of polymer (A ′) and polymer (B ′) The production method of the block copolymer will be described in detail.

[1] Production Method of Polymer (A ′) First, an olefin polymerization catalyst used for production of a polymer (A ′) comprising an olefin chain will be described. The olefin polymerization catalyst used for the production of the polymer (A ′) comprising an olefin chain may be any conventionally known catalyst. Conventionally known catalysts include, for example, magnesium-supported titanium catalysts and metallocene catalysts. For example, the catalysts described in International Patent Publications WO01 / 53369 or WO01 / 27124 are preferably used.

  The polymer (A ′) comprising the above olefin chain is produced by a polymerization method such as a solvent suspension polymerization method or a suspension polymerization method using a liquid olefin as a solvent.

  When carrying out the solvent suspension polymerization, a polymerization inert hydrocarbon can be used as a polymerization solvent. Specific examples of the inert hydrocarbon medium used here include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; fats such as cyclopentane, cyclohexane, and methylcyclopentane. Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or combinations thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon.

  When a magnesium-supported titanium catalyst system is used, in the polymerization system, the solid titanium catalyst component (a) or its prepolymerized catalyst is usually about 0.0001 to about 0.0001 to 1 in terms of titanium atoms per liter of polymerization volume. It is used in an amount of 50 mmol, preferably about 0.001 to 10 mmol. In the organometallic compound catalyst component (b), the metal atom in the catalyst component (b) is usually 1 to 2000 mol, preferably 1 mol to 1 mol of titanium atom in the solid titanium catalyst component (a) in the polymerization system. Is used in an amount of 2 to 1000 mol. The electron donor (ED) is generally used in an amount of 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, relative to 1 mol of the metal atom of the organometallic compound catalyst component (b).

  In the polymerization step, the hydrogen concentration is preferably 0 to 0.01 mol, preferably 0 to 0.005 mol, more preferably 0 to 0.001 mol with respect to 1 mol of the monomer.

  Further, the production of the polymer (A ′) comprising an olefin chain can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. As the reaction solvent for suspension polymerization, the above-mentioned inert solvent can be used, or a liquid olefin can be used at the reaction temperature. The polymerization temperature is usually in the range of 70 ° C. or higher, preferably 80 to 150 ° C., more preferably 85 to 140 ° C., particularly preferably 90 to 130 ° C., and the pressure is usually normal pressure to 10 MPa, preferably normal. The pressure is set to 5 MPa. The polymerization can be carried out by any of batch, semi-continuous and continuous methods. When the polymerization is carried out in two or more stages, the reaction conditions may be the same or different.

  The production of the polymer (A ′) comprising an olefin chain can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, and gas phase polymerization methods. As the polymerization form, it is preferable to adopt a suspension polymerization reaction form. As the reaction solvent at this time, an inert hydrocarbon solvent can be used, or a liquid olefin can be used at the reaction temperature.

  Specific examples of the inert hydrocarbon medium used here include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or combinations thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon.

  In the case of producing a polymer (A ′) comprising an olefin chain using a magnesium-supported titanium catalyst system as a catalyst, the solid titanium catalyst component (a) or the prepolymerized catalyst thereof contains titanium atoms per liter of polymerization volume. The amount is usually about 0.001 to 100 mmol, preferably about 0.005 to 20 mmol. In the organometallic compound catalyst component (b), the metal atom in the catalyst component (b) is usually about 1 to 2000 mol per 1 mol of titanium atom in the solid titanium catalyst component (a) in the polymerization system, Preferably it is used in such an amount that it is about 2 to 500 mol. The electron donor (ED) is usually used in an amount of 0 mol to 10 mol, preferably 0 mol to 5 mol, relative to 1 mol of the metal atom of the organometallic compound catalyst component (b).

  In the polymerization step, the hydrogen concentration is usually 0 to 0.25 mol, preferably 0 to 0.20 mol, more preferably 0 to 0.15, relative to 1 mol of the monomer.

  When the magnesium-supported titanium catalyst system is used, the polymerization temperature is usually in the range of about 20 to 300 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is 0.01 to 10 MPa, preferably 0.05 to The range is 5 MPa.

  When the polymer (A ′) comprising an olefin chain is produced using a metallocene catalyst as a catalyst, the concentration of the metallocene compound (c) in the polymerization system is usually from 0.000005 to 0 per 1 liter of polymerization volume. Used in an amount of 0.1 mmol, preferably 0.0001 to 0.05 mmol. The organoaluminum oxy compound (d) has a molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound (c) and is 5-1000, preferably 10-400. Used in various amounts. When the organoaluminum compound (b-2) is used, it is usually about 1 to 300 mol, preferably about 2 to 200 mol, per 1 mol of the transition metal atom in the metallocene compound (c). Used in quantity.

  The metallocene catalyst may be used as a solution in a solvent in which the metallocene is soluble, or may be used as a supported catalyst using an inorganic compound or a resin composition as a simple substance.

  When the metallocene catalyst is used, the polymerization temperature is usually in the range of −20 to 150 ° C., preferably 0 to 120 ° C., more preferably 0 to 100 ° C., and the polymerization pressure exceeds 0 to 8 MPa, preferably Is in the range of more than 0 and 5 MPa.

The polymer (A ′) is a polymer having at least one group selected from a carboxyl group and an acid anhydride group, and has crystallinity composed of an olefin chain having a repeating unit derived from ethylene as a main structural unit. It is a polymer . Also, the polymer (A ') is preferably a copolymer having at least one crystalline derived from an olefin selected from olefins of ethylene and 4 to 20 carbon atoms. Further, the polymer (A ') a propylene and ethylene, and / or copolymers having a crystallinity which is obtained from at least one olefin selected from olefins of ethylene, propylene and carbon atom number 4-20 It is preferable that

  Production of the polymer (A ′) comprising an olefin chain can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions. In olefin polymerization, an olefin homopolymer may be produced, or a random copolymer may be produced from two or more olefins.

  The obtained polymer (A ′) has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of 1,000 to 10,000,000 in terms of polystyrene. More preferably, it is 1,500-5,000,000. Moreover, it is preferable that molecular weight distribution (Mw / Mn) represented by ratio with a number average molecular weight (Mn) is 10 or less, More preferably, it is 5.0 or less.

[2] Production method of polymer (B ′) Polymer (B ′) of a compound having a reactive unsaturated bond is produced not only by the olefin polymerization catalyst used for the production of polymer (A ′), but also by a radical polymerization catalyst. , An anionic polymerization catalyst, a cationic polymerization catalyst or the like.

  In radical polymerization, any initiator used in ordinary radical polymerization can be used as the initiator, and examples thereof include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarboxyl. Azo initiators such as nitrile, azobis-2-amidinopropane hydrochloride, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride or 4,4′-azobis-4-cyanovaleric acid, benzoyl peroxide, 2,4-dichloro Benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide Peroxidation of sid, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxylaurate, di-tert-butyl peroxyphthalate, dibenzyl oxide or 2,5-dimethylhexane-2,5-dihydroperoxide Or a redox initiator such as benzoyl peroxide-N, N-dimethylaniline or peroxodisulfuric acid-sodium hydrogen sulfite.

  Of these, azo initiators or peroxide initiators are preferable, and azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, dimethyl azobisisobutyrate, Benzoyl oxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, diisopropyl dicarbonate peroxide or acetyl peroxide. These radical polymerization initiators can be used alone or in combination of two or more simultaneously or sequentially.

  Any solvent can be used as long as it does not inhibit the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane, heptane, and octane can be used as specific examples. , Aliphatic hydrocarbon solvents such as nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride And chlorinated hydrocarbon solvents such as tetrachloroethylene, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl isobutyl ketone Ketone solvents; ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, diethyl ether, di -n- amyl ether, may be mentioned tetrahydrofuran and ether solvents such as dioxy anisole and the like. Further, suspension polymerization and emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

  The reaction temperature may be any temperature as long as the polymerization reaction proceeds, and is not uniform depending on the desired degree of polymerization of the polymer, the type and amount of the radical polymerization initiator and the solvent used, but usually from −100 ° C. to 250 ° C. Preferably it is -50 degreeC-180 degreeC, More preferably, it is 0 degreeC-160 degreeC. In some cases, the reaction can be performed under reduced pressure, normal pressure, or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

In addition to the method using the above radical polymerization initiator, for example, a living radical polymerization method described in the following literature can be used as the radical polymerization.
1) J. Am. Chem. Soc., 116, 7943 (1994),
2) Macromolecules, 27, 7228 (1994),
3) J. Am. Chem. Soc., 117, 5614 (1995)
4) Macromolecules, 28, 7901 (1995)
5) WO96 / 30421 publication
6) Publication of WO97 / 18247
7) WO98 / 01480 publication
8) WO98 / 40415 publication
9) Macromolecules, 28, 1721 (1995)
10) Japanese Patent Laid-Open No. 9-208616
11) Japanese Patent Laid-Open No. 8-41117

  In anionic polymerization, as the anionic polymerization initiator, any initiator used in ordinary anionic polymerization can be used, for example, organolithium compounds such as butyl lithium, propyl lithium, ethyl lithium, methyl lithium, Grignard A reagent etc. can be used.

  Solvents that can be used include, for example, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, diethyl ether, dioxane, tetrahydrofuran (THF), Ether-based solvents such as monoglyme and diglyme are used. These solvents can be used singly or in combination of two or more. Of these, aromatic hydrocarbons and ether solvents are preferably used. The polymerization is usually performed at a polymerization temperature of −100 ° C. to 100 ° C., preferably −80 ° C. to 80 ° C., more preferably −70 ° C. to 70 ° C. for 1 minute to 500 hours, preferably 10 minutes to 300 hours, more preferably. Is carried out over 15 minutes to 150 hours.

  In cationic polymerization, any initiator used in ordinary cationic polymerization can be used as the cationic polymerization initiator. Examples of usable solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatics. Group hydrocarbons, ether solvents and the like are used. These solvents can be used singly or in combination of two or more. The polymerization is not particularly limited, but is usually −100 ° C. to 100 ° C., preferably −80 ° C. to 80 ° C., more preferably −70 ° C. to 70 ° C. for 1 minute to 500 hours, preferably 10 minutes. It is carried out for ˜300 hours, more preferably 15 minutes to 150 hours (for example, the method described in the Chemical Society of Japan, New Experimental Chemistry Course 19, “Polymer Chemistry 1”, Chapter 2, etc.).

  The polymer (B ′) of the compound having a reactive unsaturated bond part used in the present invention may be a reactive polymer having one or more reactive sites in the polymer as necessary. it can.

  Specific examples of reactive sites include hydroxyl groups, carboxyl groups, amino groups, imino groups, azide groups, vinyl groups, thiol groups, epoxy groups, isocyanate groups, halocarbonyl groups such as carbonyl chloride and carbonyl bromide, lithium Examples include alkoxide groups such as alkoxide, sodium alkoxide, potassium alkoxide, magnesium alkoxide, calcium alkoxide, aluminum alkoxide, zinc alkoxide, and silane alkoxide. Acid anhydrides formed from two carboxyl groups, carboxylates formed from carboxyl groups and metal-containing compounds, and the like can also be regarded as reactive sites.

  Moreover, when manufacturing the polymer (B ') which consists of a compound which has a reactive unsaturated bond part, it can exist without making a reactive point deactivate, and can be made into a reactive polymer. Specifically, the reactive polymer is present without causing deactivation of the polymerization active sites of the living radical polymerization reaction and the anion polymerization, which are generally produced by living anion polymerization in which the polymerization proceeds in a living manner. It can also be.

  Among these, as the at least one metal selected from alkali metals and alkaline earth metals that activate the polymer (B ′), lithium metal atoms, sodium metal atoms, and magnesium metal atoms are preferably used. When the side chain (B) is produced in a living manner using a compound containing the above metal as a catalyst, the polymer (B ′) that has not been deactivated may be used as it is for the production of an olefin block copolymer. This is advantageous in terms of manufacturing cost.

  The active site in the polymer (B ′) activated by at least one metal selected from the alkali metals and alkaline earth metals forms an ion pair with carbon in the polymer (B ′). It is desirable that the carbon in the polymer (B ′) forming the ion pair has at least three carbon chains in order to improve the stability of the ion pair and the performance of the produced copolymer. It is preferable that it is a part.

  The polymer (B ′) has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of 1,000 to 10,000,000 in terms of polystyrene. More preferably, it is 1,500-5,000,000. Moreover, it is preferable that molecular weight distribution (Mw / Mn) represented by ratio with a number average molecular weight (Mn) is 10 or less, More preferably, it is 5.0 or less.

  In the olefin block copolymer according to the present invention, the main chain (A) and the side chain (B) may be bonded by a carbon-carbon bond or bonded in a bonding mode containing a hetero atom. May be. Specific examples of the bonding mode containing a hetero atom include a bonding mode comprising a carbonyl group. Specifically, a ketone compound having a main chain (A) and a side chain (B) as a substituent of a ketone group, an ester compound having a main chain (A) and a side chain (B) as a substituent of an ester group, Amide compound having chain (A) and side chain (B) as substituents of amide group, imide compound having main chain (A) and side chain (B) as substituents of imide group, main chain (A) and side A method for producing an ether compound in which the chain (B) is bonded with an oxygen atom is preferably used. The olefin block copolymer according to the present invention is produced by a method for forming such a bond, and the bond method can be used without limitation as long as it is generally a known method in a chemical reaction ( For example, the method described in Morrison-Boyd, translated by Akihiro Nakahira et al., Organic Chemistry (5th edition, middle), Tokyo Chemical Dojin, Chapters 18, 21, 24, etc.).

  The olefin block copolymer according to the present invention has at least one group selected from a carboxyl group and an acid anhydride group in the main chain (A) of the olefin block copolymer. It is an olefin block copolymer. The carboxyl group and the acid anhydride group introduced into the main chain (A) may be introduced by providing a monomer having a group selected from a carboxyl group and an acid anhydride group during the production of the polymer (A ′). After the production of the polymer (A ′), the polymer (A ′) may be reacted and introduced in the presence of a compound having a group selected from a carboxyl group and an acid anhydride group. In addition, after producing a block copolymer comprising the main chain (A) and the side chain (B), the block copolymer is reacted and introduced in the presence of a compound having a group selected from a carboxyl group and an acid anhydride group. May be.

  Preferred examples of the functionalized vinyl compound having a group selected from a carboxyl group and an acid anhydride group that can be used in the production of the polymer (A ′) include maleic acid and maleic anhydride.

  The method of reacting with a compound having a group selected from a carboxyl group and an acid anhydride group after the production of the polymer (A ′) is not particularly limited, but the reaction may be performed using a radical generator, and the reaction may be performed by a thermal reaction. You may let them. The reaction temperature is −200 to 500 ° C., preferably −50 ° C. to 400 ° C.

[3] Method for Producing Olefin Block Copolymer Next, a method for producing an olefin block copolymer will be described. The production method is not particularly limited as long as an olefin block copolymer having at least one group selected from a carboxyl group and an acid anhydride group can be produced in the main chain of the present invention. A polymer (B ′) comprising a group selected from a carboxyl group and an acid anhydride group present in a polymer (A ′) comprising an olefin chain, and a compound having a reactive unsaturated bond as a reactive polymer. ) Can be reacted to produce an olefin block copolymer.

  Examples of the reaction include an ester group formation reaction by dehydration reaction between a carboxyl group-containing polymer (A ′) and a hydroxyl group-containing polymer (B ′), or a carboxyl group-containing polymer (A ′) and an amino group. Amide group formation reaction by dehydration reaction with polymer (B ′), reaction between polymer (A ′) having acid anhydride group and polymerization reaction point at terminal of polymer (B ′) containing alkyl metal compound Examples thereof include a ketone group forming reaction due to the reaction, an imide group forming reaction due to a reaction between the polymer (A ′) having an acid anhydride group and the polymer (B ′) having an amino group.

  An olefin comprising a polymer (A ′) having a group selected from a carboxyl group and an acid anhydride group, and a polymer (B ′) activated by at least one metal selected from an alkali metal and an alkaline earth metal The system block copolymer utilizes a reaction between a site activated by a metal atom in the polymer (B ′) and a group selected from a carboxyl group and an acid anhydride group in the polymer (A ′). Even manufactured.

  What is important in the production method of the present invention is that the number of groups selected from a carboxyl group and an acid anhydride group (Aa) in the polymer (A ′) and the number of active sites in the polymer (B ′) (B −b) satisfies the relational expression (1) of (A−a) ≧ (B−b).

  When the number of active sites in the polymer (B ′) is larger than the number of groups selected from the carboxyl group and the acid anhydride group in the polymer (A ′), after the production of the olefin block copolymer, unreacted The polymer (B ′) is not preferable because it may coexist with the copolymer and cause a decrease in physical properties of the copolymer. In the case where the number of groups selected from carboxyl groups and acid anhydride groups in the polymer (A ′) is larger than the number of active sites in the polymer (B ′), In addition, a carboxyl group or an acid anhydride group, which is a reactive group, is present, which contributes to improving the physical properties of the copolymer and has high industrial utility value.

  The reaction may be performed in a solution state using a solvent, or may be performed in a suspended state using a solvent. Moreover, you may carry out under the molten state of a polymer (A ') and / or a polymer (B'). Moreover, it can also react using a catalyst as needed.

  Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; diethyl ether, dioxane, tetrahydrofuran (THF), monoglyme, and diglyme. An ether solvent such as is used. These solvents can be used singly or in combination of two or more. Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferably used.

  The reaction is usually performed at a temperature of -100 ° C to 500 ° C, preferably -50 ° C to 300 ° C, for 1 minute to 500 hours, preferably 10 minutes to 300 hours.

  The olefin block copolymer according to the present invention has at least one side chain (B) made of a polymer of at least one substituted vinyl compound in the main chain (A) made of an olefin chain. And when the main chain (A) has more than one side chain (B), the side chain (B) may be the same type of polymer or a different type of polymer. Also good. As an example of a block copolymer having more than one side chain (B), the main chain (A): [A] has more than one same type of polymer [B] as the side chain (B). [A] / [B] binary block copolymer or main chain (A): [A] has different types of polymers [B] and [B ′] as side chains (B) [A] ] / [B] [B ′] ternary block copolymer, main chain (A): [A] side chains different types of polymers [B], [B ′] and [B ″] Examples of (B) include [A] / [B] [B ′] [B ″] quaternary block copolymer.

  As described above, a polymer containing a block copolymer in which a polyolefin segment (PO) and a compound segment (SV) having a reactive unsaturated bond portion are chemically bonded can be produced. And a compound segment SV having a reactive unsaturated bond portion include a chemically bonded polymer, for example, based on molecular weight of the polymer obtained, solubility in an organic solvent, or spectroscopic analysis can do. That is, the molecular weight of the polymer obtained by the method of the present invention shows a high value relative to the molecular weight of PO, the polymer corresponding to the segment PO of the olefin block copolymer polymer obtained by the method of the present invention and the polymer. The dissolution behavior of the compound having a reactive unsaturated bond in the organic solvent indicated by the mixture of the polymer and the polymer corresponding to the segment SV indicates that the olefinic block copolymer obtained by the method of the present invention is dissolved in the organic solvent. It is different from the dissolution behavior, or the peak derived from the chemical bond between the segment PO and the segment SV when the terminal structure of the olefin block copolymer obtained by the method of the present invention is analyzed by IR and NMR. By detecting this, it can be determined that the target block copolymer has been produced.

(Use)
The olefin block copolymer according to the present invention is a block copolymer in which a polyolefin segment constituting a main chain and a compound segment having a reactive unsaturated bond portion constituting a side chain are chemically bonded, and It is a block copolymer having a functional group in the main chain. This copolymer is a copolymer having both physical properties and characteristics of both segments and having reactivity.

  The olefin block copolymer in the present invention contains various additives such as a softening agent, a stabilizer, a filler, an antioxidant, a crystal nucleating agent and the like as long as the purpose of the present invention is not impaired. can do.

  The adhesive resin according to the present invention is an adhesive, such as a hot melt adhesive, comprising the olefin block copolymer according to the present invention, which has excellent characteristics of tackiness, heat-resistant creep property, and fluidity. And is preferably used.

  The hot melt adhesive composition according to the present invention contains the olefin block copolymer and a tackifying resin (B). The tackifier (B) is blended in order to adjust the viscosity at the time of melting of the olefin block copolymer that is the base polymer, and to improve hot tack property and wettability. The tackifier (B) is not particularly limited as long as it can be blended with the olefin block copolymer and can improve the hot tack and wetness of the olefin block copolymer during heating.

  Specific examples of tackifiers include alicyclic hydrogenated tackifiers, rosins, modified rosins or esterified products thereof, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic Examples of suitable tackifiers include copolymer petroleum resins of components and aromatic components, low molecular weight styrene resins, isoprene resins, alkyls, phenol resins, terpene resins, coumarone-indene resins, and the like. In the present invention, these tackifiers can be used singly or in combination of two or more.

  The hot-melt adhesive composition according to the present invention includes the olefin block copolymer and the tackifying resin (B), and the total amount of the olefin block copolymer and the tackifying resin (B) is 100. 10 to 90 parts by weight, preferably 20 to 85 parts by weight, more preferably 30 to 80 parts by weight, and 90 to 10 parts by weight of the tackifier resin (B) with respect to parts by weight, Preferably it is contained in an amount of 80 to 15 parts by weight, more preferably 70 to 20 parts by weight.

  The hot melt adhesive composition of the present invention is a mixture of the olefin block copolymer, tackifying resin (B), and, if necessary, the above-mentioned various additives, such as Brabender, at a predetermined blending ratio. It can be prepared by feeding to a machine, heating and melt mixing, and forming it into a desired shape, for example, granular, flake, rod or the like.

  The molded body according to the present invention is a polymer composition comprising the above-described olefin block copolymer according to the present invention, which has excellent physical properties such as strength and transparency, and a thermoplastic resin other than the present invention. It is suitably used as a molded article for building materials / civil engineering molded articles, automobile interior / exterior materials or gasoline tanks, electric / electronic parts, medical molded articles, miscellaneous goods molded articles, and the like.

  These olefin block copolymers may be used alone or in combination with an inorganic filler such as magnesium hydroxide or a crosslinking agent such as vinyltrimethoxysilane. In the present invention, an inorganic filler such as magnesium hydroxide and a crosslinking agent such as vinyltrimethoxysilane may be used in combination.

  Further, an excellent magnetic recording material can be obtained by kneading the olefin block copolymer and magnetic powder as described above. In this case, the blending ratio of the olefin block copolymer and the magnetic powder (olefin block copolymer / magnetic powder: weight ratio) is preferably 99/1 to 10/90. Moreover, these can be preferably used for stationery etc. as a plastic magnet.

  The molded product for medical / hygiene according to the present invention is calendered, extruded, injection molded, blow molded, press molded, for example, in the same manner as in the production method of the olefin block copolymer, etc. It can be manufactured by stamping molding or the like. The medical / sanitary molded article thus obtained is a sheet, a film, a hollow molded article or the like. Moreover, molded bodies, such as a nonwoven fabric laminated body, can also be obtained using the sheet | seat, film, etc. which are obtained.

  Filaments can be made, for example, by extruding the molten composition through a spinneret.

  In this invention, an inorganic filler can also be added and used as needed. These addition amounts are usually 5 to 50 parts by weight, preferably 5 to 20 parts by weight for the olefin block copolymer, and 10 to 60 parts by weight for the inorganic filler with respect to 100 parts by weight of the adhesive resin. The amount is preferably 20 to 40 parts by weight.

  The film or sheet according to the present invention is a film or sheet having a multilayer structure composed of two or more layers having different compositions, and at least one of these layers is the olefin-based block copolymer according to the present invention described above. And is suitably used as a film or sheet excellent in appearance and mechanical strength characteristics. The film or sheet obtained using the olefin block copolymer is particularly excellent in transparency, heat resistance, and cloud resistance, and is therefore preferable for agriculture and wrapping.

  Specific examples of the method for molding the film and sheet of the present invention include extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foam molding, and the like. Is mentioned.

  The modifier according to the present invention is a modifier comprising the olefin block copolymer according to the present invention, and is for resin, rubber, wax, lubrication, cement, or ink / paint. It is preferably used as a modifier.

  The modifier for various modifiers according to the present invention is an olefin polymer composition comprising the olefin block copolymer and a resin, rubber, a base material for lubricating oil, wax, cement, or ink / paint. It may be.

  The dispersion according to the present invention is preferably used as an aqueous resin dispersion or an oil-based resin dispersion as a dispersion comprising the olefin block copolymer according to the present invention and a thermoplastic resin other than the present invention. Used.

  The blending amount of the thermoplastic resin is not particularly limited, but the olefinic block copolymer is usually 0.01 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and optionally 0.01 to 150 parts by weight of filler. 300 parts by weight, preferably 0.1 to 20 parts by weight of olefinic block copolymer, 0.1 to 40 parts by weight of filler, more preferably 0.5 to 10 parts by weight of olefinic block copolymer, It is preferred to use the filler in an amount of 0.5 to 20 parts by weight.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. The degree of crystallinity was calculated from the value of heat of fusion obtained from differential scanning calorimetry. The melt flow rate was measured under a load of 2.16 kg .

[Example 1]
[Styrene polymerization]
0.36 ml of n-butyllithium hexane solution (1.6 M) was placed in a sealed flask, and 4.9 g of dry styrene (St) and 49 ml of toluene were added to initiate the reaction. After stirring at 50 ° C. for 1 hour, a terminal Li-polystyrene solution was obtained. 1 ml of the polymerization solution was added to 10 ml of methanol to stop the reaction. As a result of GPC measurement, the precipitated polymer was a polymer having Mw = 8600 and Mw / Mn = 1.1.

[Coupling reaction]
Maleic acid-modified ethylene polymer (ethylene polymer modified with maleic anhydride, melt flow rate (MFR): 30 g / 10 min, Mw: 100,000, modification rate: 0.5) in a 1000 ml glass reactor %, Crystallinity: 32%) 30.0 g and 800 ml of dry toluene were added, and the copolymer was dissolved in toluene at 50 ° C. 48 ml of the toluene solution of the terminal Li-polystyrene produced as described above was introduced into a glass reactor and stirred at 50 ° C. for 6 hours, and then 20 ml of methanol was added to stop the reaction. After completion of the reaction, the reaction solution was poured into 3 L of methanol, and the precipitated polymer was separated and collected. 80 ° C., then dried for 10 hours under reduced pressure to give a poly ethylene / polystyrene block copolymer.

The obtained polymer had an MFR value of 15 g / 10 min (load: 2.16 kg, 190 ° C.), and was subjected to IR measurement, which was derived from an acid anhydride, a carboxylic acid, and a carbonyl group of a ketone group or an ester group. A peak was observed. When the obtained polymer was subjected to NMR measurement, 2.0 polystyrene segments were bonded per olefin chain derived from the maleic anhydride-modified ethylene polymer. From the GPC measurement of the obtained polymer, no peak derived from homopolystyrene was observed .

[Example 2]
In a sealed flask, 5.0 g of dry MMA and 50 ml of cyclohexane were added, and 0.6 ml of n-butyllithium hexane solution (1.6 M) was added to initiate the reaction. After stirring at 50 ° C. for 1 hour, a terminal Li-modified polymethyl methacrylate solution was obtained.

[Coupling reaction]
30.0 g of the maleic acid-modified ethylene polymer used in Example 1 and 800 ml of dry toluene were added to a 1000 ml glass reactor, and the copolymer was dissolved in toluene at 50 ° C. 50 ml of the cyclohexane solution of the terminal Li-polymethyl methacrylate produced as described above was introduced into a glass reactor and stirred at 50 ° C. for 6 hours, and then the reaction was stopped by adding 20 ml of methanol. After completion of the reaction, the reaction solution was poured into 3 L of methanol, and the precipitated polymer was separated and collected. It was dried at 80 ° C. under reduced pressure for 10 hours to obtain a polyethylene / polymethyl methacrylate block copolymer.

The obtained polymer had an MFR value of 19.1 g / 10 min (load: 2.16 kg, 190 ° C.). When IR measurement was performed, it was found that the acid anhydride, carboxylic acid, and carbonyl group of the ketone group or ester group A derived peak was observed. When the obtained polymer was subjected to NMR measurement, 1.4 polymethyl methacrylate segments were bonded per olefin chain derived from the maleic anhydride-modified ethylene polymer. From the GPC measurement of the obtained polymer, no peak derived from homopolymethyl methacrylate was observed .

Claims (10)

Side chain comprising a polymer of at least one compound having a reactive unsaturated bond in the main chain (A) having crystallinity composed of an olefin chain having a repeating unit derived from ethylene as a main structural unit. An olefin block copolymer having at least one (B), wherein the compound having a reactive unsaturated bond is a compound selected from an aromatic ring-containing vinyl compound and a (meth) acrylic acid ester compound. The main chain (A) is composed of a polymer (A ′) having a weight average molecular weight (Mw) of 1,000 to 10,000,000 measured by gel permeation chromatography (GPC). An olefin block having at least one group selected from a carboxyl group and an acid anhydride group in the main chain of the coalescence Copolymer.   The main chain (A) is composed of a polymer (A ') having a weight average molecular weight (Mw) of 100,000 to 10,000,000 as measured by gel permeation chromatography (GPC). The olefin block copolymer described in 1. The olefinic block copolymer according to claim 1 or 2 , wherein the main chain (A) and the side chain (B) are bonded in a bonding manner comprising a carbonyl group.   A polymer (A ′) having crystallinity, comprising an olefin chain having a repeating unit derived from ethylene as a main structural unit and having at least one group selected from a carboxyl group and an acid anhydride group, an alkali metal and an alkali 4. The reaction product according to claim 1, which is a reaction product with a polymer (B ′) having an active site activated by at least one metal selected from earth metals. 5. Olefin block copolymer. A polymer (A ′) having crystallinity, comprising an olefin chain having a repeating unit derived from ethylene as a main structural unit and having at least one group selected from a carboxyl group and an acid anhydride group, an alkali metal and an alkali The olefin system according to any one of claims 1 to 4 , wherein the polymer (B ') having an active site activated by at least one metal selected from earth metals is reacted. A method for producing a block copolymer. The number (Aa) of groups selected from a carboxyl group and an acid anhydride group in the polymer (A ′) and the number (Bb) of active sites in the polymer (B ′) are (Aa ) ≧ (B−b) is satisfied, The method for producing an olefin-based block copolymer according to claim 5 . The active site activated by at least one metal selected from an alkali metal and an alkaline earth metal in the polymer (B ′) is an ion pair composed of a metal ion and a carbon ion. Item 7. The method for producing an olefin block copolymer according to Item 5 or 6 . The weight average molecular weight by gel permeation chromatography polymer measured by (GPC) (A ') ( Mw) is, any one of claims 5-7, characterized in that 1,000 10,000,000 A method for producing the olefin block copolymer according to item 1.   The weight average molecular weight (Mw) of the polymer (A ') measured by gel permeation chromatography (GPC) is 100,000 to 10,000,000. A method for producing the olefin block copolymer according to item 1. The olefin system according to any one of claims 5 to 9 , wherein the polymer (B ') measured by gel permeation chromatography (GPC) has a weight average molecular weight (Mw) of 1000 or more. A method for producing a block copolymer.