WO2017204312A1 - Copolymère d'oléfine et son procédé de préparation - Google Patents

Copolymère d'oléfine et son procédé de préparation Download PDF

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WO2017204312A1
WO2017204312A1 PCT/JP2017/019619 JP2017019619W WO2017204312A1 WO 2017204312 A1 WO2017204312 A1 WO 2017204312A1 JP 2017019619 W JP2017019619 W JP 2017019619W WO 2017204312 A1 WO2017204312 A1 WO 2017204312A1
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group
olefin
olefin copolymer
general formula
carbon atoms
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Japanese (ja)
Inventor
佐藤　智彦
小林　稔
正弘 上松
芳佳 山田
良啓 加門
学文 浅井
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Japan Polypropylene Corp
Japan Polyethylene Corp
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Japan Polypropylene Corp
Japan Polyethylene Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

Definitions

  • the present invention relates to an olefin copolymer and a method for producing the same. More specifically, the present invention relates to a novel olefin copolymer having a unique structure copolymerized from ethylene and / or an ⁇ -olefin monomer and a nitrogen-containing substituted olefin monomer.
  • Polyolefins typified by polyethylene and polypropylene are excellent in properties such as physical properties and moldability among resin materials, are highly economical and compatible with environmental problems, and are also highly resource recyclable. It is a general purpose and important industrial material. However, since polyolefin is usually non-polar, its adhesion to other materials, printability, compatibility with fillers, etc. have not been sufficient.
  • olefin and polar monomer are copolymerized as a polar functional group introduction means, but means for copolymerizing olefin and polar group-containing olefin monomer (polar comonomer) is limited to the high pressure method.
  • Patent Document 1 and Patent Document 2 Only a copolymer having many branched structures, a low elastic modulus and low mechanical properties can be obtained in the copolymer.
  • ⁇ , ⁇ -terminal functionalized olefins have non-polymerizable olefin sites even when a late transition metal complex catalyst called so-called postmetallocene is used. Since it has a conjugated structure, its polymerizability is low, and it is difficult to copolymerize with olefins. Accordingly, the present inventors have attempted to produce a copolymer of ethylene or ⁇ -olefin and an ⁇ , ⁇ -terminal functionalized olefin using a late transition metal complex catalyst.
  • a transition metal catalyst having a chelating ligand in Group 5 to 10 group particularly a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium metal.
  • / or an olefinic polar copolymer characterized by being composed of an ⁇ -olefin having 3 to 10 carbon atoms and a polar group-containing olefin monomer selected from a specific monomer group.
  • Japanese Patent No. 2792982 Japanese Laid-Open Patent Publication No. 3-229713 Japan Special Table 2002-521534 Japanese Unexamined Patent Publication No. 6-184214 Japanese Laid-Open Patent Publication No. 2008-223011 Japanese Unexamined Patent Publication No. 2010-150246 Japanese Unexamined Patent Publication No. 2010-150532 Japanese Unexamined Patent Publication No. 2010-202647 Japanese Unexamined Patent Publication No. 2013-213121
  • Patent Document 9 merely shows an example using a post metallocene catalyst, and in order to expand the application range of the copolymer, development of a novel olefinic polar copolymer is eagerly desired. It was. In addition, it has been desired to develop an olefinic polar copolymer that can be easily converted into a copolymer that has been difficult to synthesize directly. For example, it has been desired to develop a copolymer that can be easily decomposed and converted into a copolymer having an amino group.
  • An object of the present invention is to provide a novel olefin copolymer using a post metallocene catalyst having a protective group that can be easily decomposed, and a method for producing the same.
  • the first invention of the present invention is at least selected from the group consisting of a structural unit derived from ethylene (a-1) and a structural unit derived from an ⁇ -olefin (a-2) having 3 to 20 carbon atoms.
  • One kind of structural unit (A); A structural unit derived from a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1), and a nitrogen-containing substituted olefin having a substituent represented by the following general formula (2) (b And an at least one structural unit (B) selected from the group consisting of structural units derived from -2).
  • R 1 represents a hydrocarbon group having 1 to 20 carbon atoms
  • R 2 represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group.
  • R 3 is a divalent organic group having 1 to 10 carbon atoms.
  • At least one of the nitrogen-containing substituted olefin (b-1) and the nitrogen-containing substituted olefin (b-2) has a structure represented by the following general formula (3).
  • the olefin copolymer according to the first invention which is characterized by the above.
  • R 4 represents a hydrogen atom or a methyl group.
  • the nitrogen-containing substituted olefin (b-1) has a structure represented by the following general formula (4): It is a coalescence.
  • R 1 is a hydrocarbon group having 1 to 20 carbon atoms
  • R 2 is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group
  • R 4 is a hydrogen atom. Or it is a methyl group and Z is a divalent organic group.
  • a fourth invention of the present invention is the olefin copolymer according to the second invention, wherein the nitrogen-containing substituted olefin (b-2) has a structure represented by the following general formula (5): .
  • R 3 represents a divalent organic group having 1 to 10 carbon atoms
  • R 4 represents a hydrogen atom or a methyl group
  • Z represents a divalent organic group.
  • Z in at least one of the general formula (4) and the general formula (5) is — (CH 2 ) n —, —COO (CH 2 ) m —, —O. (CH 2 ) m — or —CO (CH 2 ) m —, wherein n is an integer of 2 to 30, and m is an integer of 0 to 30, It is an olefin copolymer as described in the invention.
  • Z in at least one of the general formula (4) and the general formula (5) is — (CH 2 ) n —, —COO (CH 2 ) m —, or —O.
  • the olefin copolymer according to the fifth invention characterized in that it is represented by (CH 2 ) m- , n is an integer of 2 to 30, and m is an integer of 0 to 30.
  • Z in at least one of the general formula (4) and the general formula (5) is represented by — (CH 2 ) n — or —COO (CH 2 ) m —.
  • N is an integer of 2 to 30
  • m is an integer of 0 to 30.
  • Z in at least one of the general formula (4) and the general formula (5) is represented by —COO (CH 2 ) m —, and m is an integer of 0 to 30.
  • the olefin copolymer according to the seventh invention which is characterized in that
  • a ninth aspect of the present invention is the olefin copolymer according to the eighth aspect, wherein R 1 in the general formula (4) is a tert-butyl group.
  • Z in at least one of the general formula (4) and the general formula (5) is —COOCH 2 CH 2 —.
  • the olefin copolymer is —COOCH 2 CH 2 —.
  • An eleventh aspect of the present invention is the olefin copolymer according to the tenth aspect, wherein R 4 in at least one of the general formula (4) and the general formula (5) is a hydrogen atom. It is a polymer.
  • a twelfth aspect of the present invention is the invention according to any one of the first to eleventh aspects, wherein the number of methyl branches calculated by 13 C-NMR is 50 or less per 1,000 carbon atoms.
  • the olefin copolymer is the invention according to any one of the first to eleventh aspects, wherein the number of methyl branches calculated by 13 C-NMR is 50 or less per 1,000 carbon atoms.
  • the thirteenth aspect of the present invention is the olefin copolymer according to the twelfth aspect, wherein the number of methyl branches is 5 or less per 1,000 carbon atoms.
  • the fourteenth invention of the present invention is at least one selected from the group consisting of ethylene (a-1) and ⁇ -olefin (a-2) having 3 to 20 carbon atoms, A nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1) and a nitrogen-containing substituted olefin (b-2) having a substituent represented by the following general formula (2) At least one selected from the group, A method for producing an olefin copolymer, wherein polymerization is carried out in the presence of a transition metal catalyst of a Group 5-11 metal of a periodic table having a chelating ligand.
  • R 1 represents a hydrocarbon group having 1 to 20 carbon atoms
  • R 2 represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group.
  • R 3 is a divalent organic group having 1 to 10 carbon atoms.
  • the fifteenth aspect of the present invention is the method for producing an olefin copolymer according to the fourteenth aspect, wherein the transition metal catalyst is a transition metal catalyst belonging to Group 10 of the periodic table.
  • a novel olefin copolymer having a protecting group that can be easily decomposed is provided. Since this is a novel olefinic polar copolymer, it can be used in a wide range of applications.
  • This olefin copolymer is a novel olefinic polar copolymer produced by a simple and efficient polymerization method and having a protective group that can be easily decomposed.
  • a novel olefin copolymer having a protective group that can be easily decomposed can be produced easily and efficiently.
  • FIG. 1 (a) is an image diagram of the molecular structure of an olefin copolymer polymerized by a high-pressure radical polymerization process
  • FIG. 1 (b) is an olefin copolymer polymerized using a metal catalyst and has no long chain branching
  • FIG. 1C is an image diagram of a molecular structure in the case of an olefin copolymer polymerized using a metal catalyst and having a small amount of long chain branching.
  • the olefin copolymer of the present invention comprises a structural unit derived from ethylene (a-1) and a structural unit derived from an ⁇ -olefin (a-2) having 3 to 20 carbon atoms. At least one structural unit (A) selected from the group; A structural unit derived from a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1), and a nitrogen-containing substituted olefin having a substituent represented by the following general formula (2) (b -2) and at least one structural unit (B) selected from the group consisting of structural units derived from (2).
  • R 1 represents a hydrocarbon group having 1 to 20 carbon atoms
  • R 2 represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group.
  • R 3 is a divalent organic group having 1 to 10 carbon atoms.
  • the olefin copolymer of the present invention is at least one selected from the group consisting of a structural unit derived from ethylene (a-1) and a structural unit derived from an ⁇ -olefin (a-2) having 3 to 20 carbon atoms. It is characterized by having the structural unit (A).
  • the ethylene or ⁇ -olefin having 3 to 20 carbon atoms to be used for polymerization is not particularly limited, but preferably contains ethylene (a-1) as an essential component, and if necessary, the ⁇ -olefin having 3 to 20 carbon atoms ( a-2) may be further included.
  • the ethylene (a-1) or ⁇ -olefin (a-2) having 3 to 20 carbon atoms to be used for polymerization may be used alone or in combination of two or more. Further, other monomers not containing a polar group may be further subjected to polymerization as long as they do not depart from the spirit of the present invention.
  • the proportion of structural units derived from ethylene (a-1) and ⁇ -olefin (a-2) is not particularly limited, but when the total amount of olefin copolymer is 100 mol%, it is usually 80 to 99. It is desirable to select from a range of .999 mol%, preferably 85 to 99.99 mol%, more preferably 90 to 99.98 mol%, and more preferably 95 to 99.97 mol%.
  • the ⁇ -olefin according to the present invention is an ⁇ -olefin having 3 to 20 carbon atoms and represented by the structural formula: CH 2 ⁇ CHR 18 (R 18 has 1 to 18 carbon atoms). It is a hydrocarbon group and may have a straight chain structure or a branch).
  • ⁇ -olefins having 3 to 12 carbon atoms
  • propylene 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene and
  • the ⁇ -olefin used for polymerization may be used alone or in combination of two or more.
  • a monomer not containing a polar group according to the present invention is a monomer having one or more carbon-carbon double bonds in the molecular structure, and the elements constituting the molecule are It is not limited as long as it is only carbon and hydrogen, and examples thereof include diene, triene, aromatic vinyl monomer, cyclic olefin and the like, and preferred are butadiene, isoprene, styrene, vinylcyclohexane, cyclohexene, vinylnorbornene and norbornene.
  • the structural unit (B) includes a structural unit derived from a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1), and a substituent represented by the following general formula (2). It is selected from the group consisting of structural units derived from the nitrogen-containing substituted olefin (b-2).
  • R 1 represents a hydrocarbon group having 1 to 20 carbon atoms
  • R 2 represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group.
  • R 3 is a divalent organic group having 1 to 10 carbon atoms.
  • the hydrocarbon group having 1 to 20 carbon atoms in R 1 of the general formula (1) is not particularly limited, but is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group. Examples thereof include a group, n-butyl group, tert-butyl group, n-octyl group, n-eicosyl group, phenyl group, benzyl group, o-toluyl group, m-toluyl group, p-toluyl group and the like.
  • the trialkylsilyl group in R 2 of the general formula (1) is not particularly limited, and examples thereof include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.
  • the divalent organic group having 1 to 10 carbon atoms in R 3 of the general formula (2) is not particularly limited, but an alkylene group (for example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentane group) Methylene group, hexamethylene group, etc.), cycloalkylene group (for example, cyclohexylene group, etc.), aromatic hydrocarbon group (for example, phenylene group (o, m or p-phenylene group), methylphenylene group, dimethylphenylene group, etc. And naphthylene group).
  • an alkylene group for example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentane group
  • cycloalkylene group for example, cyclohexylene group, etc.
  • aromatic hydrocarbon group for example, phenylene group (o, m or p-phenylene group), methylphenylene group
  • the nitrogen-containing substituted olefin (b-1) preferably has a structure represented by the following general formula (3).
  • R 4 represents a hydrogen atom or a methyl group.
  • the nitrogen-containing substituted olefin (b-2) preferably has a structure represented by the following general formula (3).
  • R 4 represents a hydrogen atom or a methyl group.
  • the nitrogen-containing substituted olefin (b-1) preferably has a structure represented by the following general formula (4).
  • R 1 is a hydrocarbon group having 1 to 20 carbon atoms
  • R 2 is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group
  • R 4 is a hydrogen atom. Or it is a methyl group and Z is a divalent organic group.
  • the divalent organic group in Z of the general formula (4) is not particularly limited, but is — (CH 2 ) n —, —COO (CH 2 ) m —, —O (CH 2 ) m — or —CO ( A group represented by CH 2 ) m — is preferred (where n is an integer of 2 to 30, and m is an integer of 0 to 30).
  • a divalent organic group in Z a more preferred embodiment is — (CH 2 ) n —, —COO (CH 2 ) m — or —O (CH 2 ) m — (where n is 2 to 30).
  • m is an integer of 0 to 30).
  • a particularly preferred embodiment of the divalent organic group in Z is — (CH 2 ) n — or —COO (CH 2 ) m — (wherein n is an integer of 2 to 30, and m is 0 to An integer of 30).
  • the most preferred embodiment of the divalent organic group for Z is —COO (CH 2 ) m — (where m is an integer of 0 to 30), and the most preferred embodiment is —COOCH 2 CH 2- .
  • R 1 in the general formula (4) is a hydrocarbon group having 1 to 20 carbon atoms.
  • the hydrocarbon group having 1 to 20 carbon atoms in R 1 of the general formula (4) is not particularly limited, but is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group. Examples thereof include a group, n-butyl group, tert-butyl group, n-octyl group, n-eicosyl group, phenyl group, benzyl group, o-toluyl group, m-toluyl group, p-toluyl group and the like.
  • a tert-butyl group is particularly preferable.
  • R 2 in the general formula (4) is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group.
  • the trialkylsilyl group in R 2 of the general formula (4) is not particularly limited, and examples thereof include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.
  • R 4 in the general formula (4) is a hydrogen atom or a methyl group. As R 4 in the general formula (4), a hydrogen atom is preferable.
  • the nitrogen-containing substituted olefin (b-2) preferably has a structure represented by the following general formula (5).
  • R 3 represents a divalent organic group having 1 to 10 carbon atoms
  • R 4 represents a hydrogen atom or a methyl group
  • Z represents a divalent organic group.
  • the divalent organic group in Z of the general formula (5) is not particularly limited, but is — (CH 2 ) n —, —COO (CH 2 ) m —, —O (CH 2 ) m — or —CO ( A group represented by CH 2 ) m — is preferred (where n is an integer of 2 to 30, and m is an integer of 0 to 30).
  • a divalent organic group in Z a more preferred embodiment is — (CH 2 ) n —, —COO (CH 2 ) m — or —O (CH 2 ) m — (where n is 2 to 30).
  • m is an integer of 0 to 30).
  • a particularly preferred embodiment of the divalent organic group in Z is — (CH 2 ) n — or —COO (CH 2 ) m — (wherein n is an integer of 2 to 30, and m is 0 to An integer of 30).
  • the most preferred embodiment of the divalent organic group for Z is —COO (CH 2 ) m — (where m is an integer of 0 to 30), and the most preferred embodiment is —COOCH 2 CH 2- .
  • R 3 in the general formula (5) is a divalent organic group having 1 to 10 carbon atoms.
  • the divalent organic group having 1 to 10 carbon atoms in R 3 of the general formula (5) is not particularly limited, but an alkylene group (for example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentane group) Methylene group, hexamethylene group, etc.), cycloalkylene group (for example, cyclohexylene group, etc.), aromatic hydrocarbon group (for example, phenylene group (o, m or p-phenylene group), methylphenylene group, dimethylphenylene group, etc. And naphthylene group).
  • alkylene group for example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentane group
  • cycloalkylene group for example, cyclohexylene group, etc.
  • aromatic hydrocarbon group for example
  • R 4 in the general formula (5) is a hydrogen atom or a methyl group.
  • R 4 in the general formula (5) is preferably a hydrogen atom.
  • Amount of structural unit of nitrogen-containing substituted olefin The ratio of the structural unit derived from the nitrogen-containing substituted olefin (b-1) and the total structural unit of the structural unit derived from the nitrogen-containing substituted olefin (b-2) is: Although not particularly limited, when the entire olefin copolymer is 100 mol%, it is usually in the range of 20 to 0.001 mol%, preferably in the range of 15 to 0.01 mol%, more preferably in the range of 10 to 0.02 mol%. It is selected from the range, more preferably from 5 to 0.03 mol%.
  • 1 H-NMR was measured at a pulse angle of 1 °, a pulse interval of 1.8 seconds, and the number of integrations of 512 or more.
  • the chemical shift was set so that the peak of methyl proton of hexamethyldisiloxane was 0.088 ppm, and the chemical shift of the peak due to other protons was based on this.
  • the number of methyl branches in the olefin copolymer described later can be determined by 13 C-NMR.
  • 13 C-NMR was measured by a proton complete decoupling method with a pulse angle of 90 °, a pulse interval of 20 seconds, and a cumulative number of 512 times or more.
  • the chemical shift was set such that the methyl carbon peak of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shifts of peaks due to other carbons were based on this.
  • the olefin copolymer according to the present invention is derived from a structural unit derived from ethylene (a-1) and an ⁇ -olefin (a-2) having 3 to 20 carbon atoms.
  • Examples of the molecular structure of the olefin copolymer of the present invention are shown in the following paragraphs.
  • the random copolymer means that the probability of finding each structural unit at a position in a given molecular chain of the A structural unit and the B structural unit in the molecular structure example shown below is the type of the adjacent structural unit. It is an unrelated copolymer.
  • the molecular chain terminal of the olefin copolymer may be ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, such as a nitrogen-containing substituted olefin (b-1) or a nitrogen-containing substituted olefin (b-2). There may be.
  • ethylene or an ⁇ -olefin having 3 to 20 carbon atoms and a nitrogen-containing substituted olefin form a random copolymer.
  • ethylene (a-1) and / or ⁇ -olefin (a-2) having 3 to 20 carbon atoms was copolymerized.
  • a part of the olefin copolymer is graft-modified with the nitrogen-containing substituted olefin (b-1) and / or the nitrogen-containing substituted olefin (b-2).
  • the olefin copolymer of the present invention is preferably produced in the presence of a transition metal catalyst, and its molecular structure is preferably linear.
  • An image diagram of an olefin copolymer polymerized by a high pressure radical polymerization process is shown in FIG. 1 (a), and an image diagram of an olefin copolymer polymerized using a metal catalyst is shown in FIG. 1 (b) and FIG. 1 (c).
  • the molecular structure varies depending on the production method. This difference in molecular structure can be controlled by selecting a production method. For example, as described in the patent publication “Japanese Unexamined Patent Publication No. 2010-150532”, the complex structure measured by a rotary rheometer is used. The molecular structure can also be estimated from the elastic modulus.
  • the molecular structure is as shown in FIG. As shown in (b) and FIG. 1 (c), a structure containing no long chain branches (FIG. 1 (b)) or a structure containing a small amount of long chain branches that does not affect the mechanical strength. (FIG. 1C) is shown.
  • Weight average molecular weight of olefin copolymer (Mw) The weight average molecular weight (Mw) of the olefin copolymer according to the present invention is usually 1,000 to 2,000,000, preferably 10,000 to 1,500,000, more preferably 20,000 to 1,000. The preferred range is 31,000 to 800,000, and the more preferred range is 33,000 to 800,000. If the Mw is less than 1,000, the physical properties such as mechanical strength and impact resistance are not sufficient, and the adhesion with a different material with high polarity may be inferior. When Mw exceeds 2,000,000, the melt viscosity becomes very high, and molding may be difficult.
  • the copolymer of ethylene and / or ⁇ -olefin and polar group-containing olefin of the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of usually from 1.5 to 3 0.5, preferably 1.6 to 3.3, more preferably 1.7 to 3.0. If Mw / Mn is less than 1.5, various workability tends to be insufficient, whereas if Mw / Mn exceeds 3.5, performance such as adhesion tends to be insufficient. Mw / Mn may be expressed as a molecular weight distribution parameter.
  • the weight average molecular weight (Mw) of the olefin copolymer of the present invention is determined by gel permeation chromatography (GPC).
  • the molecular weight distribution parameter (Mw / Mn) is a value obtained by further obtaining the number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculating the ratio of Mw to Mn, Mw / Mn.
  • the olefin copolymer of the present invention has a methyl branch number calculated by 13 C-NMR of 50 or less per 1,000 carbon atoms. Preferably there is. Of these, the number of methyl branches is particularly preferably 5 or less per 1,000 carbon atoms. When the number of methyl branches satisfies this value, the elastic modulus is high and the mechanical strength of the molded article is also high.
  • the number of methyl branches can be controlled by selecting the transition metal catalyst to be used and the polymerization temperature. As a specific means for reducing the number of methyl branches in the copolymer, a reduction in polymerization temperature is effective. For example, it is required to adjust these factors to control the target copolymer region.
  • the measurement of the number of methyl branches is performed as follows. Total sum of integral intensities of peaks due to carbon of 2 to 60 ppm and 170 to 180 ppm I is normalized to 1,000, and the integral intensity of signals from methyl carbon of 20 ppm methyl branch and the integration of signals from methine carbon of 33 ppm methyl branch The number of methyl branches per 1,000 carbons in total was calculated using the following formula using the value I B1 obtained by dividing the sum of the intensity and the integrated intensity of the signal by methylene carbon of 37 ppm methyl branches by 4.
  • the method for producing an olefin copolymer of the present invention is selected from the group consisting of ethylene (a-1) and ⁇ -olefin (a-2) having 3 to 20 carbon atoms.
  • a nitrogen-containing substituted olefin (b-1) having at least one kind and a substituent represented by the following general formula (1), and a nitrogen-containing substituted olefin having a substituent represented by the following general formula (2) (b -2) is polymerized in the presence of a transition metal catalyst of a metal of Group 5 to 11 of the periodic table having a chelating ligand.
  • R 1 represents a hydrocarbon group having 1 to 20 carbon atoms
  • R 2 represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group.
  • R 3 is a divalent organic group having 1 to 10 carbon atoms.
  • R 1 and R 2 in general formula (1) in, R 3 in the general formula (2) is ⁇ 1.
  • the explanation of R 1 , R 2 , and R 3 described in the item of >> for the olefin copolymer is applied as it is (including preferred embodiments), and the description thereof is omitted.
  • the type of the polymerization catalyst according to the present invention includes ethylene (a-1) and / or ⁇ -olefin (a-2) having 3 to 20 carbon atoms and the above general formula ( 1) selected from the group consisting of a nitrogen-containing substituted olefin (b-1) having a substituent represented by 1) and a nitrogen-containing substituted olefin (b-2) having a substituent represented by the above general formula (2)
  • a-1 nitrogen-containing substituted olefin having a substituent represented by 1
  • b-2 nitrogen-containing substituted olefin
  • it is not particularly limited as long as it can be copolymerized with at least one selected from the above for example, there is a polymerization method using a transition metal compound of Group 5 to 11 having a chelating ligand as a catalyst. .
  • transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, A copper atom etc. are mentioned.
  • preferred are Group 8 to 11 transition metals, more preferred are Group 10 transition metals, and particularly preferred are nickel (Ni) and palladium (Pd). These metals may be single or plural.
  • the transition metal of the transition metal complex of the present invention is an element in which M is selected from the group consisting of nickel (II), palladium (II), platinum (II), cobalt (II) and rhodium (III). Is more preferable from the viewpoint of polymerization activity, and nickel (II) is particularly preferable from the viewpoint of price and the like.
  • the chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S, and is bidentate or multidentate. It contains a ligand and is electronically neutral or anionic. The structure is illustrated in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169).
  • examples of the bidentate anionic P and O ligand include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate.
  • Other examples of the bidentate anionic N and O ligand include salicyl. Examples thereof include aldoiminate and pyridinecarboxylic acid, and other examples include diimine ligands, diphenoxide ligands, and diamide ligands.
  • the structure of the metal complex obtained from the chelating ligand is represented by the following structural formula ( ⁇ ) and / or ( ⁇ ) coordinated by an arylphosphine compound, arylarsine compound or arylantimony compound which may have a substituent. expressed.
  • M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of elements, that is, various transition metals as described above.
  • X 1 represents oxygen, sulfur, —SO 3 —, or —CO 2 —.
  • Y 1 represents carbon or silicon.
  • n represents 0 or 1.
  • E 1 represents phosphorus, arsenic or antimony.
  • R 3 and R 4 each independently represent hydrogen or a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms.
  • R 5 each independently represents hydrogen, halogen, or a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms.
  • R 6 and R 7 are each independently hydrogen, halogen, a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms, OR 2 , CO 2 R 2 , CO 2 M ′, C (O) N (R 1 ) 2 , C (O) R 2 , SR 2 , SO 2 R 2 , SOR 2 , OSO 2 R 2 , P (O) (OR 2 ) 2-y (R 1 ) y , CN, NHR 2 , N (R 2 ) 2 , Si (OR 1 ) 3-x (R 1 ) x , OSi (OR 1 ) 3-x (R 1 ) x , NO 2 , SO 3 M ′, PO 3 M ′ 2 , P (O) (OR 2 ) 2 M ′ or an epoxy-containing group.
  • M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium
  • x represents an integer from 0 to 3
  • y represents an integer from 0 to 2.
  • R 6 and R 7 may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. At this time, the number of ring members is 5 to 8, and it may or may not have a substituent on the ring.
  • R 1 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 2 represents a hydrocarbon group having 1 to 20 carbon atoms.
  • L 1 represents a ligand coordinated to M.
  • R 3 and L 1 may be bonded to each other to form a ring.
  • the structure of the metal complex obtained from the chelating ligand is more preferably a transition metal complex represented by the following structural formula ( ⁇ ).
  • M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of elements, that is, the aforementioned transition metal.
  • X 1 represents oxygen, sulfur, —SO 3 —, or —CO 2 —.
  • Y 1 represents carbon or silicon.
  • n represents 0 or 1.
  • E 1 represents phosphorus, arsenic or antimony.
  • R 3 and R 4 each independently represent hydrogen or a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms.
  • R 5 each independently represents hydrogen, halogen, or a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms.
  • R 8 , R 9 , R 10 and R 11 are each independently hydrogen, halogen, a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms, OR 2 , CO 2 R 2 , CO 2 M ', C (O) N (R 1 ) 2 , C (O) R 2 , SR 2 , SO 2 R 2 , SOR 2 , OSO 2 R 2 , P (O) (OR 2 ) 2-y (R 1 ) Y , CN, NHR 2 , N (R 2 ) 2 , Si (OR 1 ) 3-x (R 1 ) x , OSi (OR 1 ) 3-x (R 1 ) x , NO 2 , SO 3 M ′ , PO 3 M ′ 2 , P (O) (OR 2 ) 2 M ′ or an epoxy-containing group.
  • M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium
  • x represents an integer from 0 to 3
  • y represents an integer from 0 to 2.
  • a plurality of groups appropriately selected from R 8 to R 11 may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. Good. At this time, the number of ring members is 5 to 8, and it may or may not have a substituent on the ring.
  • R 1 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 2 represents a hydrocarbon group having 1 to 20 carbon atoms.
  • L 1 represents a ligand coordinated to M.
  • R 3 and L 1 may be bonded to each other to form a ring.
  • the Shop-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to nickel metal (see, for example, WO 2010-050256).
  • the Drent system is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to palladium metal (see, for example, Japanese Patent Application Laid-Open No. 2010-202647).
  • Organometallic compound In the production of the olefin copolymer according to the present invention, at least one selected from the group consisting of the above-mentioned nitrogen-containing substituted olefin (b-1) and nitrogen-containing substituted olefin (b-2); , After contacting with a small amount of an organometallic compound, in the presence of the transition metal catalyst, ethylene (a-1) and / or ⁇ -olefin (a-2) having 3 to 20 carbon atoms and nitrogen-containing substitution By copolymerizing at least one selected from the group consisting of olefin (b-1) and nitrogen-containing substituted olefin (b-2), the polymerization activity can be further enhanced.
  • the organometallic compound is an organometallic compound including a hydrocarbon group which may have a substituent, and can be represented by the following structural formula (H).
  • R 30 represents a hydrocarbon group which may have a substituent having 1 to 12 carbon atoms
  • M 30 represents Group 1, Group 2, Group 12 and Group 13 of the periodic table.
  • Examples of the organometallic compound represented by the structural formula (H) include alkylaluminums such as tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and methylaluminum.
  • alkylaluminum halides such as dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, and diethylaluminum ethoxide, and trialkylaluminum is preferably selected.
  • a trialkylaluminum having a hydrocarbon group having 4 or more carbon atoms more preferably a trialkylaluminum having a hydrocarbon group having 6 or more carbon atoms, more preferably tri-n-hexylaluminum or trialkylaluminum.
  • -N-octylaluminum and tri-n-decylaluminum are selected, and tri-n-octylaluminum can be most preferably used.
  • the organometallic compound has a molar ratio of 10 ⁇ 5 to 0.9, preferably 10 ⁇ 4 to 0 with respect to the polar group-containing comonomer (nitrogen-containing substituted olefin (b-1) and nitrogen-containing substituted olefin (b-2)). 2, more preferably 10 ⁇ 4 to 0.1 is preferably contacted from the viewpoint of polymerization activity and cost.
  • Aluminum (Al) content remaining in 1g of the olefin copolymer according to the remaining amount present invention aluminum (Al) is preferably not more than 100,000 micrograms Al / g, more or less 70,000 ⁇ g Al / g preferably, more preferably less 20,000 Al / g, or less and particularly preferably 10,000 [Al / g, a preferable less 5,000 micrograms Al / g, and more preferably less 1,000 .mu.g Al / g, 500 [mu] g Al / g or less is most preferred.
  • the amount is larger than this, the mechanical properties of the olefin copolymer are lowered, and the discoloration or deterioration of the polymerization product is likely to occur.
  • Residual amounts of aluminum (Al) may have the smaller to the extent possible, for example, may be a very small amount of about 1 [mu] g Al / g, it may be a 0 Pg Al / g.
  • ⁇ g Al / g means that the amount of aluminum (Al) contained in 1 g of the polar group-containing olefin copolymer is expressed in ⁇ g.
  • the amount of aluminum (Al) contained in the olefin copolymer according to the present invention is the amount of aluminum contained in the alkylaluminum subjected to the polymerization, and the obtained olefin copolymer. It can be calculated as a value divided by the yield.
  • the amount of aluminum (Al) contained in the olefin copolymer is calculated from the amount of alkyl aluminum polymerized, but it may be measured by fluorescent X-ray analysis or inductively coupled plasma emission (ICP) analysis. When using fluorescent X-ray analysis or ICP analysis, it can be measured, for example, by the following method.
  • X-ray fluorescence analysis 3 to 10 g of a measurement sample is weighed, and heated and pressure-molded by a heating press to produce a flat plate sample having a diameter of 45 mm.
  • the measurement is performed on a portion having a central diameter of 30 mm of the flat sample, and measurement is performed under the following conditions using a scanning fluorescent X-ray analyzer “ZSX100e” (Rh tube 4.0 kW) manufactured by Rigaku Denki Kogyo.
  • the aluminum content can be obtained from a calibration curve prepared in advance and the results measured under the above conditions.
  • a calibration curve can be prepared by measuring the aluminum content of a plurality of polyethylene resins by ICP analysis and further subjecting these polyethylene resins to fluorescent X-ray analysis under the above conditions.
  • ICP Inductively Coupled Plasma Luminescence
  • Teflon registered trademark
  • a microwave decomposition apparatus Using a milestone general (MLS-1200MEGA), a thermal decomposition operation is performed at a maximum of 500 W to make a measurement sample into a solution.
  • the aluminum content can be measured by subjecting the measurement sample in solution to an ICP emission spectroscopic analyzer (IRIS-AP manufactured by Thermo Jarrel Ash). The aluminum content is quantified using a calibration curve prepared using a standard solution having a known aluminum element concentration.
  • the polymerization method of the olefin copolymer according to the present invention is not limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization carried out in the vaporized monomer, or polymer produced in a monomer liquefied at high temperature and high pressure High-pressure ionic polymerization in which at least a part of the polymer is dissolved is preferably used.
  • the polymerization format may be any of batch polymerization, semi-batch polymerization, and continuous polymerization.
  • chain shunting agent CSA
  • CCTP coordinative chain transfer polymerization
  • the olefin copolymer according to the present invention includes an antioxidant, an ultraviolet absorber, a lubricant, an antistatic agent, a colorant, a pigment, a cross-linking agent, a foaming agent, a nucleating agent, a difficulty, and the like without departing from the gist of the present invention. You may mix
  • the olefin copolymer of the present invention has a specific molecular structure and physical properties of resin, so that it exhibits high adhesiveness with other base materials and enables production of industrially useful laminates. I made it.
  • the adhesion performance with various substrates is the structural unit derived from the nitrogen-containing substituted olefin (b-1) and the nitrogen-containing substituted olefin (b-2) in the olefin copolymer described above.
  • the laminate is a laminate comprising a layer made of the olefin copolymer of the present invention and a base material layer, and the base material layer is an olefin resin such as polyethylene or polypropylene, a polyamide resin, Examples thereof include base materials such as polyester resins, thermoplastic resins with high polarity such as ethylene-vinyl alcohol copolymer (EVOH), metal materials such as adhesive fluororesin, aluminum, and steel.
  • EVOH ethylene-vinyl alcohol copolymer
  • the substrate include high density polyethylene, medium density polyethylene, low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ionomer, homopolypropylene resin, propylene and other ⁇ -olefins.
  • Copolymers olefin resins such as poly-1-butene and poly-4-methyl-1-pentene, vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate and polyacrylonitrile, nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, polyamide resin such as polymetaxylylene adipamide, polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, polylactic acid, poly Thermoplastic resin film having film-forming ability such as polyester resin such as tylene succinate, aromatic polyester, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polycarbonate resin, adhesive fluororesin, cellophane, etc.
  • vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate and polyacrylonitrile, nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon
  • inorganic oxides such as sheets (and stretched products and printed materials thereof), metal foils or metal plates such as aluminum, iron, copper, or alloys based on these, silica-deposited plastic films, alumina-deposited plastic films, etc.
  • Films, metallized films such as gold, silver and aluminum, or compounds other than oxides of these metals, paper such as fine paper, kraft paper, paperboard, glassine paper, synthetic paper, cellophane, woven fabric, non-woven fabric, etc. Can be mentioned.
  • a base material layer can be suitably selected according to a use and the kind of to-be-packaged object.
  • the package is a perishable food, such as polyamide, polyvinylidene chloride, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyester, it has transparency, rigidity and gas permeation resistance. An excellent resin can be used.
  • the package is a confectionery or a fiber, it is preferable to use polypropylene having good transparency, rigidity and water permeation resistance.
  • resins having excellent fuel permeation prevention performance such as EVOH, polyamides, and fluororesins can be used.
  • barrier resin examples include polyamide resin, polyester resin, EVOH, polyvinylidene chloride resin, polycarbonate resin, stretched polypropylene (OPP), stretched polyester (OPET), stretched polyamide, alumina vapor deposition film, silica vapor deposition film, and the like.
  • examples include metal, inorganic oxide vapor deposition films, metal vapor deposition films such as aluminum vapor deposition, and metal foils.
  • the laminate is suitable as a food packaging material, for example.
  • Specific examples of food include snacks such as potato chips, confectionery such as biscuits, rice crackers and chocolates, powder seasonings such as powdered soup, foods such as shavings and smoked foods, and the like.
  • the ethylene-type copolymer layer surfaces of the said laminated body can be faced, and it can form by heat-sealing at least one part.
  • water packaging bags, liquid soup bags, liquid paper containers, lami raw fabrics, special shape liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, semi-heavy bags, wrap films, sugar It is suitably used for bags, oil packaging bags, various packaging containers for food packaging, infusion bags and the like.
  • the processing methods for laminates include normal press molding, air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, flat die molding (T-die molding), and water-cooled inflation molding.
  • Conventionally known methods such as extrusion molding, extrusion lamination processing, sand lamination processing, dry lamination processing, etc., blow molding, pressure forming, injection molding, rotational molding, etc. may be mentioned.
  • a laminated laminate is a laminate that can be produced by a known laminating method such as extrusion laminating, sand laminating, or dry laminating. It is a laminate that can be produced by laminating a laminate material containing the olefin copolymer and at least one base material layer.
  • the laminate material in the present invention is a resin material containing the olefin copolymer of the present invention that can be used in various known laminating methods.
  • Extrusion laminating is a molding method in which a molten resin film extruded from a T-die is continuously coated and pressure-bonded on a substrate, and coating and adhesion are performed simultaneously.
  • Sand laminating is a method in which a molten resin is poured between paper and a film to be laminated, and the molten resin acts as an adhesive to bond and laminate.
  • the dry laminating process dehumidifies the atmospheric humidity in the vicinity of the adhesive and / or adhesive application roll for laminating the film to be laminated with the base material, or heats the temperature of the adhesive and / or the adhesive application roll. Or it is the method of drying the bonding surface of a film sheet.
  • Extruded product The olefin copolymer of the present invention can be used in an extruded product.
  • the extrusion molded product is an extrusion molded product obtained by molding the olefin copolymer of the present invention by extrusion molding.
  • Extrusion products related to the present invention are known in various forms such as air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, water-cooled inflation molding, flat die molding, profile extrusion molding, tubular product molding, calendar molding, etc. It can be manufactured by extrusion.
  • it may be further shaped by various known methods such as sandwiching in a mold or the like, or applying deformation in a state where the extruded product obtained by extrusion molding is not completely solidified. Further, post-processing may be added by various known methods such as bending, cutting, and reheating after the obtained extrusion-molded product.
  • the olefin copolymer of the present invention can be used for a multilayer coextrusion molded product.
  • the multilayer coextrusion product is a multilayer coextrusion product that can be molded by a known multilayer coextrusion molding, and includes at least a layer comprising the olefin copolymer of the present invention. It is a molded product.
  • Multi-layer co-extrusion products are multi-layer structures that can be manufactured by simultaneously extruding a plurality of thermoplastic materials into a plurality of layers and molding them by various shaping methods. It is a molded product with
  • Multi-layer coextrusion molded products include multilayer air-cooled inflation molding, multilayer air-cooled two-stage cooling inflation molding, multilayer high-speed inflation molding, multilayer water-cooled inflation molding, multilayer flat die molding (T-die molding), multilayer tubular product molding, Known multilayer coextrusion molding such as multilayer corrugated pipe molding can be mentioned.
  • a multilayer coextruded product is obtained by processing a layer containing the olefin copolymer of the present invention and a suitable base material by a suitable molding method, so that a multilayer film, a multilayer sheet, a multilayer pipe, a multilayer hose, a multilayer tube, It can be manufactured as a known multilayer coextrusion product such as a multilayer corrugated pipe.
  • the multilayer coextrusion molded product obtained by the multilayer coextrusion molding may be further shaped by various known methods such as being sandwiched in a mold or the like or being deformed in a state where it is not solidified.
  • post-processing may be added by various known methods such as bending, cutting, and re-heating after the obtained multilayer co-extruded product.
  • the olefin copolymer of this invention can be used for a multilayer coextrusion molded article.
  • the multilayer film is a multilayer film that can be produced by a known multilayer film molding method, and is a multilayer film including at least a layer containing the olefin copolymer of the present invention and a base material layer. is there.
  • known multilayer film molding methods such as multilayer air-cooled inflation molding, multilayer air-cooled two-stage cooling inflation molding, multilayer high-speed inflation molding, multilayer water-cooled inflation molding, multilayer flat die molding (T-die molding), etc. Can be used.
  • T-die molding multilayer flat die molding
  • various various materials as described above can be appropriately used.
  • the olefin copolymer of the present invention can be used in a multilayer blow molded article.
  • the multilayer blow-molded product is a multilayer blow-molded product that can be produced by a known multilayer blow molding, and includes at least a layer comprising the olefin copolymer of the present invention and a base material layer. It is a multilayer blow molded product.
  • known blow molding methods such as multilayer direct blow molding, multidimensional multilayer blow molding, multilayer rotary blow molding and the like can be mentioned.
  • the base material layer of the multilayer blow molded product according to the present invention various kinds of materials as described above can be appropriately used.
  • the olefin copolymer of the present invention can be used for multilayer tubular molded articles.
  • the multilayer tubular molded article is a multilayer tubular molded article that can be molded by a known multilayer tubular molding method, and includes at least a layer comprising the olefin copolymer of the present invention and a base material layer. It is a multilayer tubular molded article containing.
  • the multi-layer tubular molding method is, for example, a method in which a plurality of materials are compounded in layers by simultaneously extruding a plurality of thermoplastic materials, and are continuously shaped according to the shape of the discharge port by discharging from a circular or irregular discharge port. And a method of obtaining a tubular molded product by molding and cooling and solidifying by an appropriate shaping method and a cooling method.
  • the discharge port shape of the multilayer tubular molding method is not particularly limited, and a circular, elliptical, polygonal, or other known discharge port shape can be selected.
  • the molding method of the multilayer tubular molding method is not particularly limited, and the sizing plate method, the internal pressure sizing method, the inner diameter sizing method, the vacuum sizing method, the extruded molten material is sandwiched between the molds, the pressure air from the mandrel side or the mold side
  • a known molding method such as a method of cooling while shaping by vacuuming or the like can be used, and the cooling method can be appropriately used, such as water cooling, air cooling, sandwiching with a mold or the like.
  • the multilayer tubular molded article once cooled and solidified can be reheated and further processed into another shape.
  • various various materials as described above can be appropriately used.
  • the olefin copolymer of this invention can be used for a multilayer sheet.
  • the multilayer sheet is a multilayer sheet that can be produced by known multilayer sheet molding, and is a multilayer sheet that includes at least the layer containing the olefin copolymer of the present invention and a base material layer.
  • Various known methods can be used as a method for producing a multilayer sheet. For example, a plurality of thermoplastic materials can be simultaneously extruded to form a composite of a plurality of materials in a layered manner, and from a known die such as a flat die or a circular die. A method of forming into a sheet by discharging can be mentioned.
  • the edge of the sheet may be slit or a process of opening a circular sheet may be added.
  • various types such as vacuum forming, pressure forming, vacuum pressure forming, stamping forming, press forming, etc. It may be further shaped by a known molding method.
  • the base material layer of the multilayer sheet according to the present invention various various materials as described above can be appropriately used.
  • the olefin copolymer of the present invention can be used for injection-molded articles.
  • the injection molded product is an injection molded product obtained by molding the olefin copolymer of the present invention by injection molding.
  • a well-known method can be used for manufacture of an injection molded product.
  • the olefin copolymer of the present invention can be used for a multilayer injection molded product.
  • the multilayer injection-molded article is a multilayer injection-molded article that includes at least a layer containing the olefin copolymer of the present invention and can be manufactured by compositing a plurality of layers using injection molding.
  • the multilayer injection-molded article only needs to be a composite of two or more types of materials.
  • a layer containing two different types of the olefin copolymer of the present invention may be laminated.
  • a layer comprising an olefin copolymer and a layer comprising a substrate may be multilayered. Further, three or more layers may be multilayered.
  • the multilayer injection-molded product can be molded by a known injection molding method. It may be a multilayer injection-molded product formed by multilayering two or more types of layers containing the olefin copolymer of the present invention, but has a high adhesiveness with different materials, which is a feature of the present invention. Considering this, it is preferable to use a composite injection-molded product in which a layer made of different materials is laminated.
  • a known method can be exemplified.
  • the olefin copolymer of the present invention is processed into a member in advance by a known method such as injection molding, extrusion molding, press molding, or cutting, and the base material is further inserted in a state in which the member is inserted into the injection mold.
  • a multi-color injection molding machine having a plurality of injection units, and a method of multilayering by sequentially injecting the olefin copolymer of the present invention and a base material into a mold in an appropriate order can be exemplified.
  • various kinds of base materials as described above can be appropriately used as the kind of the member to be combined with the olefin copolymer of the present invention.
  • Coated metal member The olefin copolymer of the present invention can be used for a coated metal member.
  • the coated metal member is a coated metal member that can be produced by coating the metal with the metal coating material using the olefin copolymer of the present invention as a metal coating material.
  • the coated metal member can be produced by a known metal coating method.
  • coated metal member examples include, for example, a coated steel pipe in which a coating material is coated on an outer surface or an inner surface of a steel pipe through an undercoat as necessary, a coated metal wire coated with a metal coating material, a metal coating material Electric wire coated with powder, Coated metal coated with powdered coated metal material by flow dipping method, Coated metal coated with electrostatic coated method using coated metal material with powdered property, sheet or film in advance Examples thereof include a coated metal coated by thermally welding a metal coating material processed into a metal material.
  • the olefin copolymer of the present invention is not only suitably used as the above adhesive resin material, but also polyolefin resin such as polypropylene resin, polyamide resin, polyester resin, polycarbonate resin, acrylic resin, poly As a modifier for various resins such as vinyl chloride resin, or as a compatibilizer for polyolefin resins such as polypropylene and engineering plastics such as polycarbonate resin, polyphenylene ether resin, polyamide resin, polyester resin, polyphenylene sulfide resin, and liquid crystal resin It is preferably applied.
  • polyolefin resin such as polypropylene resin, polyamide resin, polyester resin, polycarbonate resin, acrylic resin, poly
  • poly a modifier for various resins such as vinyl chloride resin, or as a compatibilizer for polyolefin resins such as polypropylene and engineering plastics such as polycarbonate resin, polyphenylene ether resin, polyamide resin, polyester resin, polyphenylene sulfide resin, and liquid crystal resin It is
  • Evaluation method (1) Melting point Tm The melting point Tm of the produced olefin copolymer was determined by the following DSC measurement. Using “EXSTAR6000” manufactured by Seiko Denshi Kogyo Co., Ltd., isothermal at 40 ° C. for 1 minute, heated to 40-160 ° C. at 10 ° C./minute, isothermal at 160 ° C. for 10 minutes, 160-10 ° C. at 10 ° C./minute The temperature was measured until the temperature decreased to 10 to 160 ° C. at 10 ° C./min after the temperature was lowered to 10 ° C. for 5 minutes.
  • I ⁇ 1.62 to 1.78 ppm ⁇ -methylene proton integrated intensity
  • I br 2.32 to 2.50 ppm main chain methine proton integrated intensity
  • I NCH2 3.08 to 3.78 ppm methylene proton integral
  • I E 0.25 ⁇ (I 0-3 ⁇ I NCH2 ⁇ 9)
  • I 0-3 Integral intensity of proton signal detected from 0 ppm to 3 ppm
  • Metal catalyst B-27DM / Ni complex and B-111 / Ni complex were synthesized according to the synthesis example described in Japanese Patent Application Laid-Open No. 2013-038771, and the ligands B-27DM and B- 111 was used. Further, according to the examples of WO 2010/050256, B-27DM and Ni (COD) were used using bis-1,5-cyclooctadiene nickel (0) (referred to as Ni (COD) 2 ). Nickel complexes were prepared by reacting 2 and B-111 with Ni (COD) 2 on a one-to-one basis.
  • CM concentration means the comonomer concentration, that is, the concentration of 2- (t-butoxycarbonylamino) ethyl acrylate.
  • content means the content of structural units derived from 2- (t-butoxycarbonylamino) ethyl acrylate when the total constituent units of the olefin copolymer are 100 mol%.
  • Example 2 Ethylene-BOCAEA copolymerization was carried out in the same manner as in Example 1 except that 4.3 g (20 mmol) of BOCEAA, the amount of B-27DM / Ni catalyst was 24 ml (240 ⁇ mol), and the polymerization time was 30 minutes. The results are shown in Table 1.
  • Example 3 Ethylene-BOCAEA copolymerization was carried out in the same manner as in Example 1 except that 4.3 g (20 mmol) of BOCEAA, the amount of B-111 / Ni catalyst was 18 ml (180 ⁇ mol), and the polymerization time was 25 minutes. The results are shown in Table 1.
  • Example 4 Ethylene-BOCAEA copolymerization was carried out in the same manner as in Example 1 except that 1.0 g (4.7 mmol) of BOCEAA, the amount of B-111 / Ni catalyst was 2.5 ml (25 ⁇ mol), and the polymerization time was 55 minutes. It was. The results are shown in Table 1.
  • Example 5 The same as Example 1 except that 0.8 g (3.9 mmol) of BOCEAA, the amount of B-111 / Ni catalyst was 3.0 ml (30 ⁇ mol), the autoclave temperature was 110 ° C., and the polymerization time was 50 minutes. Ethylene-BOCAEA copolymerization was performed. The results are shown in Table 1.
  • Example 6 Example 1 was repeated except that 0.7 g (3.3 mmol) of BOCEAA, the amount of B-111 / Ni catalyst was 3.0 ml (30 ⁇ mol), the autoclave temperature was 130 ° C., and the polymerization time was 45 minutes. Ethylene-BOCAEA copolymerization was performed. The results are shown in Table 1.
  • Example 7 Example 1 was repeated except that 0.6 g (2.9 mmol) of BOCEAA, the amount of B-111 / Ni catalyst was 5.5 ml (55 ⁇ mol), the autoclave temperature was 150 ° C., and the polymerization time was 55 minutes. Ethylene-BOCAEA copolymerization was performed. The results are shown in Table 1.
  • CM concentration means comonomer concentration, that is, N-methylmaleimide concentration.
  • content in NMR means the content of structural units derived from N-methylmaleimide when the entire structural unit of the olefin copolymer is 100 mol%.
  • a novel olefin copolymer having an easily decomposable protecting group is provided, and since this is a novel olefinic polar copolymer, it can be used for a wide range of applications.
  • This olefin copolymer can be produced by a simple and efficient polymerization method and has high industrial applicability.

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Abstract

L'invention concerne un nouveau copolymère d'oléfine. La présente invention concerne un copolymère d'oléfine caractérisé en ce qu'il comprend : une unité constitutive (A) comprenant une unité structurelle dérivée d'un éthylène (a-1), et/ou une unité structurelle dérivée d'une α-oléfine (a-2) ayant 3 à 20 atomes de carbone; et une unité constitutive (B) comprenant une unité structurelle dérivée d'une oléfine substituée azotée (b-1) ayant un substituant de formule générale (1) ci-dessous, et/ou une unité structurelle dérivée d'une oléfine substituée azotée (b-2) ayant un substituant de formule générale (2) ci-dessous.
PCT/JP2017/019619 2016-05-25 2017-05-25 Copolymère d'oléfine et son procédé de préparation Ceased WO2017204312A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-104204 2016-05-25
JP2016104204 2016-05-25

Publications (1)

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WO2017204312A1 true WO2017204312A1 (fr) 2017-11-30

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JP7456225B2 (ja) * 2019-03-28 2024-03-27 日本ポリエチレン株式会社 アイオノマー樹脂を含む電線・ケーブル
JP7547811B2 (ja) * 2019-07-01 2024-09-10 日本ポリエチレン株式会社 ゴルフボール用樹脂

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JP2008223011A (ja) * 2007-02-28 2008-09-25 Rohm & Haas Co 実質的に線状のコポリマーおよびその製造方法
JP2011068881A (ja) * 2009-08-28 2011-04-07 Univ Of Tokyo 極性基含有アリルモノマー共重合体の製造方法

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US2402136A (en) * 1941-11-12 1946-06-18 Du Pont Process for polymerization of ethylene with other polymerizable substances
GB1155322A (en) * 1965-08-14 1969-06-18 Hoechst Ag Polymeric Emulsifiable Ointment Bases.
GB1417251A (en) * 1972-04-14 1975-12-10 Basf Ag Polymers containing urethane groups and/or vinylene urethane groups
JPS5184888A (fr) * 1974-12-12 1976-07-24 Aquitaine Petrole
JP2001089519A (ja) * 1999-09-20 2001-04-03 Hitachi Chem Co Ltd エポキシ変性ポリエチレン系樹脂及びその製造法
JP2008223011A (ja) * 2007-02-28 2008-09-25 Rohm & Haas Co 実質的に線状のコポリマーおよびその製造方法
JP2011068881A (ja) * 2009-08-28 2011-04-07 Univ Of Tokyo 極性基含有アリルモノマー共重合体の製造方法

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