JP2009215374A - Olefin-polar monomer random copolymer and method for producing the same - Google Patents

Abstract

The present invention provides an olefin-polar monomer random copolymer that balances various properties of a polar monomer-olefin copolymer and an olefin polymer, and a method for producing the olefin-polar monomer random copolymer.
When the total number of repeating units in a random copolymer is 100 mol, the repeating unit derived from a polar monomer in the random copolymer is 0.01 mol or more and less than 50 mol, and Olefin-polar monomer random, characterized in that the repeating unit derived from olefin in the random copolymer is 50 mol or more and less than 99.99 mol, and has a halogen atom at the end of the random copolymer A copolymer and a method for producing the same are provided.
[Selection figure] None

Description

  The present invention relates to an olefin-polar monomer random copolymer obtained by copolymerizing an olefin and a polar monomer, and a method for producing the olefin-polar monomer random copolymer.

  The polar monomer-olefin copolymer obtained by copolymerizing an olefin and a polar monomer is compatible with the water resistance and mechanical properties of the olefin polymer and the polar monomer polymer represented by the methacrylic polymer. And a polymer having both properties such as paintability.

  For example, Patent Document 1 discloses a polar monomer-olefin copolymer obtained by copolymerizing a polar monomer and an olefin, wherein the content of the monomer unit derived from the olefin in the copolymer is 25 to 50 mol%. (However, the total monomer unit in the copolymer is 100 mol%.) And the monomer unit derived from the olefin in the copolymer contains a structure in which two or more chains are formed. A copolymer is described, and a method for producing the copolymer using a radical polymerization method and a method for producing the copolymer using a compound containing a transition metal atom of Group 8 of the periodic table are described. Has been.

  Patent Document 2 also contains about 80 to about 150 branched chains per 1000 methylene groups, and about 30 to about 90 ethyl branched chains per 100 branched chains that are methyl, about 4 to about Contains about 20 propyl branches, about 15 to about 50 butyl branches, about 3 to about 15 amyl branches, and about 30 to about 140 hexyl branches or longer And a polymer having a long branch chain longer than a hexyl branch chain produced by using a compound containing a transition metal atom of Group 10 of the Periodic Table is described. Yes.

JP 2006-283939 A Japanese National Patent Publication No. 10-513289

However, the polymer described in Patent Document 1 is a copolymer of an olefin and a polar monomer, and in the production method described therein, it is extremely difficult to produce a polymer having an ethylene content exceeding 50 mol%. There was a problem that it was difficult. In general, it is known that a side chain consisting of a methyl group contained in a copolymer inhibits crystal growth and lowers the heat resistance of the copolymer, and the copolymer described in Patent Document 1 is a methyl group. It contains a lot of side chains and has a low heat resistance because it does not show a melting point.
The olefin polymer described in Patent Document 2 is a polymer having an ethylene content exceeding 50 mol%, but has a multi-branched structure in which the total number of branched chains in the polymer reaches 50 or more. Therefore, there is a problem that rigidity and heat resistance are not good.

  For this reason, there has been a demand for a polymer having the characteristics of a copolymer of an olefin and a polar monomer, having a branched structure, a narrow molecular weight distribution, and good physical properties such as heat resistance.

  The object of the present invention is to solve the problems under such circumstances and to have the characteristics of a copolymer of an olefin and a polar monomer, and to have a branched structure, a narrow molecular weight distribution, heat resistance, etc. An object is to provide an olefin-polar monomer random copolymer having various physical properties and a method for producing the same.

  The first aspect of the present invention is an olefin-polar monomer random copolymer obtained by copolymerizing an olefin and a polar monomer, and when the total number of repeating units in the random copolymer is 100 mol, The repeating unit derived from the polar monomer in the random copolymer is 0.01 mol or more and less than 50 mol, and the repeating unit derived from the olefin in the random copolymer is 50 mol or more and 99.99. An object of the present invention is to provide an olefin-polar monomer random copolymer having a halogen atom at the end of the random copolymer, which is less than a mole.

  The second aspect of the present invention is a method for producing an olefin-polar monomer random copolymer obtained by copolymerizing an olefin and a polar monomer, and comprises at least one polymerization selected from the group of transition metal compounds When the total number of repeating units in the random copolymer is 100 mol using the agent, the repeating unit derived from the polar monomer in the random copolymer is 0.01 mol or more and less than 50 mol, And producing a random copolymer having a repeating unit derived from an olefin in the random copolymer of 50 mol or more and less than 99.99 mol and having a halogen atom at the end of the random copolymer. An object of the present invention is to provide a method for producing a random olefin-polar monomer random copolymer.

  According to the present invention, an olefin-polar monomer random copolymer having the characteristics of a copolymer of an olefin and a polar monomer, having a branched structure, a narrow molecular weight distribution, and good physical properties such as heat resistance. Polymers and methods for their production are provided.

Hereinafter, the present invention will be described in detail.
In the first aspect of the present invention described above, in the olefin-polar monomer random copolymer obtained by copolymerizing an olefin and a polar monomer, when the total number of repeating units in the random copolymer is 100 mol, The repeating unit derived from the polar monomer in the random copolymer is 0.01 mol or more and less than 50 mol, and the repeating unit derived from the olefin in the random copolymer is 50 mol or more and 99.99. By having a halogen atom at the end of the random copolymer that is less than a mole, it has a long-chain branching structure with a polar group and a narrow molecular weight distribution, and a balance of physical properties An olefin-polar monomer random copolymer excellent in the above can be obtained.

  In one preferred embodiment of the first aspect of the present invention, the total number of side chains comprising hydrocarbon groups per 1,000 carbon atoms of the random copolymer is 0.001-50, and An olefin-polar monomer random copolymer in which the total number of side chains having 6 or more carbon atoms among the hydrocarbon groups is 0.001 to 20 can be provided. By adopting such a configuration, an olefin-polar monomer random copolymer having a long-chain branched structure, a narrow molecular weight distribution, and an excellent balance of physical properties can be obtained while having a polar group. .

  As another preferred embodiment of the first aspect of the present invention, there can be provided an olefin-polar monomer random copolymer, wherein the olefin is an olefin having 2 to 8 carbon atoms. More preferred of such embodiments may provide an olefin-polar monomer random copolymer, wherein the olefin is ethylene and / or propylene. Thus, by using an olefin having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, particularly preferably ethylene and / or propylene, it has a long chain branched structure while having a polar group, and An olefin-polar monomer random copolymer having a narrow molecular weight distribution and excellent balance of physical properties can be obtained.

  In another preferred embodiment of the first aspect of the present invention, the repeating unit derived from the polar monomer in the random copolymer is 0.01 mol or more and less than 40 mol, more preferably 0.01 mol or more. The olefin-polarity is less than 35 mol, and the repeating unit derived from the olefin in the random copolymer is 60 mol or more and less than 99.99 mol, more preferably 65 mol or more and less than 99.99 mol. Monomer random copolymers can be provided. By adopting such a configuration, an olefin-polar monomer random copolymer having a polar group, excellent compatibility, a long-chain branched structure, and excellent moldability can be obtained.

  As another preferred embodiment of the first aspect of the present invention, an olefin-polar monomer random copolymer having a melting point of 50 ° C. or higher can be provided. The differential scanning calorie | heat amount of said random copolymer whose repeating unit derived from an olefin is 60 mol or more and less than 99.99 mol when the sum total of the repeating unit in the random copolymer is 100 mol ( When DSC) is measured, an endothermic signal is preferably observed in a temperature region of 50 ° C. or higher, and a melting point is more preferably observed in a temperature region of 50 ° C. or higher. Thus, the olefin-polar monomer random copolymer excellent in heat resistance can be obtained by having a melting point of 50 ° C. or higher. That is, the monomer random copolymer of this embodiment balances having a polar group, having a long-chain branched structure, a narrow molecular weight distribution, and high heat resistance.

  In the second aspect of the present invention described above, in the method for producing an olefin-polar monomer random copolymer obtained by copolymerizing an olefin and a polar monomer, at least one selected from the group of transition metal compounds is included. By using a polymerization initiator, when the total number of repeating units in the random copolymer is 100 mol, the repeating unit derived from the polar monomer in the random copolymer is 0.01 mol or more and less than 50 mol. And a random copolymer having a repeating unit derived from an olefin in the random copolymer of 50 mol or more and less than 99.99 mol, and having a halogen atom at the end of the random copolymer. Can be manufactured.

  In one preferred embodiment of the second aspect of the present invention, the polymerization initiator is a living radical polymerization initiator comprising at least one selected from the group of transition metal compounds and at least one selected from the group of halogen compounds. A method for producing a certain olefin-polar monomer random copolymer may be provided. As a more preferable embodiment of this aspect, there is provided a method for producing an olefin-polar monomer random copolymer using a living radical polymerization initiator, wherein the transition metal compound is a compound containing an iron atom and the halogen compound is an organic iodine compound. Can be provided. Thus, by using a specific living radical polymerization initiator, an olefin-polar monomer random copolymer excellent in productivity can be advantageously obtained.

  As another preferred embodiment of the second aspect of the present invention, there can be provided a method for producing an olefin-polar monomer random copolymer, further comprising deashing the random copolymer. Thus, by further decalcifying the produced random copolymer, the inclusion of impurities such as catalyst residues is suppressed, and an olefin-polar monomer random copolymer having excellent versatility is advantageously obtained.

  The olefin referred to in the present invention is an olefin having 2 to 8 carbon atoms having a carbon-carbon double bond site. The olefin is not conjugated with other functional groups having π electrons, and does not have a carbon-carbon double bond directly bonded to a heteroatom such as oxygen, nitrogen, or sulfur like vinyl ether. As long as this condition is satisfied, a compound containing one or more substituents such as a carbonyl group, a cyano group, an amino group, a hydroxyl group, and a halogeno group, or an ether bond, regardless of whether it is cyclic or chain-like, a hydrocarbon compound It may be. The above olefins may be used alone or in combination.

  Examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 1- Octene, vinylcyclohexane, isobutene, 2-methyl-1-butene, 2-methyl, -1-pentene, 2-methyl-1-pentene, 2,4,4-trimethyl-1-pentene, methylidenecyclohexane, ethylidenecyclohexane , Cyclohexene, norbornene and the like. Among these, preferred olefins are propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- 1-pentene, 1-octene and vinylcyclohexane. The above olefins may be used alone or in combination.

The polar monomer as used in the present invention is a compound represented by the following formula (1), and as long as the following conditions are satisfied, a carbonyl group, a cyano group, an amino group, a hydroxyl group, And one or more substituents such as a halogeno group.
R ¹ (R ² ) C═C (R ³ ) R ⁴ (1)
However, in the above formula (1), at least one of R ¹ , R ² , R ³ and R ⁴ is independently a halogen atom, aldehyde group, ester group, ketone group, siloxy group, acetyloxy group, acetylamide Represents a polar functional group such as a group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, an amide group, an imide group, and the other R ¹ , R ² , R ³ and R ⁴ are independently a hydrogen atom Represents a hydrocarbon group or an aryl group. R ¹ , R ² , R ³ and R ⁴ may be bonded to each other.

  Examples of the polar monomer include acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide, methacrylamide, N-alkyl substituted acrylamide, N-alkyl substituted methacrylamide, N, N-dialkyl substituted Examples include acrylamide, N, N-dialkyl-substituted methacrylamide, acrylonitrile, methacrylonitrile, acrolein, methacrolein, methyl vinyl ketone, vinyl chloride, and the like, preferably acrylic acid ester, methacrylic acid ester, acrylonitrile, and more. Acrylic acid esters and methacrylic acid esters are preferred. These polar monomers may be used alone or in combination.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-sec-butyl, and acrylic acid- tert-butyl, acrylate-n-pentyl, isopentyl acrylate, acrylate-sec-pentyl, acrylate-tert-pentyl, neopentyl acrylate, cyclopentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, acrylic acid -N-heptyl, acrylate-n-octyl, acrylate-2-ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, isobornyl acrylate, dicyclopentyl acrylate, menthyl acrylate, acrylic Acrylic acid alkyl esters such as noradamantyl and adamantyl acrylate, and aryl acrylates such as phenyl acrylate, toluyl acrylate and benzyl acrylate, and 2-methoxyethyl acrylate and -3-methoxybutyl acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, γ- (acryloyloxypropyl) trimethoxysilane, γ- (acryloyloxypropyl) Dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-par acrylate Fluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acrylate, acrylic acid 2 -Perfluorohexylethyl, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate and the like. Such an acrylate ester is preferably an alkyl acrylate ester, and more preferably methyl acrylate.

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, methacrylic acid isobutyl, methacrylic acid-sec-butyl, methacrylic acid- tert-butyl, methacrylate-n-pentyl, isopentyl methacrylate, methacrylate-sec-pentyl, methacrylate-tert-pentyl, neopentyl methacrylate, cyclopentyl methacrylate, methacrylate-n-hexyl, cyclohexyl methacrylate, methacrylic acid -N-heptyl, methacrylate-n-octyl, methacrylate-2-ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, methacrylate Methacrylic acid alkyl esters such as dicyclopentyl acid, menthyl methacrylate, noradamantyl methacrylate and adamantyl methacrylate, and aryl methacrylates such as phenyl methacrylate, toluyl methacrylate and benzyl methacrylate, and methacrylic acid-2- Methoxyethyl, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) tri Methoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacrylic acid ethylene oxide adduct, trifluoromethyl methyl methacrylate, methacrylate 2-trifluoromethylethyl acid, 2-perfluoroethylethyl methacrylate, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, dipermethacrylate Fluoromethylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl methacrylate, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate, etc. . The methacrylic acid esters may be used alone or in combination.

  As said N-alkyl substituted acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-phenyl acrylamide etc. are mentioned, for example. Examples of the N, N-dialkyl-substituted acrylamide include N, N-dimethylacrylamide, N, N-diethylacrylamide, and N, N-diphenylacrylamide. Examples of the N-alkyl-substituted methacrylamide include N-methyl methacrylamide, N-ethyl methacrylamide, N-phenyl methacrylamide, N-isopropyl methacrylamide, and the like. Examples of the N, N-dialkyl-substituted methacrylamide include N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N, N-diphenylmethacrylamide and the like. The N-alkyl-substituted acrylamide, N-alkyl-substituted methacrylamide, N, N-dialkyl-substituted acrylamide and N, N-dialkyl-substituted methacrylamide may be used alone or in combination. Good.

  The content of the olefin-derived repeating unit in the olefin-polar monomer random copolymer in the present invention is as long as the effect of the present invention is obtained when the total number of repeating units in the random copolymer is 100 mol. Although it will not specifically limit if it exists in the range of 50-99.99 mol, Preferably it is 60-99.9 mol, Most preferably, it is 80-99 mol.

  In the olefin-polar monomer random copolymer of the present invention, the total number of side chains that are hydrocarbon groups per 1000 carbon atoms of the polymer determined by carbon 13 nuclear magnetic resonance spectroscopy is 0.001. -50, preferably 0.1-40, and the total number of side chains having 6 or more carbon atoms in the hydrocarbon group is 0.001-20, preferably 0.1-10. Further, the number of side chains having 4 carbon atoms is larger than the total number of side chains having 6 or more carbon atoms.

  In the olefin-polar monomer random copolymer of the present invention, the total number of side chains having 6 or more carbon atoms per 1000 carbon atoms of the random copolymer, determined by carbon 13 nuclear magnetic resonance spectroscopy. The total number of side chains having 8 or more carbon atoms contained in is preferably in the range of 0.001 to 10, more preferably in the range of 0.01 to 5, particularly preferably 0.2 to. 3 range.

  In the olefin-polar monomer random copolymer of the present invention, the melting point by differential scanning calorimetry (DSC) is 50 ° C. or more, preferably in the range of 50 to 170 ° C., particularly preferably in the range of 50 to 140 ° C. It is.

  The molecular weight of the olefin-polar monomer random copolymer in the present invention is not particularly limited, but is a number average molecular weight (Mn), preferably 5,000 to 10,000,000, particularly preferably 10,000 to 1, 000,000.

  In the olefin-polar monomer random copolymer of the present invention, the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1.0 to 10. 0, particularly preferably 1.3 to 5.0.

  In the olefin-polar monomer random copolymer of the present invention, halogen atoms are bonded at the end of the polymer, and the number of such halogen atoms is preferably 0.001 to 100 per polymer chain. Preferably it is 0.01-10 pieces, Most preferably, it is 0.1-3 pieces. The halogen atom at the end of the random copolymer, i.e., the growth terminal, enables further polymerization reaction between the copolymer and the olefin or polar monomer used in the present invention, and the olefin-polar monomer random of the present invention. A block copolymer having a block portion made of a copolymer and a block portion (B) made of a random copolymer different from the block portion can be produced.

  The production method of the olefin-polar monomer random copolymer of the present invention is not particularly limited as long as it is a polymerization method using a transition metal compound. For example, coordination polymerization method, anionic polymerization method, cationic polymerization method, radical living Examples thereof include a polymerization method.

  Examples of the transition metal compound used in the above production method include, for example, at least one metal complex (hereinafter referred to as component (A) among metal compounds containing metal atoms of Groups 8 to 12 of the Periodic Table of Elements (IUPAC 1985). Can be used). In addition, although the metal complex of a component (A) may be used independently, you may use a some complex simultaneously. Even in that case, the same effect as when used alone can be expected.

  As a mononuclear metal complex having a transition metal atom of Group 8 of the periodic table of elements of component (A) (IUPAC 1985) as a central metal, which can be used in the method for producing such an olefin-polar monomer random copolymer, Preferably, dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzeneruthenium, dichloro-p-cymenruthenium, dichloro (norbornadiene) ruthenium, cis-dichlorobis (2 , 2′-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, chlorocyclopentadienylbis (tripheny) Phosphine) ruthenium, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium, chloroindenylbis (triphenylphosphine) ruthenium, chloro (2-N, N-dimethylaminoindenyl) bis (triphenylphosphine) ruthenium Mononuclear metal complexes having ruthenium as a central metal such as ethylene indenyl bistriphenylphosphine ruthenium (pentafluorophenyl) borate, ethylene indenyl bistriphenylphosphine ruthenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate Can be mentioned.

  As mononuclear metal complexes, ferrocene, acetyl ferrocene, 1,1′-bis (diphenylphosphino) ferrocene, 1,1′-bis (di-isopropylphosphino) ferrocene, bis (ethylcyclopentadienyl) iron Bis (pentamethylcyclopentadienyl) iron, bis (isopropylcyclopentadienyl) iron, bis (tetramethylcyclopentadienyl) iron, n-butylferrocene, tert-butylferrocene, cyclohexadieneiron tricarbonyl, cyclo Octatetraene iron tricarbonyl, α- (N, N-dimethylamino) ethylferrocene, N, N-dimethylaminomethylferrocene, 1,1′-dimethylferrocene, ethylferrocene, α-hydroxyethylferrocene, Hydroxymethylferrocene, iron (II) acetate, iron (III) acetylacetonate, iron (II) bromide, iron (II) chloride, iron (II) iodine, iron (III) bromide, iron (III) chloride, iron ( II) Phthalocyanine, dichlorobis (triphenylphosphine) iron, bromodicarbonylcyclopentadienyl iron, bromodicarbonyl (pentamethylcyclopentadienyl) iron, dicarbonylcyclopentadienyl iodoiron, dicarbonyl (pentamethylcyclopenta) And mononuclear metal complexes having iron as a central metal, such as dienyl) iodoiron and 1,1′-diacetylferrocene.

In addition, as a binuclear metal complex having a transition metal atom of Group 8 as a central metal in the periodic table of elements of component (A) (IUPAC 1985), for example, a transition metal compound represented by the following formula (2) may be mentioned. Can do.
(CpR ¹ _m ) M ¹ (CO) ₄ M ² (CpR ² _n ) (2)
In the above formula (2), Cp represents a cyclopentadienyl ring, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and at least one R ¹ and at least one R ² is a hydrocarbon group having 5 to 20 carbon atoms, and m and n each independently represents an integer of 1 to 5. M ¹ and M ² each independently represent a transition metal atom of Group 8 of the periodic table of elements. (CO) represents a carbonyl group that is coordinated by bridging M ¹ and M ² , or coordinated to each of M ¹ and M ² .

M ¹ and M ^{2 in} the transition metal compound of the above formula (2) are each independently a transition metal atom of Group 8 of the periodic table of elements (IUPAC 1985). Examples of Group 8 transition metal atoms include iron atoms, ruthenium atoms, and osmium atoms. The combination of Group 8 transition metal atoms M ¹ and M ² is not particularly limited. For example, iron atom and iron atom, iron atom and ruthenium atom, iron atom and osmium atom, ruthenium atom and ruthenium atom, ruthenium atom and osmium Combinations of atoms, osmium atoms, osmium atoms, and the like can be given. Among these, a combination in which both M ¹ and M ² are iron atoms is preferable from the viewpoint of economy.

(CO) of the transition metal compound of the above formula (2) is a carbonyl group that coordinates by bridging M ¹ and M ² or coordinates to M ¹ and M ² , respectively.

As the bonding state between the transition metal atoms M ¹ and M ² of the transition metal compound of the above formula (2) and the carbonyl group (CO), for example,
[1] One carbonyl group (CO) is coordinated to each of transition metal atoms M ¹ and M ² bonded to each other, and ^two (CO) are coordinated by bridging M ¹ and M ^2. Binding state,
[2] One carbonyl group (CO) is coordinated to each of transition metal atoms M ¹ and M ² that have no bond to each other, and two (CO) bridges M ¹ and M ^2. [3] a bonded state in which two carbonyl groups (CO) are coordinated to each of transition metal atoms M ¹ and M ² bonded to each other;
Or the like.

Cp of the transition metal compound of the above formula (2) is a cyclopentadienyl ring, and R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms. (CpR ¹ _m ) is a substituted cyclopentadienyl ring coordinated to the transition metal atom M ¹ , and (CpR ² _n ) is a substituted cyclopentadienyl ring coordinated to the transition metal atom M ² , m and n are each independently an integer of 1 to 5. The substituted cyclopentadienyl ring (CpR ¹ _m ) coordinated to M ¹ is a cyclopentadienyl ring represented by the following formula (2), and the substituted cyclopentadienyl ring (CpR) coordinated to M ^{2 2} _n ) is also expressed by a formula in which all R ¹ in the following formula (3) are replaced with R ² .

Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² of the transition metal compound of the above formula (2) include, for example, a linear saturated hydrocarbon group, a saturated hydrocarbon group having a branched structure, and a cyclic structure Saturated hydrocarbon having a straight chain, a linear unsaturated hydrocarbon group, an unsaturated hydrocarbon group having a branched structure, and an unsaturated hydrocarbon group having a cyclic structure.

R ¹ and R ² of the transition metal compound of the above formula (2) are at least one R ¹ and at least one R ² are each a hydrocarbon group having 5 to 20 carbon atoms, and are soluble in a hydrocarbon solvent. Preferably, at least one R ¹ and at least one R ² are both a saturated hydrocarbon group having 8 to 20 carbon atoms, more preferably at least one R ¹ and at least one R 2. ² is a straight-chain saturated hydrocarbon group having 8 to 20 carbon atoms.

As the transition metal compound of the above formula (2), m is preferably 5, n is 5, and one R ¹ and one R ² are both carbon from the viewpoint of stability and ease of raw material procurement. It is a transition metal compound which is a hydrocarbon group having 5 to 20 atoms, and other R ¹ and other R ² are all methyl groups.

Preferred examples of the transition metal compound include n-pentyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-hexyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, and n-heptyl (tetramethyl) cyclopentadimer. Enyl iron carbonyl dimer, n-octyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-nonyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-decyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-undecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-dodecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-tridecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer , N-tetradecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-pentadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-hexadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-heptadecyl (Tetramethyl) cyclopentadienyl iron carbonyl dimer, n-octadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-nonadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-icosyl (tetramethyl) cyclo Pentadienyl iron carbonyl dimer, sec-pentyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, neopentyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, s c-hexyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-heptyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-octyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-nonyl (tetra Methyl) cyclopentadienyl iron carbonyl dimer, sec-decyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-undecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-dodecyl (tetramethyl) cyclopentadimer Enyl iron carbonyl dimer, sec-tridecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-tetradecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-pentadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-hexadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-heptadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-octadecyl (tetra Methyl) cyclopentadienyl iron carbonyl dimer, sec-nonadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, sec-icosyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cyclopentyl (tetramethyl) cyclopentadienyl iron Carbonyl dimer, cyclohexyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cycloheptyl (tetramethyl) cyclopentadienyl iron carbon Dimer, cyclooctyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cyclononyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cyclodecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cycloundecyl (tetramethyl) cyclo Pentadienyl iron carbonyl dimer, cyclododecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cyclotridecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cyclotetradecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer , Cyclopentadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cyclohexadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer -, Cycloheptadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cyclooctadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cyclononadecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, cycloicosyl (tetramethyl) cyclo such as pentadienyl iron carbonyl dimer, transition metal combinations of atoms M ¹ and M ² are transition metal compound is iron atoms and iron atoms, the transition metal atom M ¹ and combination of iron atoms and iron M ² transition metal compound Transition metal compounds with atoms replaced with iron and ruthenium atoms, transition metal compounds with iron and osmium atoms, transition metal compounds with ruthenium and ruthenium atoms, transition metal compounds with ruthenium and osmium atoms Things, the transition metal compounds is replaced with osmium atom and osmium atom.

A more preferable transition metal compound of the above formula (2) is a transition metal compound in which both M ¹ and M ² are iron atoms from the viewpoint of economy. These transition metal compounds can be used in combination of two or more different transition metal compounds.

  Examples of the metal complex having cobalt as the central metal of the component (A) include cobaltocene.

  Examples of the metal complex having copper as a central metal as the component (A) include a complex in which a ligand containing a group 13-17 atom of the periodic table (IUPAC 1985) is coordinated to a copper atom. Can be mentioned.

  The transition metal compounds can be used alone or in combination. Among these, cyclopentadienyl iron carbonyl dimer, pentamethylcyclopentadienyl iron carbonyl dimer, n-hexyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, n-octyl (tetramethyl) cyclopentadienyl are preferable. These are iron carbonyl dimer, n-decyl (tetramethyl) cyclopentadienyl iron carbonyl dimer, and n-dodecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer.

  Examples of the halogen compound (hereinafter referred to as component (B)) that can be used in the method for producing an olefin-polar monomer random copolymer of the present invention include, for example, an α-halogenocarbonyl compound, an α-halogenocarboxylic acid ester, Examples thereof include halogenated hydrocarbons and (1-halogenoalkyl) benzene derivatives.

  Examples of the α-halogenocarbonyl compound include 1-chloro-2-propanone, 1,1,1-trichloro-2-propanone, 2-chloroacetophenone, 2,2-dichloroacetophenone, 1-bromo-2-propanone, 1,1,1-tribromo-2-propanone, 2-bromoacetophenone, 2,2-dibromoacetophenone, 1-iodo-2-propanone, 1,1,1-triiodo-2-propanone, 2-iodoacetophenone, 2 , 2-Diiodoacetophenone, 1-bromo-2-butanone, 1-bromo-2-pentanone, 3-bromo-2-butanone, 3-bromo-2-pentanone, 2-bromo-3-pentanone, 3-bromo -4-heptanone, 1-iodo-2-butanone, 1-iodo-2-pentanone, 3-iodo-2-butanone 3-iodo-2-pentanone, 2-iodo-3-pentanone, 3-iodo-4-heptanone, 1-chloro-2-butanone, 1-chloro-2-pentanone, 3-chloro-2-butanone, 3- Examples include chloro-2-pentanone, 2-chloro-3-pentanone, and 3-chloro-4-heptanone.

  Examples of the α-halogenocarboxylic acid ester include, for example, methyl 2-chloroacetate, methyl 2-bromoacetate, methyl 2-iodoacetate, ethyl 2-chloroacetate, ethyl 2-bromoacetate, ethyl 2-iodoacetate, 2-chloro Propyl acetate, 2-bromopropyl acetate, 2-iodopropyl acetate, 2-chloroacetate butyl, 2-bromoacetate butyl, 2-iodoacetate butyl, 2,2,2-trichloroacetate methyl, 2,2-dichloroacetate methyl 2,2,2-tribromoacetic acid methyl, 2,2-dibromoacetic acid methyl, 2,2,2-triiodoacetic acid methyl, 2,2-diiodoacetic acid methyl, 2,2,2-trichloroacetic acid ethyl, 2,2 -Ethyl dichloroacetate, ethyl 2,2,2-tribromoacetate, ethyl 2,2-dibromoacetate, ethyl 2,2,2-triiodoacetate, 2, -Ethyl diiodoacetate, methyl 2-chloropropionate, methyl 2-bromopropionate, methyl 2-iodopropionate, methyl 2-chlorobutyrate, methyl 2-bromobutyrate, methyl 2-iodobutyrate, ethyl 2-chloropropionate , Ethyl 2-bromopropionate, ethyl 2-iodopropionate, ethyl 2-chlorobutyrate, ethyl 2-bromobutyrate, ethyl 2-iodobutyrate, propyl 2-chloropropionate, propyl 2-bromopropionate, 2-iodo Propyl propionate, propyl 2-chlorobutyrate, propyl 2-bromobutyrate, propyl 2-iodobutyrate, butyl 2-chloropropionate, butyl 2-bromopropionate, butyl 2-iodopropionate, butyl 2-chlorobutyrate, 2 -Butyl bromobutyrate, 2-butyl iodobutyrate, 2-chloro Methyl ro-2-methylpropionate, methyl 2-bromo-2-methylpropionate, methyl 2-iodo-2-methylpropionate, ethyl 2-chloro-2-methylpropionate, 2-bromo-2-methylpropionate Ethyl acetate, ethyl 2-iodo-2-methylpropionate, methyl 2-chloro-2-methylbutyrate, methyl 2-bromo-2-methylbutyrate, methyl 2-iodo-2-methylbutyrate, 2-chloro-2- Ethyl methylbutyrate, ethyl 2-bromo-2-methylbutyrate, ethyl 2-iodo-2-methylbutyrate, propyl 2-chloro-2-methylpropionate, propyl 2-bromo-2-methylpropionate, 2-iodo- Propyl 2-methylpropionate, propyl 2-chloro-2-methylbutyrate, propyl 2-bromo-2-methylbutyrate, 2-iodo-2 Propyl methylbutyrate, butyl 2-chloro-2-methylpropionate, butyl 2-bromo-2-methylpropionate, butyl 2-iodo-2-methylpropionate, butyl 2-chloro-2-methylbutyrate, 2-bromo Butyl-2-methylbutyrate, butyl 2-iodo-2-methylbutyrate, dimethyl 2-chloro-2,4,4-trimethylglutarate, dimethyl 2-bromo-2,4,4-trimethylglutarate, 2-iodo Dimethyl 2,4,4-trimethylglutarate, 1,2-bis (2′-bromo-2′-methylpropionyloxy) ethane, 1,2-bis (2′-iodo-2′-methylpropionyloxy) Ethane, 1,2-bis (2′-bromopropionyloxy) ethane, 1,2-bis (2′-iodopropionyloxy) ethane, 2- (2 ′ Bromo-2'-methyl-propionyloxy) ethyl alcohol, 2- (2'-iodo-2'-methyl-propionyloxy) ethyl alcohol and the like.

  Examples of the halogenated hydrocarbon include carbon tetrachloride, chloroform, dichloromethane, chloromethane, carbon tetrabromide, bromoform, dibromomethane, bromomethane, carbon tetraiodide, iodoform, diiodomethane, iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 1-iodoisobutane, 2-iodoisobutane, 1-iodopentane, 2-iodopentane, 3-iodopentane, 1-iodoisopentane, 2-iodoisopentane, 3- Iodoisopentane, 1-iodohexane, 2-iodohexane, 3-iodohexane, 1-iodoisohexane, 2-iodoisohexane, 3-iodoisohexane, iodocyclopropane, iodocyclobutane, iodocyclopentane Iodocyclohexane, 1,1-diiodoethane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexane, 1,8-di Iodooctane, 1,10-diiododecane, 1,12-diiododecane, bromoethane, 1-bromopropane, 2-bromopropane, 1-bromobutane, 2-bromobutane, 1-bromoisobutane, 2-bromoisobutane, 1-bromo Pentane, 2-bromopentane, 3-bromopentane, 1-bromoisopentane, 2-bromoisopentane, 3-bromoisopentane, 1-bromohexane, 2-bromohexane, 3-bromohexane, 1-bromoisohexane, 2- Bromoisohexane, 3-bromoisohexane, bromocyclohexane Bread, bromocyclobutane, bromocyclopentane, bromocyclohexane, 1,1-dibromoethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6 -Dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane, 1,12-dibromododecane and the like can be mentioned.

  Further, as halogenated hydrocarbons, for example, chloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloroisobutane, 2-chloroisobutane, 1-chloropentane, 2-chloropentane, 3-chloro Pentane, 1-chloroisopentane, 2-chloroisopentane, 3-chloroisopentane, 1-chlorohexane, 2-chlorohexane, 3-chlorohexane, 1-chloroisohexane, 2-chloroisohexane, 3-chloroisohexane, Chlorocyclopropane, chlorocyclobutane, chlorocyclopentane, chlorocyclohexane, 1,1-dichloroethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6 -Dichlorohex 1,8-dichlorooctane, 1,10-dichlorodecane, 1,12-dichlorododecane, 1-chloro-1-iodoethane, 1-chloro-2-iodoethane, 1-chloro-3-iodopropane, 1- Chloro-4-iodobutane, 1-chloro-5-iodopentane, 1-chloro-6-iodohexane, 1-chloro-8-iodooctane, 1-chloro-10-iododecane, 1-chloro-12-iodododecane, 1-bromo-1-iodoethane, 1-bromo-2-iodoethane, 1-bromo-3-iodopropane, 1-bromo-4-iodobutane, 1-bromo-5-iodopentane, 1-bromo-6-iodohexane 1-bromo-8-iodooctane, 1-bromo-10-iododecane, 1-bromo-12-iodododecane, 1-bromo- -Chloroethane, 1-bromo-2-chloroethane, 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 1-bromo-6-chlorohexane, 1-bromo-8 -Chlorooctane, 1-bromo-10-chlorodecane, 1-bromo-12-chlorododecane and the like.

  Examples of (1-halogenoalkyl) benzene derivatives include 1-bromo-1-phenylethane, 4- (1-bromoethyl) benzoic acid, methyl 4- (1-bromoethyl) benzoate, and 4- (1-bromoethyl). Ethyl benzoate, 1-chloro-1-phenylethane, 4- (1-chloroethyl) benzoic acid, methyl 4- (1-chloroethyl) benzoate, ethyl 4- (1-chloroethyl) benzoate, 1-iodo-1 -Phenylethane, 4- (1-iodoethyl) benzoic acid, methyl 4- (1-iodoethyl) benzoate, ethyl 4- (1-iodoethyl) benzoate and the like.

  The halogen compound is preferably an α-halogenocarbonyl compound, an α-halogenocarboxylic acid ester, or a halogenated hydrocarbon, and more preferably ethyl 2-bromo-2-methylpropionate, ethyl 2-iodopropionate, 2- Iodobutane. These halogen compounds can be used in combination of two or more different halogen compounds.

  In the method for producing an olefin-polar monomer random copolymer of the present invention, the amount of olefin used is usually 0.01 to 1000 mol / L, preferably 0 to 100 mol / L, and the amount of polar monomer used is usually 0.001. -100 mol / L, preferably 0.01-10 mol / L. Moreover, the molar ratio of the usage-amount of the polar monomer with respect to an olefin becomes like this. Preferably it is 0.001-100, Most preferably, it is 0.01-10.

  The concentration of the transition metal compound of component (A) that can be used in the method for producing an olefin-polar monomer random copolymer of the present invention is preferably 0.0001 to 500 mmol / L, particularly preferably 0.001 to 10 mmol. / L.

  The concentration of the halogen compound of component (B) that can be used in the method for producing the olefin-polar monomer random copolymer of the present invention is preferably 0.0001 to 500 mmol / L, particularly preferably 0.001 to 10 mmol / L. L.

  In the method for producing an olefin-polar monomer random copolymer of the present invention, the component (A) and the component (B) may be added individually in any order, or may be added after mixing in advance. In this case, the ratio of the concentration of the component (B) to the concentration of the component (A) is preferably 0.01 to 100, particularly preferably 0.1 to 10.

  In the method for producing an olefin-polar monomer random copolymer of the present invention, a Lewis acid such as a triarylboron compound or a trialkylaluminum compound as an additive component only when the effect of the present invention is maintained, or An amine compound such as monoalkylamine, dialkylamine, and trialkylamine can be used at a desired concentration, but is preferably 0.001 to 5000 mmol / L, particularly preferably 0.01 to 100 mmol / L. .

  In the method for producing an olefin-polar monomer random copolymer of the present invention, the polymerization temperature can be usually carried out over a range of −30 to 400 ° C., preferably 0 to 300 ° C., Especially preferably, it is 130-250 degreeC. The polymerization pressure is not particularly limited, but is preferably normal pressure to 400 MPa, particularly preferably 0.5 to 300 MPa. Performing the polymerization at such a high temperature and pressure is advantageous in terms of forming an olefin chain in the polymer chain. In general, the polymerization time is appropriately determined depending on the type of the target polymer and the reaction apparatus, and may be in the range of, for example, 10 seconds to 40 hours.

  As the polymerization reactor that can be used in the method for producing an olefin-polar monomer random copolymer of the present invention, any of a continuous reactor, a batch reactor, and a semi-batch reactor can be adopted, but preferably a continuous reactor. Reactor.

  In the method for producing the olefin-polar monomer random copolymer of the present invention, a solvent can be used. For example, an inert hydrocarbon solvent such as propane, pentane, hexane, heptane, octane, benzene, toluene, xylene is preferable. Can be used.

  As a polymerization method that can be used in the method for producing the olefin-polar monomer random copolymer of the present invention, any of bulk polymerization, slurry polymerization, solvent polymerization, liquid phase polymerization, or gas phase polymerization can be employed.

  In order to adjust the molecular weight of the olefin-polar monomer random copolymer of the present invention, a chain transfer agent such as hydrogen may be added during the polymerization.

  In this invention, it can deash by mixing the solution which melt | dissolved the random copolymer manufactured with said manufacturing method, and the mixed solution of an acid and alcohol.

  The solvent for the polymer solution is not particularly limited as long as the purpose of dissolving the random copolymer is achieved, but n-butane, n-pentane, n-hexane, n-heptane, n-octane, n- Nonane, n-decane, cyclobutane, cyclopentane, cycloheptane, cyclooctane, cyclononane, cyclodecane, benzene, toluene, anisole, ethylbenzene, paraxylene, metaxylene, orthoxylene, chlorobenzene, paradichlorobenzene, metadichlorobenzene, orthodichlorobenzene, Tetrahydronaphthalene, decahydronaphthalene, tetrahydrofuran, dimethyl ether, diethyl ether, t-butyl methyl ether, cyclohexane, methylcyclohexane, 1,3-dioxolane, 1,3-dioxane 1,4-dioxane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, N, N-dimethylformamide, N, N- dimethylacetamide, dimethyl sulfoxide, carbon disulfide and supercritical carbon dioxide, and the like. Among these, n-hexane, n-heptane, n-octane, toluene, xylene, and cyclohexane are preferable in terms of affinity with the polymer and easy availability.

  Acids used in the above acid-alcohol mixed solution include hydrochloric acid, acetic acid, formic acid, propionic acid, butyric acid, ascorbic acid, oxalic acid, benzoic acid, paratoluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, sulfuric acid, nitric acid and Meldrum's acid and the like can be mentioned, and hydrochloric acid, acetic acid, oxalic acid and ascorbic acid are preferably used.

  Examples of the alcohol used in the acid-alcohol mixed solution include methanol, ethanol, 2,2,2-trichloroethanol, 1-propanol, isopropanol, 1,1,1,3,3,3-hexafluoroisopropanol, 1- Examples include butanol and 2-butanol, and methanol and ethanol are preferably used.

  The volume percentage of acid to alcohol in the acid-alcohol mixed solution is preferably 0.01 to 1.0%. In addition, the volume ratio of the polymer solution to the acid-alcohol mixed solution is preferably 0.01 to 10, particularly preferably 0.1 to 1.0.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the scope of the present invention is not limited only to an Example.
In addition, the measured value of each item in an Example was measured with the following method.
(1) Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)
It measured on the following conditions by the gel permeation chromatography (GPC). A calibration curve was prepared using standard polystyrene.
Measuring machine 150CV type column made by Millipore Waters Shodex M / S 80
Measurement temperature 145 ° C, solvent: orthodichlorobenzene,
Sample concentration 5mg / 8ml

(2) Measurement of differential scanning calorimetry (DSC) Measurement was performed under the following conditions using DSC-VII manufactured by Perkin-Elmer.
Temperature rise: 20 ° C. to 200 ° C. (20 ° C./min) 10 min hold cooling: 200 ° C. to −100 ° C. (20 ° C./min) 10 min hold measurement: −100 ° C. to 300 ° C. (temperature rise at 20 ° C./min) )

(3) Measurement of ¹³ C nuclear magnetic resonance spectrum (NMR) Using JNM-AL400 manufactured by JEOL, in a temperature range of 20-25 ° C. in a chloroform-d solvent, or in an orthodichlorobenzene-d ⁴ solvent, 135 The measurement was performed at a temperature of ° C.
(4) Measurement of melt flow rate (MFR, unit: g / 10 min) Measured according to JIS K7210. The test load was 21.18 N (2.16 kgf), and the measurement temperature was 190 ° C.

(5) Measurement of melting | fusing point Melting | fusing point was obtained by said DSC measurement.
(6) Measurement of repeating unit derived from polar monomer and repeating unit derived from olefin The repeating unit derived from the polar monomer and the repeating unit derived from the olefin were measured by the ¹³ C-NMR analysis.
(7) Measurement of the number of side chains consisting of hydrocarbon groups The number of side chains consisting of hydrocarbon groups was measured by the ¹³ C-NMR analysis.

Examples 1 to 3 (ethylene-methyl acrylate random copolymer)
Ethylene-methyl acrylate polymerization was performed using a tank-type continuous reactor with a stirring blade having an internal volume of 1.94 liters. n-dodecyl (tetramethyl) cyclopentadienyliron carbonyl dimer in heptane solution (3.0 wt%), 2-iodobutane (Tokyo Chemical Industry Co., Ltd.) heptane solution (15.0 wt%), and methyl acrylate (Manufactured by Tokyo Chemical Industry Co., Ltd.) are prepared in separate containers, and are continuously supplied so as to have a predetermined concentration in the tank, and the inside of the tank is in the range of 136 to 201 ° C. under the condition of a residence time of 2 minutes. Ethylene was pressurized and supplied at the temperatures shown in Table 1 so that the polymerization pressures shown in the table were obtained. The product obtained continuously was washed and subjected to structural analysis by ¹ H, ¹³ C-NMR measurement. The implementation conditions and the obtained random copolymer are shown in Table 1 below. In addition, n-dodecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer was synthesized by the method described in Japanese Patent Application No. 2006-036164 (see Japanese Patent Application Laid-Open No. 2007-217290) and used. As shown in Table 1 below, the obtained ethylene-methyl acrylate random copolymer was a polymer having a long-chain branched structure and a narrow molecular weight distribution.

Example 4 (Ethylene-methyl methacrylate random copolymer)
Ethylene-methyl methacrylate polymerization was carried out using a tank-type continuous reactor with a stirring blade having an internal volume of 1.94 liters. n-dodecyl (tetramethyl) cyclopentadienyliron carbonyl dimer in heptane solution (3.0 wt%), 2-iodobutane (Tokyo Chemical Industry Co., Ltd.) heptane solution (15.0 wt%), and methyl methacrylate (Manufactured by Tokyo Chemical Industry Co., Ltd.) are prepared in separate containers, and are continuously supplied so as to have a predetermined concentration in the tank, and the inside of the tank is in the range of 136 to 201 ° C. under the condition of a residence time of 2 minutes. Ethylene was pressurized and supplied at the temperatures shown in Table 1 so that the polymerization pressures shown in the table were obtained. The product obtained continuously was washed and subjected to structural analysis by ¹ H, ¹³ C-NMR measurement. The implementation conditions and the obtained random copolymer are shown in Table 1 below. In addition, n-dodecyl (tetramethyl) cyclopentadienyl iron carbonyl dimer was synthesized by the method described in Japanese Patent Application No. 2006-036164 (see Japanese Patent Application Laid-Open No. 2007-217290) and used. As shown in Table 1 below, the obtained ethylene-methyl methacrylate random copolymer was a polymer having a long-chain branched structure and a narrow molecular weight distribution.

Reference Example 1 (Restart of polymerization)
92 mL of styrene was added to 96 mL of an orthoxylene solution prepared by dissolving 12 g of the ethylene-methyl acrylate random copolymer produced in Example 2 in orthoxylene at 130 ° C., and polymerized at 130 ° C. for 60 minutes. The obtained polymer solution was added dropwise to a 1% hydrochloric acid-ethanol solution to precipitate the polymer, and further dried. As a result, the obtained polymer was 48 g. The number average molecular weight Mn by GPC of the obtained polymer was 51,000, the weight average molecular weight Mw was 96,000, and the molecular weight distribution Mw / Mn was 1.9. The styrene content in the copolymer determined by NMR was 39 mol%. This result shows that the polymerization can be resumed, that is, it supports that the random copolymer of the present invention has a halogen atom at the growing terminal.

Example 5
When the random copolymer produced in Examples 1 to 4 was dissolved in toluene at 105 ° C., the toluene solution obtained was poured into a 1% hydrochloric acid-ethanol solution and purified by deashing to precipitate a white polymer. did. When the obtained polymer was dissolved in toluene and compared before and after purification, the polymer solution before purification was clearly colored, but the polymer solution after purification was clear.

Example 6
When the xylene solution obtained by dissolving the random copolymer prepared in Examples 1 to 4 at 130 ° C. in xylene was put into a 1% hydrochloric acid-ethanol solution and purified by deashing, a white polymer was precipitated. did. When the obtained polymer was dissolved in toluene and compared before and after purification, the polymer solution before purification was clearly colored, but the polymer solution after purification was clear.

Claims (10)

  An olefin-polar monomer random copolymer obtained by copolymerizing an olefin and a polar monomer, and the total number of repeating units in the random copolymer is 100 mol, the polarity in the random copolymer The repeating unit derived from the monomer is 0.01 mol or more and less than 50 mol, and the repeating unit derived from the olefin in the random copolymer is 50 mol or more and less than 99.99 mol. An olefin-polar monomer random copolymer comprising a halogen atom at an end of the random copolymer.   The total number of side chains composed of hydrocarbon groups is 0.001 to 50 per 1000 carbon atoms of the random copolymer, and the hydrocarbon group has 6 or more carbon atoms. The olefin-polar monomer random copolymer according to claim 1, wherein the total number of chains is 0.001-20.   The olefin-polar monomer random copolymer according to claim 1 or 2, wherein the olefin is an olefin having 2 to 8 carbon atoms.   The olefin-polar monomer random copolymer according to claim 3, wherein the olefin having 2 to 8 carbon atoms is ethylene and / or propylene.   The repeating unit derived from the polar monomer in the random copolymer is 0.01 mol or more and less than 40 mol, the repeating unit derived from the olefin in the random copolymer is 60 mol or more and 99 mol. The olefin-polar monomer random copolymer according to any one of claims 1 to 4, which is less than .99 mol.   The olefin-polar monomer random copolymer according to any one of claims 1 to 5, which has a melting point of 50 ° C or higher.   A method for producing an olefin-polar monomer random copolymer obtained by copolymerizing an olefin and a polar monomer, wherein the random copolymer is prepared using a polymerization initiator containing at least one selected from the group of transition metal compounds When the total number of repeating units in the coal is 100 mol, the number of repeating units derived from the polar monomer in the random copolymer is 0.01 mol or more and less than 50 mol, and the random copolymer The random copolymer having a repeating unit derived from the olefin in the range of 50 mol or more and less than 99.99 mol and having a halogen atom at the end of the random copolymer is produced. The manufacturing method of an olefin-polar monomer random copolymer.   The olefin-polar monomer random copolymer according to claim 7, wherein the polymerization initiator is a living radical polymerization initiator composed of at least one selected from the group of transition metal compounds and at least one selected from the group of halogen compounds. A method for producing a polymer.   The method for producing an olefin-polar monomer random copolymer according to claim 8, wherein the transition metal compound is a compound containing an iron atom, and the halogen compound is an organic iodine compound.   The method for producing an olefin-polar monomer random copolymer according to any one of claims 7 to 9, further comprising deashing the random copolymer.