JP6774723B2 - Olefin copolymer containing fluorine atom and polar group - Google Patents

Description

The present invention relates to an olefin copolymer containing a fluorine atom and a polar group. Specifically, the present invention contains an α-olefin containing a fluorine atom and a specific polar group, ethylene and / or having 3 to 20 carbon atoms, and a polar group. It relates to an olefin copolymer composed of an olefin monomer and having excellent moldability, mechanical strength and water repellency.

In general, olefin resins have high mechanical properties, excellent long-term durability, chemical resistance, corrosion resistance, etc., are inexpensive, have good moldability, and are also suitable for environmental problems and resource reusability. Therefore, it is heavily used as an industrial material, and is molded into films, laminates, containers, blow bottles, etc. by injection molding, extrusion molding, blow molding, etc., and is used in a wide range of applications.

The olefin polymer is generally non-polar, has low adhesive strength to different materials, and has poor printability. Therefore, ethylene and a polar group-containing monomer are copolymerized to form a polar group-containing olefin. The method of obtaining a polymer is widely used.

Further, it has been well known that a halogen atom such as a fluorine atom is introduced in order to improve the heat resistance and water repellency of the olefin polymer, but such a polymer has poor moldability and is mechanical. It also has the inherent drawback of being inferior in strength.
For example, Patent Document 1 presents a fluorine-containing ethylene copolymer such as a radical polymer of ethylene containing a fluorine atom and an acrylate, but its moldability is low and it is insufficient for practical use. Patent Document 2 presents a fluorinated ethylene-based acrylate copolymer and the like, but the number of Me branches is large and the mechanical strength is not sufficient. Patent Document 3 presents a fluorine-containing ethylene copolymer having improved water repellency, but it cannot be said that the water repellency and moldability are sufficient.

Therefore, in the polar group-containing fluorine-based olefin resin, a resin material having excellent moldability, good mechanical properties, and sufficient water repellency is desired.

Japanese Unexamined Patent Publication No. 2005-591174 Japanese Unexamined Patent Publication No. 2005-307218 Republished 2006-22122

The object of the present invention, that is, the problem to be solved by the invention, is excellent in moldability, good mechanical properties, sufficient water repellency, and a polar group in view of the above-mentioned conventional problems as background technology. It is to develop a fluorine-based olefin resin that also contains.

In order to solve the above problems, the present inventors have selected polar groups and polymerization catalysts in fluoroolefin resins, molecular structures of polar group-containing olefin copolymers, and structure and water repellency of copolymers. We have examined and verified the correlation of adhesive performance in consideration of various factors, and as a result, we have found a fluoroolefin resin that has excellent moldability, good mechanical properties, sufficient water repellency, and also contains polar groups. This led to the creation of the present invention.
That is, the fluorine-based olefin resin of the present invention contains a fluorine atom and a specific polar group, and is composed of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a polar group-containing olefin monomer, and is particularly water repellent. It is an excellent olefin resin material containing a fluorine atom and a polar group.

Specifically, the present invention is composed of ethylene and / or an α-olefin having 3 to 20 carbon atoms and an olefin monomer containing a polar group selected from the monomer group represented by the general formula (1), and has a fluorine atom. It is a fluorine-based olefin copolymer characterized by containing the above, and the present invention is a basic invention.

[In the formula, T ¹ , T ² , T ³ and T ⁴ each have 2 to 20 carbon atoms having a fluorine atom which may be substituted with a hydrogen atom, a hydrocarbon group or a hetero atom-containing substituent, respectively. A hydrocarbon group, an ester group having 2 to 20 carbon atoms having a fluorine atom, an alkoxy group having 1 to 20 carbon atoms having a fluorine atom, a substituted amino group having 1 to 12 carbon atoms having a fluorine atom, and a carbon number having a fluorine atom. It is a substituent selected from the substituted silyl groups 1 to 18, and any one of T ^{1 to} T ⁴ is a substituent containing a fluorine atom, and the number of fluorine atoms is any number of 1 or more. Further, any one or more of T ^{1 to} T ⁴ may be polar groups other than fluorine atoms, and T ¹ , T ² , T ³ and T ⁴ may be bonded to each other to form a ring. .. ]

T ^{1 to} T ⁴ are specified as the accompanying embodiment inventions (inventions of the dependent claims) with respect to the above-mentioned basic invention (invention of the independent claim of claim 1) (claim 2). -4), the number of methyl branches is defined (claims 5 and 6), and the transition metal catalyst for producing the olefin copolymer is defined (claims 7-9).

As described above, the fluorine-based olefin resin of the present invention contains a fluorine atom and a specific polar group, and is composed of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a polar group-containing olefin monomer. Due to the correlation of these components, formability and mechanical strength are good, and water repellency is particularly excellent. Such specific and novel configurations and performances cannot be found in the literature of the prior art.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been generally described. Therefore, the overall configuration of the present invention can be summarized as follows [1]. ] To [9].
Here, the olefin copolymer in [1] is configured as the basic invention [1], and each of the inventions below [2] adds ancillary requirements to the basic invention or indicates an embodiment thereof. Is.

[1] It is composed of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a polar group-containing olefin monomer selected from the monomer group represented by the general formula (1), and is characterized by containing a fluorine atom. Olefin copolymer.

[In the formula, T ¹ , T ² , T ³ and T ⁴ each have 2 to 20 carbon atoms having a fluorine atom which may be substituted with a hydrogen atom, a hydrocarbon group or a hetero atom-containing substituent, respectively. A hydrocarbon group, an ester group having 2 to 20 carbon atoms having a fluorine atom, an alkoxy group having 1 to 20 carbon atoms having a fluorine atom, a substituted amino group having 1 to 12 carbon atoms having a fluorine atom, and a carbon number having a fluorine atom. It is a substituent selected from the substituted silyl groups of 1 to 18, and any one or more of T ^{1 to} T ⁴ is a substituent containing a fluorine atom, and the number of fluorine atoms is any number of 1 or more. .. Further, any one or more of T ^{1 to} T ⁴ may be polar groups other than fluorine atoms, and T ¹ , T ² , T ³ and T ⁴ may be bonded to each other to form a ring. .. ]

[2] The olefin copolymer according to [1], wherein T ¹ and T ² are hydrogen atoms and T ³ is a hydrogen atom or a methyl group.
[3] A hydrocarbon having 2 to 15 carbon atoms in which T ⁴ is substituted with a fluoroalkyl group having 2 to 15 carbon atoms, a fluoroaryl group having 6 to 15 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms and having a fluorine atom. A group, a hydrocarbon group having 3 to 20 carbon atoms having a fluorine atom substituted with an ester group having 2 to 10 carbon atoms, an ester group having 2 to 15 carbon atoms having a fluorine atom, and 1 to 10 carbon atoms having a fluorine atom. It is a substituent selected from an alkoxy group, a substituted amino group having 1 to 12 carbon atoms having a fluorine atom, and a substituted silyl group having 1 to 18 carbon atoms having a fluorine atom, and has a polar group other than the fluorine atom. The olefin copolymer according to [1] or [2], which is also good.
[4] T ⁴ is a fluoroalkyl group having 2 to 15 carbon atoms having a polar group other than a fluorine atom, a fluoroaryl group having 6 to 15 carbon atoms, an ester group having 2 to 15 carbon atoms having a fluorine atom, and fluorine. The olefin copolymer according to any one of [1] to [3], which is a substituent selected from an alkoxy group having 1 to 10 carbon atoms having an atom.

[5] The olefin copolymer according to any one of [1] to [4], wherein the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbons.
[6] The olefin copolymer according to [5], wherein the number of methyl branches calculated by ¹³ C-NMR is 5 or less per 1,000 carbons.

[7] The olefin copolymer is a copolymer 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 [1]. ] To [6], the olefin copolymer.
[8] The olefin copolymer according to [7], wherein the transition metal catalyst is a metal catalyst of Group 10 of the periodic table.
[9] The olefin copolymer according to [8], wherein the transition metal catalyst is a nickel or palladium metal catalyst.

Since the polar group-containing olefin copolymer according to the present invention contains a fluorine atom and a specific polar group, and is composed of ethylene and / or α-olefin having 3 to 20 carbon atoms and a polar group-containing olefin monomer. Due to these correlations, formability and mechanical strength are good, and water repellency is particularly excellent.
Further, the copolymer in the present invention has a methyl branching number of 50 or less per 1,000 C calculated by ¹³ C-NMR, and when the methyl branching satisfies this value, the elastic modulus is high and the mechanical strength of the molded product is high. Can be expected to increase.

In the following, the olefin copolymer containing a fluorine atom and a polar group of the present invention, its structure and characteristics, the method for producing each monomer and its copolymer, the transition metal catalyst used for the production, and the like will be described for each item. It will be explained concretely and in detail.

[I] Olefin copolymer containing fluorine atom and polar group (1) Olefin copolymer containing fluorine atom and polar group
The olefin copolymer containing a fluorine atom and a polar group, which is the basic invention of the present invention, is selected from ethylene and / or α-olefin having 3 to 20 carbon atoms and the monomer group represented by the general formula (1). It is an olefin copolymer composed of a polar group-containing olefin monomer and containing a fluorine atom, and in particular, a random copolymer in which the monomer unit is randomly copolymerized.

[In the formula, T ¹ , T ² , T ³ and T ⁴ each have 2 to 20 carbon atoms having a fluorine atom which may be substituted with a hydrogen atom, a hydrocarbon group or a hetero atom-containing substituent, respectively. A hydrocarbon group, an ester group having 2 to 20 carbon atoms having a fluorine atom, an alkoxy group having 1 to 20 carbon atoms having a fluorine atom, a substituted amino group having 1 to 12 carbon atoms having a fluorine atom, and a carbon number having a fluorine atom. It is a substituent selected from the substituted silyl groups of 1 to 18, and any one or more of T ^{1 to} T ⁴ is a substituent containing a fluorine atom, and the number of fluorine atoms is any number of 1 or more. .. Further, any one or more of T ^{1 to} T ⁴ may be polar groups other than fluorine atoms, and T ¹ , T ² , T ³ and T ⁴ may be bonded to each other to form a ring. .. ]

The polar group-containing olefin copolymer obtained by copolymerizing ethylene and / or an α-olefin having 3 to 20 carbon atoms with a polar group-containing olefin monomer is known, but the present invention. In the above, since it is an olefin copolymer having a fluorine atom and further containing a specific polar group-containing olefin monomer, and has good moldability and mechanical strength, and is exceptionally excellent in water repellency. It is significantly different from the above-mentioned known copolymers.

(2) α-olefin The α-olefin is an α-olefin having 3 to 20 carbon atoms, and is not particularly limited, but is preferably ethylene having 3 to 20 carbon atoms or ethylene used together with ethylene for polymerization. -The olefin may be used alone, or two or more kinds may be used.

The α-olefin according to the present invention is an α-olefin having 3 to 20 carbon atoms represented by the structural formula: CH ₂ = CHR (R is a hydrocarbon group having 1 to 18 carbon atoms and has a linear structure. It may have branches). More preferably, it is an α-olefin having 3 to 12 carbon atoms, and even more preferably, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, It is an α-olefin selected from 4-methyl-1-pentene, and particularly preferably an α-olefin selected from propylene, 1-butene, 1-hexene and 1-octene.

In the copolymer of ethylene and / or α-olefin and polar group-containing olefin of the present invention, the proportion of structural units derived from ethylene and / or α-olefin is usually 80 to 99.999 mol%, preferably 85 to 85. It is desirable to select from the range of 99.99 mol%, more preferably 90 to 99.97 mol%.

(3) Polar Group-Containing Olefin Monomer The polar group-containing olefin monomer in the present invention is a polar group-containing olefin monomer selected from the monomer group represented by the general formula (1).

[In the formula, T ¹ , T ² , T ³ and T ⁴ each have 2 to 20 carbon atoms having a fluorine atom which may be substituted with a hydrogen atom, a hydrocarbon group or a hetero atom-containing substituent, respectively. A hydrocarbon group, an ester group having 2 to 20 carbon atoms having a fluorine atom, an alkoxy group having 1 to 20 carbon atoms having a fluorine atom, a substituted amino group having 1 to 12 carbon atoms having a fluorine atom, and a carbon number having a fluorine atom. It is a substituent selected from the substituted silyl groups of 1 to 18, and any one or more of T ^{1 to} T ⁴ is a substituent containing a fluorine atom, and the number of fluorine atoms is any number of 1 or more. .. Further, any one or more of T ^{1 to} T ⁴ may be polar groups other than fluorine atoms, and T ¹ , T ² , T ³ and T ⁴ may be bonded to each other to form a ring. .. ]

In T ¹ , T ² , T ³ and T ⁴ , examples of hydrocarbon groups having 2 to 20 carbon atoms include ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group and 1 alkyl group. -Hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1, 1-diethylpropyl group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl Group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, tricyclohexylmethyl group, cyclo Heptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbonyl group, 2-bicyclo [2.2.2] octyl group, nopinyl group, decahydronaphthyl Group, mentyl group, neomentyl group, neopentyl group, 5-decyl group and the like.
Among these, preferred substituents are ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1 -It is a decyl group.

Examples of the alkenyl group include a vinyl group, a butenyl group, a cinnamyl group and a styryl group. Of these, preferred substituents are vinyl groups and styryl groups.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and a fluorenyl group, and examples of substituents that can be present in the aromatic ring of these aryl groups are an alkyl group, an aryl group and a fused aryl group. Specifically, it is a phenylcyclohexyl group, a phenylbutenyl group, a tolyl group, a xsilyl group, a p-ethylphenyl group and the like. Of these, the preferred aryl group is a phenyl group.

Further, T ¹ , T ² , T ³ and T ⁴ may be connected to form an annular structure. Preferred specific examples are cyclic norbornene structures, and specific examples thereof include 5,6-dimethylnorbornene, 5,6-diethylnorbornene, and 5,6-di-t-butylnorbornene. Of these, a more preferred substituent is 5,6-dimethylnorbornene.

In T ¹ , T ² , T ³ and T ⁴ , the hydrocarbon groups having 2 to 20 carbon atoms having a fluorine atom which may be substituted with a heteroatom-containing substituent include oxygen in the above hydrocarbon groups. It may have a substituent containing a heteroatom such as nitrogen and silicon, and is a hydrocarbon group having a fluorine atom and having 2 to 20 carbon atoms.

In T ¹ , T ² , T ³ and T ⁴ , preferred specific examples of ester groups having 2 to 20 carbon atoms having a fluorine atom are methoxycarbonyl groups, ethoxycarbonyl groups, n-propoxys having a fluorine atom in each group. Carbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, n-hexitoxycarbonyl group, n-heptoxycarbonyl group, n-octoxycarbonyl group, n- Examples thereof include a nonaxycarbonyl group and an n-decaxycarbonyl group.
Among these, preferred substituents are an n-hexitoxycarbonyl group, an n-heptoxycarbonyl group, an n-octoxycarbonyl group, an n-nonaxicarbonyl group and an n-decaxicarbonyl group having a fluorine atom. Is.

In T ¹ , T ² , T ³ and T ⁴ , preferred specific examples of the alkoxy groups having 1 to 20 carbon atoms having a fluorine atom are methoxy group, ethoxy group, n-propoxy group having a fluorine atom in each group. Isopropoxy group, n-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, phenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 2,6-Dimethylphenoxy group, 2,6-di-t-butylphenoxy group and the like.
Among these, more preferable substituents are an ethoxy group and an n-octoxy group.

In T ¹ , T ² , T ³ and T ⁴ , preferred specific examples of the substituted amino groups having 1 to 12 carbon atoms having a fluorine atom are monomethylamino groups, dimethylamino groups and monoethyls having a fluorine atom in each group. Examples thereof include an amino group, a diethylamino group, a monoisopropylamino group, a diisopropylamino group, a monophenylamino group, a diphenylamino group, a bis (trimethylsilyl) amino group and a morpholinyl group. Among these, more preferable substituents are a diphenylamino group and a bis (trimethylsilyl) amino group.

In T ¹ , T ² , T ³ and T ⁴ , preferred specific examples of the silyl group having a fluorine atom and having ^{3 to} 18 carbon atoms are a trimethylsilyl group and a (dimethyl) (phenyl) silyl group having a fluorine atom in each group. , (Diphenyl) (methyl) silyl group, triphenylsilyl group. Of these, a more preferred substituent is a trimethylsilyl group.

In T ¹ , T ² , T ³ and T ⁴ , more preferred specific examples are T ¹ and T ² being a hydrogen atom and T ³ being a hydrogen atom or a methyl group.
In a more preferable specific example, T ⁴ has a fluoroalkyl group having 2 to 15 carbon atoms having a polar group other than the fluorine atom, a fluoroaryl group having 6 to 15 carbon atoms, a polar group other than the fluorine atom and a fluorine atom. It has a hydrocarbon group having 2 to 15 carbon atoms, an ester group having 2 to 10 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms having a fluorine atom, an ester group having 2 to 15 carbon atoms having a fluorine atom, and a fluorine atom. It is an alkoxy group having 1 to 10 carbon atoms, a substituted amino group having 1 to 12 carbon atoms having a fluorine atom, and a substituted silyl group having 1 to 18 carbon atoms having a fluorine atom.
A more preferable specific example is that T ⁴ has a fluoroalkyl group having 2 to 15 carbon atoms having a polar group other than a fluorine atom, a fluoroaryl group having 6 to 15 carbon atoms, and 2 to 15 carbon atoms having a fluorine atom. It is an alkoxy group having an ester group and a fluorine atom and having 1 to 10 carbon atoms.

(4) Ratio of monomer units The ratio of structural units derived from ethylene and / or α-olefin is usually 80 to 99.999 mol% in order to exhibit moldability, mechanical properties and water repellency in a well-balanced manner. It is preferably selected from the range of 85 to 99.99 mol%, more preferably 90 to 99.98 mol%, and more preferably 95 to 99.97 mol%.
Therefore, the amount of structural units derived from at least one polar group-containing olefin monomer is usually 0.001 to 20 mol%, preferably 0.01 to 15 mol%, and more preferably 0.02 to 10 mol%. It is preferably selected from the range of 0.03 to 5 mol%.

The structural unit amount of the polar group-containing olefin monomer in the polar group-containing olefin copolymer according to the present invention is determined by using a ¹ H-NMR spectrum. ^{1 1} H-NMR spectrum was measured by the following method.
200 to 250 mg of sample with o-dichlorobenzene / benzene deuterated bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift, with an inner diameter of 10 mmφ It was placed in an NMR sample tube, replaced with nitrogen, sealed, heated and dissolved, and subjected to NMR measurement as a uniform solution. The NMR measurement was performed at 120 ° C. using an AV400M type NMR apparatus of Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe. ^{1 1} H-NMR was measured with a pulse angle of 4.5 °, a pulse interval of 2.0 seconds, and an integration number of 512 times or more. For the chemical shift, the peak of the methyl proton of hexamethyldisiloxane was set to 0.088 ppm, and the chemical shift of the peak due to other protons was based on this. ¹³ C-NMR was measured by the proton complete decoupling method with a pulse angle of 90 °, a pulse interval of 20 seconds, and an integration number of 256 times or more. For the chemical shift, the peak of methyl carbon of hexamethyldisiloxane was set as 1.98 ppm, and the chemical shift of peaks due to other carbons was based on this.

As a specific example of the structural unit amount of the polar group-containing olefin monomer, the polar group-containing olefin monomer content was determined from the ¹ H-NMR spectrum by the following method.
[Structural unit amount of acrylic acid 1H, 1H, 2H, 2H-nonafluorohexyl (FHA)]
The integrated intensity of the peak due to the polar group-containing olefin copolymer in the range of 4.0~4.8ppm when the _{I FHA,} was calculated according to the following formula.
FHA content (mol%) = (I _FHA ) x 100 / (I _FHA + _IE )
_{I M = 0.5 × (I 4.8~4.0} -I V × 2),
_IV = I _{5.7 to 5.9-} (I _{5.1 to 4.8} ) / 2,
Is an amount represented by _{I E = 0.25 × (I 0~4} -I M × 5-I V × 2).
However, for example, I _4.8 to 4.0 indicate the integrated intensity of the proton signal detected between 4.8 ppm and 4.0 ppm. _{Also, I total} is 1/2 of the integral intensities of proton signals detected in 6ppm from 0.5 ppm.

(5) Molecular Weight of Copolymer In the copolymer of ethylene and / or α-olefin of the present invention and a polar group-containing olefin, the weight average molecular weight (Mw) is usually 10,000 to 1,000,000. It is preferably in the range of 12,000 to 500,000, more preferably 15,000 to 300,000. When Mw exceeds 1,000,000, the melt viscosity becomes very high and molding processing becomes difficult. If it is less than 10,000, the moldability is insufficient.

The copolymer of ethylene and / or α-olefin and polar group-containing olefin of the present invention usually has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 1.5 to 3. It is preferably in the range of 5.5, preferably 1.6 to 3.3, and more preferably 1.7 to 3.0. If Mw / Mn is less than 1.5, various processability tends to be insufficient, while if Mw / Mn exceeds 3.5, performance such as adhesiveness tends to be insufficient. In addition, Mw / Mn may be expressed as a molecular weight distribution parameter.

The weight average molecular weight (Mw) according to the present invention is determined by gel permeation chromatography (GPC). Further, the molecular weight distribution parameter (Mw / Mn) is obtained by further obtaining the number average molecular weight (Mn) by gel permeation chromatography (GPC) and calculating the ratio of Mw and Mn and Mw / Mn.

[II] Properties of olefin copolymer (1) Water repellency Water repellency can be mentioned as a specific property of the olefin copolymer containing a fluoropolymer and a polar group of the present invention, that is, the olefin copolymer is It has excellent water repellency, surpassing polyethylene and exhibiting water repellency close to that of fluororesin PTFE (polytetrafluoroethylene).
Water repellency is a property for hydrophilicity, which is the ability to repel water on the surface of an object, and is quantified by the contact angle at which water droplets contact the surface of the object. The larger the contact angle, the higher the water repellency. In polyethylene, the contact angle is 95 to 100 ° (degrees) on the surface of the molded product, in PTFE of fluororesin, it is 114 °, and in the olefin copolymer of the present invention, 2- (par) of Examples described later. This is an example of a copolymer of fluorobutyl) ethyl acrylate, which is about 98 to 106 °, although it depends on the content of comonomer.

(2) Number of Methyl Branches As a specific property of the olefin copolymer containing a fluorine atom and a polar group of the present invention, the number of methyl branches calculated by ¹³ C-NMR can be mentioned, and the number of methyl branches is the polymer chain. It is quantified by the number of methyl branches for 1,000 carbon atoms in the above, and the smaller the number of methyl branches, the better the mechanical strength of the copolymer.
The olefin copolymer of the present invention has a small number of methyl branches, and the number of methyl branches can be reduced to 50 or less, more preferably 5 or less, particularly by copolymerizing with the transition metal catalyst of the present invention (so-called SHOP catalyst). In the olefin copolymer of the present invention, the number of methyl branches is 1.0 or less in the example of the 2- (perfluorobutyl) ethyl acrylate copolymer described later.

The number of methyl branches is measured as follows. The total I _total of the integrated intensity of the peaks of 2 to 60 ppm and 170 to 180 ppm of carbon is standardized to 1,000, and the integrated intensity of the signal of 20 ppm methyl-branched methyl carbon and the integrated of 33 ppm of methyl-branched methine carbon are integrated. the number of methyl branches per total 1000 carbon were calculated using the following equation using the values I _B1 divided by the sum of integrated intensity of the intensity and 37ppm signal with methylene carbon of methyl branch at 4.
Methyl branches number (number / Total _{1000C) = I B1 × 1000 /} I _Total
For the chemical shift, the peak of methyl carbon of hexamethyldisiloxane was set as 1.98 ppm, and the chemical shift of peaks due to other carbons was based on this.

[III] Production of olefin copolymer
(1) Production of Olefin Copolymer The method for producing an olefin copolymer containing a fluorine atom and a polar group of the present invention comprises ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a fluorine atom and a polar group. It is obtained by copolymerizing the contained olefin monomer with a transition metal catalyst.

(2) Polymerization catalyst of olefin copolymer The type of polymerization catalyst according to the present invention is that ethylene and / or α-olefin having 3 to 20 carbon atoms is copolymerized with an olefin monomer containing a fluorine atom and a polar group. It is not particularly limited as long as it is possible, but for example, a method of polymerizing using a Group 5 to 11 transition metal compound having a chelating ligand known as a post-metallocene catalyst as a catalyst is preferable. ..
The transition metal catalyst is a metal catalyst of Group 10 of the periodic table, preferably the transition metal catalyst is a metal catalyst of nickel or palladium, and even if it has a substituent, an arylphosphine or arylalcin compound is coordinated. Transition metal catalysts are more preferred.

The preferred metal catalyst of the present invention is a metal catalyst coordinated with an arylphosphine compound or an arylarcin compound which may have a substituent, has a phosphorus or antimony element in the molecule, and has a substituent. It is a metal catalyst coordinated with a compound having a good aryl group.
As the arylphosphine compound or arylarsine compound which may have a substituent, those known in the art can be exemplified.

Examples of metal catalysts coordinated with these arylphosphine compounds include catalysts of the following general formula (2).

(Y is phosphorus or arsenic, Z is −SO ₃ − or −CO ₂ −. R ^{1 to} R ¹³ are each independently a hydrocarbon atom, a halogen atom, and a hydrocarbon having 1 to 20 carbon atoms. Hydrogen group, hydrocarbon group having 1 to 20 carbon atoms substituted with halogen atom, hydrocarbon group having 2 to 20 carbon atoms substituted with alkoxy group, alkoxy group having 1 to 20 carbon atoms, carbon number 6 to 20 Indicates a substituent selected from the group consisting of an aryloxy group or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. R ¹⁴ is via any of a carbon atom, a silicon atom, and an oxygen atom. Indicates a substituent having 1 to 20 carbon atoms, which is bonded to the aromatic ring.
M represents a metal atom selected from the group consisting of transition metals of groups 8 to 10, and A is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and 1 carbon number substituted with a halogen atom. ~ 30 hydrocarbon groups, 1 to 30 carbons substituted with an alkoxy group, 1 to 30 carbons substituted with an aryloxy group, 1 to 30 alcohols alkoxy groups, or carbon The substituents selected from the group consisting of the number 1 to 30 aryloxy groups are shown. B represents any ligand coordinated to M. Further, A and B may be bonded to each other to form a ring. )

Further, the metal catalyst of the present invention is preferably a Ni catalyst (SHOP-based catalyst) represented by the following general formula (3) from the viewpoint of polymerization activity.

[In the formula, R ³ represents a hydrocarbon group which may contain a hydrogen atom or a hetero atom having 1 to 20 carbon atoms. L ¹ represents a nickel-coordinated ligand. Further, R ³ and L ¹ may be bonded to each other to form a ring. X ¹ represents oxygen or sulfur. R ⁴ and R ⁵ are hydrocarbon groups that may independently contain heteroatoms having 1 to 40 carbon atoms, and at least one of R ⁴ and R ⁵ has two or more heteroatoms. Represents the hydrocarbon group contained. R ¹⁰ , R ¹¹ , R ¹² and R ¹³ independently contain a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 30 carbon atoms, which may contain a hetero atom, 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, PO 3 M ", P (O) (oR 2) represents a ₂ M 'or epoxy containing group (wherein, ^{R 1} is hydrocarbon of hydrogen atom or a C 1-20 R ² represents a hydrogen group, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, M'represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, and M'represents an alkaline earth metal. , X represents an integer of 0 to 3, and y represents an integer of 0 to 2). In addition, a plurality of groups appropriately selected from R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , R ¹² or R ¹³ are linked to each other to form an alicyclic ring, an aromatic ring or a hetero selected from oxygen, nitrogen or sulfur. A heterocycle containing an atom may be formed, and at this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent. ]

Further, in the compound represented by the general formula (3) of the present invention, it is preferable that X ¹ in the formula is oxygen from the viewpoint of polymerization activity.

In the present invention, R ³ represents a hydrocarbon group which may contain hydrogen or a heteroatom having 1 to 20 carbon atoms. The copolymerization reaction in the present invention are believed to ethylene and / or α- olefin or a polar group-containing olefin in the present invention the binding of nickel and R ³ is initiated by inserting. Therefore, the number of carbon atoms of R ³ is excessively large, there is a tendency that the initiation reaction is inhibited. Thus, preferred ^{R 3,} 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms.

Specific examples of R ³ include hydride group, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, n- hexyl, n- octyl group, n- decyl group, Examples thereof include an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a p-methylphenyl group, a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.

In the present invention, L ¹ represents a nickel-coordinated ligand. Ligand L ¹ in the present invention, as coordination bondable atom, an oxygen, nitrogen, a hydrocarbon compound having 1 to 20 carbon atoms having a sulfur. Further, as L ¹ , a hydrocarbon compound having a carbon-carbon unsaturated bond that can be coordinated to the transition metal (which may contain a hetero atom) can also be used. Preferably, L ¹ has 1 to 16 carbon atoms, and more preferably 1 to 10 carbon atoms. Further, as L ¹ for coordination bond with nickel in the general formula (3), a compound having no electric charge is preferable.
L ¹ forms a coordination bond with nickel, but in the present invention, L ¹ is used to promote the polymerization of ethylene and / or α-olefin and the copolymerization of ethylene and / or α-olefin and polar group-containing olefin. ^It is not necessary to use a compound (scavenger) that removes ¹ from nickel.

In the so-called SHOP type metal complex, instead of L ¹ in the present invention, phosphine, for example, be used trimethylphosphine and triphenylphosphine, it can be synthesized similar complexes with the present invention. However, when such a ligand is used, it is known that it is essential to use a scavenger that removes the ligand from M in order to express the polymerizable ability of the olefin.

Preferred L ¹ in the present invention, pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitriles derivatives, aryl nitrile derivatives, alcohols, amides, fatty esters , Aromatic esters, amines, cyclic unsaturated hydrocarbons and the like.
Further preferable L ¹ includes pyridines, cyclic ethers, aliphatic esters, aromatic esters, and cyclic olefins, and particularly preferable L ¹ is pyridine, lutidine (dimethylpyridine), picoline (methylpyridine). , R ¹ CO ₂ R ² (the definitions of R ¹ and R ² are as described above in paragraph 0059).
In addition, R ³ and L ¹ may be bonded to each other to form a ring. An example of such is the cycloocta-1-enyl group, which is also a preferred mode in the present invention.

In the general formula (3) of the present invention, R ⁴ and R ⁵ are hydrocarbon groups that may independently contain a heteroatom having 1 to 40 carbon atoms, and are at least R ⁴ and R ⁵ . One is a hydrocarbon group containing two or more heteroatoms. R ⁴ and R ⁵ are in the vicinity of nickel and interact sterically and / or electronically with nickel. In order to exert such an effect, it is preferable that R ⁴ and R ⁵ are bulky. The preferred carbon number of R ⁴ and R ⁵ is 3 to 40, more preferably 6 to 20.

In R ⁴ and R ⁵ , examples of the hetero atom contained in the hetero atom-containing group include oxygen, nitrogen, phosphorus, sulfur, selenium, silicon, fluorine, and boron. Of these heteroatoms, oxygen, silicon and fluorine are preferred. Examples of the hetero atom-containing group containing these hetero atoms include an alkoxy group, an aryloxy group, an acyl group, an aloyl group and a carboxylate group as oxygen-containing groups, and an amino group and an amide group as nitrogen-containing groups. Examples of the sulfur-containing group include a thioalkoxy group and a thioaryroxy, a phosphorus-containing substituent includes a phosphino group, a selenium-containing group includes a selenyl group, and a silicon-containing group includes. Examples include a trialkylsilyl group, a dialkylarylsilyl group, and an alkyldiarylsilyl group. Examples of the fluorine-containing group include a fluoroalkyl group and a fluoroaryl group, and examples of the boron-containing group include an alkylboron group and an arylboron group. Can be mentioned.
Of these heteroatom-containing groups, the alkoxy group or the aryloxy group is most preferable.

As the heteroatom contained in the heteroatom-containing group described above, one capable of coordinating with the transition metal is preferable.
Specific examples of the heteroatom-containing group containing a heteroatom that can be coordinated to such a transition metal include the following.
That is, as oxygen-containing groups, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, phenoxy group, p-methylphenoxy group, p-methoxyphenoxy group, acetyl group, Examples thereof include a benzoyl group, an acetoxy group, an ethyl carboxylate group, a t-butyl carboxylate group, and a phenyl carboxylate group.
Examples of the nitrogen-containing group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a cyclohexylamino group and the like.
Sulfur-containing groups include thiomethoxy group, thioethoxy group, thio-n-propoxy group, thioisopropoxy group, thio-n-butoxy group, thio-t-butoxy group, thiophenoxy group, p-methylthiophenoxy group, p- Examples thereof include a methoxythiophenoxy group.
Examples of the phosphorus-containing substituent include a dimethylphosphino group, a diethylphosphino group, a di-n-propylphosphino group, a cyclohexylphosphino group and the like.
Examples of the selenium-containing group include a methylselenyl group, an ethylserenyl group, an n-propylserenyl group, an n-butylserenyl group, a t-butylserenyl group, a phenylserenyl group and the like.

In R ⁴ and R ^5, it is sufficient that either R ⁴ or R ⁵ has two or more heteroatom-containing groups, and in particular, both R ⁴ and R ⁵ are hetero two or more. Those containing an atom-containing group are preferable.

In the present invention, R ⁴ and R ⁵ are hydrocarbon groups that may independently contain a heteroatom having 1 to 40 carbon atoms, but more specifically, they contain a hydrogen or a heteroatom. It contains a linear hydrocarbon group that may contain a heteroatom, a branched chain hydrocarbon group that may contain a heteroatom, an alicyclic hydrocarbon group that may contain a heteroatom, and a heteroatom. Also good aryl groups are mentioned.
As described above, it is preferable that R ⁴ and R ⁵ are bulky. Therefore, among these, an alicyclic hydrocarbon group which may contain a heteroatom or an aryl group which may contain a heteroatom is preferable, and an aryl group which may contain a heteroatom is the most preferable. preferable. Examples of such an aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like.

In R ⁴ and R ⁵ of the present invention, when the heteroatom-containing group described above is bonded to the aromatic skeleton of these aryl groups, the heteroatom-containing group may be directly bonded to the aromatic skeleton as a bonding mode. , May be attached to the aromatic skeleton via a spacer such as a methylene group.
When a heteroatom-containing group is bonded to an aromatic skeleton via a methylene group, the number of methylene groups is preferably one. Further, as the substitution position, among the aromatic skeletons in R ⁴ and R ⁵ , the ortho position is preferable with respect to the carbon bonded to phosphorus. By doing so, the heteroatoms in R ⁴ and R ⁵ can take the spatially arrayed so as to interact with nickel.

Specific examples of preferred R ⁴ and R ⁵ are 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-methyl-2,6-dimethoxyphenyl group, 4-t-butyl-. 2,6-dimethoxyphenyl group, 1,3-dimethoxy-2-naphthyl group, 2,6-diethoxyphenyl group, 2,4,6-triethoxyphenyl group, 4-methyl-2,6-diethoxyphenyl Group, 4-t-butyl-2,6-diethoxyphenyl group, 1,3-diethoxy-2-naphthyl group, 2,6-diphenoxyphenyl group, 2,4,6-triphenoxyphenyl group, 4- Methyl-2,6-diphenoxyphenyl group, 4-t-butyl-2,6-diphenoxyphenyl group, 1,3-diphenoxy-2-naphthyl group, 2,6-dimethoxymethylphenyl group, 2,4 6-Trimethoxymethylphenyl group, 4-methyl-2,6-dimethoxymethylphenyl group, 4-t-butyl-2,6-dimethoxymethylphenyl group, 1,3-dimethoxymethyl-2-naphthyl group, 2, 6-Diphenoxymethylphenyl group, 2,4,6-triphenoxymethylphenyl group, 4-methyl-2,6-diphenoxymethylphenyl group, 4-t-butyl-2,6-diphenoxymethylphenyl group, 1,3-Diphenoxymethyl-2-naphthyl group, 2,6-di (2-methoxyethyl) phenyl group, 2,4,6-tri (2-methoxyethyl) phenyl group, 4-methyl-2,6 -Di (2-methoxyethyl) phenyl group, 4-t-butyl-2,6-di (2-methoxyethyl) phenyl group, 1,3-di (2-methoxyethyl) -2-naphthyl group, 2, 6-di (2-phenoxyethyl) phenyl group, 2,4,6-tri (2-phenoxyethyl) phenyl group, 4-methyl-2,6-di (2-phenoxyethyl) phenyl group, 4-t- Examples thereof include a butyl-2,6-di (2-phenoxyethyl) phenyl group and a 1,3-di (2-phenoxyethyl) -2-naphthyl group.

R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are as described above in paragraph 0059, but among these, R ¹³ is preferable because it tends to give a high molecular weight polymer. The carbon number of R ¹³ is 1 to 30, but it is preferably 3 to 30 carbon atoms.
Specific examples of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl as hydrocarbon groups. Group, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group, 4-t-butylphenyl group, 2,4-di-t-butylphenyl group, A trifluoromethyl group, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triphenylsilyl group, a 2,6-difluorophenyl group, using a 9-fluorenyl group, a cyclohexyl group, etc. as a heteroatom-containing hydrocarbon group. , 2,4,6-trifluorophenyl group, pentafluorophenyl group, cyclohexylamino group and the like.
Among these, particularly preferred as ^{R 13,} t-butyl group, a trimethylsilyl group, a phenyl group, 9-anthracenyl group, 4-t-butylphenyl group, 2,4-di -t- butyl group, a pentafluorophenyl group Can be mentioned.

The metal catalyst according to the present invention may be used in combination with an activator, a carrier and the like, if necessary. Examples of the activator include alkylarmoxane and boron-containing compounds, which are cocatalysts used in ordinary metallocene catalysts.
The transition metal complex according to the present invention can be used in combination with an activator, a carrier and the like, if necessary.

Further, as the carrier, any carrier can be used as long as the gist of the present invention is not impaired. In general, inorganic oxides and polymer carriers can be preferably used. Specific examples thereof include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and mixtures thereof, and SiO ₂ −Al ₂ O ₃ , SiO _2- V ₂ O ₅ , SiO _2- TIO ₂ , SiO _2- MgO, SiO _2- Cr ₂ O ₃ and other mixed oxides can also be used, and inorganic silicates, polyethylene carriers, polypropylene carriers, etc. Polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, polyimide carriers and the like can be used. As for these carriers, there are no particular restrictions on the particle size, particle size distribution, pore volume, specific surface area, etc., and any carrier can be used.

As the inorganic silicate, silica, alumina, clay, clay mineral, zeolite, diatomaceous earth and the like can be used. As these, synthetic products may be used, or naturally occurring minerals may be used.
Specific examples of clay and clay minerals include allophane such as allophane, kaolinite such as dikite, nacrite, kaolinite and anokisite, halosite such as metahalosite and halosite, and serpentine such as chrysotile, lizardite and antigolite. Smectites such as stones, montmorillonite, zauconite, byderite, nontronite, saponite, and hectrite, vermiculite minerals such as vermiculite, mica minerals such as illite, serpentine, and sea green stone, attapargit, sepiolite, paigolskite, bentonite, and wood. Examples include knot clay, gairome clay, hisingel stone, pyrophyllite, and rhokuday stones. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Of these specific examples, preferred are kaolins such as dikite, nacrite, kaolinite and anoxite, halosites such as metahalosites and halosites, vermiculites such as chrysotile, risardite and antigolite, and montmorillonite. Smectites such as zauconite, biderite, nontronite, saponite and hectrite, vermiculite minerals such as vermiculite, mica minerals such as illite, serpentine and seagreen stone, synthetic mica, synthetic hectrite, synthetic saponite and synthetic teniolite Particularly preferred are smectites such as montmorillonite, zauconite, byderite, nontronite, saponite and hectolite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectrite, synthetic saponite and synthetic teniolite.

These carriers may be used as they are, but may be treated with acid such as hydrochloric acid, nitrate, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , Li ₂ SO ₄ , dsm ₄ , ZnSO ₄ , Ti ( Salt treatment such as SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ may be performed. In the treatment, the corresponding acid and base may be mixed to form a salt in the reaction system for the treatment. Further, shape control such as crushing and granulation and drying treatment may be performed.

(3) Method for Producing Copolymer In the present invention, the polymerization form is not particularly limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as a medium, vapor phase polymerization performed in a vaporized monomer, or a polymer produced in a monomer liquefied at high temperature and high pressure. High-pressure ion polymerization or the like in which at least a part is dissolved is preferably used.
Further, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. It may be a living polymerization, or it may be polymerized while causing chain transfer.

The copolymerization temperature, copolymerization pressure, and copolymerization time are not particularly limited, but usually, the optimum setting can be made from the following ranges in consideration of productivity and process capacity. That is, the copolymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0. It can be selected from the range of 1 minute to 10 hours, preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours.

In the present invention, the copolymerization is generally carried out in an inert gas atmosphere. For example, a nitrogen, argon or carbon dioxide atmosphere can be used, and a nitrogen atmosphere is preferably used. In addition, a small amount of oxygen or air may be mixed.

The method of supplying the catalyst and the monomer to the copolymerization reactor is not particularly limited, and various methods can be adopted depending on the purpose. For example, in the case of batch polymerization, it is possible to supply a predetermined amount of polar monomer to the copolymerization reactor in advance, add an organometallic compound, form a contact catalyst, and then copolymerize. is there. In this case, additional monomers and additional catalysts may be supplied to the copolymerization reactor. Further, in the case of continuous polymerization, after adding a predetermined amount of monomer and an organometallic compound and contacting them, the contacted catalyst is continuously or intermittently supplied to the copolymerization reactor to carry out the copolymerization reaction continuously. You can take the approach.

Regarding the control of the composition of the copolymer, a method of controlling by supplying a plurality of monomers to the reactor and changing the supply ratio thereof can be generally used. In addition, there are a method of controlling the copolymerization composition by utilizing the difference in the monomer reactivity ratio due to the difference in the structure of the catalyst, and a method of controlling the copolymerization composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. Can be mentioned.

A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, the molecular weight is controlled by controlling the polymerization temperature to control the molecular weight, controlling the monomer concentration to control the molecular weight, controlling the molecular weight using a chain transfer agent, and controlling the ligand structure in the metal catalyst. For example, control.
When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl and the like can be used. Further, when the polar group-containing olefin itself serves as a kind of chain transfer agent, the molecular weight can be adjusted by controlling the ratio of the polar group-containing olefin to the α-olefin and the concentration of the polar group-containing olefin.
When controlling the ligand structure in the metal catalyst to control the molecular weight, a bulky substituent may be arranged around the transition metal M, or an aryl group or a hetero atom which may have a substituent on the transition metal M. It can be arranged so that electron-donating groups such as contained substituents can interact with each other.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples, and the Examples describe the rationality, significance and usefulness of the configuration of the present invention, as well as the prior art. It demonstrates the excellence of. The evaluation methods and metal catalysts used in Examples and Comparative Examples are as follows.

1. 1. Evaluation method (1) Tm
It was determined by the following DSC measurement. Using "EXSTAR6000" manufactured by Seiko Electronics Co., Ltd., maintain isothermal temperature at 40 ° C for 1 minute, raise temperature to 40 to 160 ° C at 10 ° C / min, maintain isothermal temperature at 160 ° C for 10 minutes, and maintain isothermal at 10 ° C / min. The temperature was lowered to 10 ° C., maintained at 10 ° C. for 5 minutes at an isothermal temperature, and then measured at 10 ° C./min when the temperature was raised to 10 to 160 ° C.

(2) Mw / Mn: Measured by GPC.
Equipment: Alliance GPCV2000 type manufactured by Japan Waters Corp.
Detector: Differential refractometer detector with built-in GPCV2000
Sample preparation: Weigh 3 mg of sample and 3 mL of ortodichlorobenzene (containing 0.1 mg / mL 1,2,4-trimethylphenol) in a 4 mL vial and use a resin scoop cap and Teflon® septum. After the lid was closed, melting was carried out for 2 hours using an SSC-9300 type high temperature shaker manufactured by Senshu Kagaku Co., Ltd., which was set at a temperature of 150 ° C. After completion of dissolution, it was visually confirmed that there were no insoluble components.
Column: Showa Denko Shodex HT-806M x 2 + HT-G
Calibration curve preparation: Prepare four 4 mL glass bottles, each weighing 0.2 mg of monodisperse polystyrene standard sample or n-alkane of the combination of (i) to (iv) below, followed by orthodichlorobenzene (orthodichlorobenzene). Weigh 3 mL (containing 0.1 mg / mL 1,2,4-trimethylphenol), cover with a resin screw cap and Teflon® septum, and then set the temperature to 150 ° C. manufactured by Senshu Kagaku. Melting was carried out for 2 hours using an SSC-9300 type high temperature shaker.

(I) Shodex S-1460, S-66.0, n-eicosane (ii) Shodex S-1950, S-152, n-tetracontane (iii) Shodex S-3900, S-565, S -5.05
(Iv) Shodex S-7500, S-1010, S-28.5
A vial containing the sample solution was set in the apparatus, measurements were performed under the above conditions, and chromatograms (data set of retention time and response of the differential refractometer detector) were recorded at a sampling interval of 1 s. The retention time (peak apex) of each polystyrene standard sample was read from the obtained chromatogram and plotted against the logarithmic value of the molecular weight. Here, the molecular weights of n-icosane and n-tetracontane were set to 600 and 1,200, respectively. The nonlinear least squares method was applied to this plot, and the obtained quartic curve was used as the calibration curve.

Calculation of molecular weight: Measurement was performed under the above conditions, and chromatograms were recorded at a sampling interval of 1 s. Using this chromatogram, Sadao Mori, "Size Exclusion Chromatography" (Kyoritsu Shuppan), Chapter 4, p. The differential molecular weight distribution curve and the average molecular weight value (Mn, Mw and Mz) were calculated by the method described in 51-60. However, in order to correct the molecular weight dependence of dn / dc, the height H from the baseline in the chromatogram was corrected by the following formula.
H'= H / [1.032 + 189.2 / M (PE)]
Chromatogram recording (data acquisition) and average molecular weight calculation were performed using an in-house program (created with Microsoft Visual Basic 6.0) on a PC on which Microsoft OS, Windows (registered trademark), and XP were installed. ..
The following formula was used for the molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 x M (PS)
Measurement temperature: 145 ° C Concentration: 20 mg / 10 mL Injection amount: 0.3 ml Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min

(3) Water Contact Angle Test The water repellency of the polar group-containing olefin copolymer according to the present invention was measured by the following water contact angle test.
(I) Method for preparing sample for water contact angle test The polar group-containing olefin copolymer was placed in a heating press mold having dimensions: 50 mm × 60 mm and a thickness of 1 mm, and preheated for 5 minutes in a hot press machine having a surface temperature of 180 ° C. After that, the resin was melted by repeating pressurization and depressurization, and the residual gas in the molten resin was degassed, further pressurized at 4.9 MPa, and held for 5 minutes. Then, it was gradually cooled at a rate of 10 ° C./min under a pressure of 4.9 MPa, and when the temperature dropped to around room temperature, the molded plate was taken out from the mold. The state of the obtained molded plate was adjusted for 48 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5%.

(Ii) Water contact angle test conditions Using the above test piece, the water contact angle was measured with distilled water with reference to the static solution method of JIS R 3257-1999. The only difference from JIS R 3257-1999 is the test piece. Regarding other measurement conditions, the test was carried out by a method according to JIS R 3257-1999.
・ Measuring device: Kyowa Interface Science Co., Ltd., contact angle meter DM-501 type ・ Measurement atmosphere: temperature 23 ± 2 ° C, humidity 50 ± 5% ・ Water droplet capacity: 1 to 4 μL ・ Contact angle calculation method: θ / 2 Law

2. Metal catalyst The metal catalyst was synthesized as a B-27DM / Ni complex according to a synthesis example described in JP2013-043871, and the ligand B-27DM represented by the following chemical formula was used. In addition, B-27DM and Ni (COD) ₂ using bis-1,5-cyclooctadiene nickel (0) (referred to as Ni (COD) ₂ ) according to the examples of International Publication WO2010 / 050256. A nickel complex in which and was reacted 1: 1 was synthesized.

(Example 1) Copolymer of 2- (perfluorobutyl) ethyl acrylate Copolymerization of ethylene with acrylic acid 1H, 1H, 2H, 2H-nonafluorohexyl (FHA; manufactured by Daikin Industries, Ltd., trade name: R1420). :
In an autoclave with a stirring blade having an internal volume of 2.4 liters, dry toluene (1.0 liters), 36.6 mg (0.1 mmol) of tri-n-octyl aluminum (TNOA) and a predetermined amount of acrylic acid 1H, 1H, 2.2 ml (10 mmol) of 2H, 2H-nonafluorohexyl (FHA) was charged. The temperature of the autoclave was raised to 90 ° C. with stirring, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave to adjust the pressure to 3.0 MPa. After completion of the adjustment, 12 ml (120 μmol) of the B-27DM / Ni catalyst was press-fitted with nitrogen to initiate copolymerization.
After polymerizing for 90 minutes, the reaction was stopped by cooling and depressurizing. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, which was then collected by filtration and washing, and further dried under reduced pressure until the amount became constant. The results are shown in Table 1.

(Example 2)
Ethylene-FHA copolymerization was carried out in the same manner as in Example 1 except that the amount of the B-27DM / Ni catalyst was 6 ml (60 μmol) and the polymerization time was 14 minutes. The results are shown in Table 1.
(Example 3)
Ethylene-FHA copolymerization was carried out in the same manner as in Example 1 except that the FHA was 8.7 ml (40 mmol) and the polymerization time was 30 minutes. The results are shown in Table 1.

(Example 4) Copolymer of 1,1,1,3,3,3-hexafluoroisopropylacrylate Ethylene and acrylic acid 1,1,1,3,3,3-hexafluoroisopropyl (HFiPA; Daikin Industries, Ltd.) Manufactured, trade name: R7210) Copolymerization:
In an autoclave with a stirring blade having an internal volume of 2.4 liters, dry toluene (1.0 liters), tri-n-octyl aluminum (TNOA) 36.6 mg (0.1 mmol) and a predetermined amount of acrylic acid 1,1, 1.6 ml (10 mmol) of 1,3,3,3-hexafluoroisopropyl was charged. The temperature of the autoclave was raised to 90 ° C. with stirring, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave to adjust the pressure to 3.0 MPa. After completion of the adjustment, 24 ml (240 μmol) of the B-27DM / Ni catalyst was press-fitted with nitrogen to initiate copolymerization.
After polymerizing for 30 minutes, the reaction was stopped by cooling and depressurizing. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, which was then collected by filtration and washing, and further dried under reduced pressure until the amount became constant. The results are shown in Table 1.

(Example 5) Copolymer of 2,2,2-trifluoroethyl acrylate Copolymerization of ethylene with 2,2,2-trifluoroethyl acrylate (TFEA; manufactured by Daikin Industries, Ltd., trade name: R1110):
In an autoclave with a stirring blade with an internal volume of 2.4 liters, dry toluene (1.0 liters), tri-n-octyl aluminum (TNOA) 36.6 mg (0.1 mmol) and a predetermined amount of acrylic acid 2,2. 1.3 ml (10 mmol) of 2-trifluoroethyl was charged. The temperature of the autoclave was raised to 90 ° C. with stirring, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave to adjust the pressure to 3.0 MPa. After completion of the adjustment, 12 ml (120 μmol) of the B-27DM / Ni catalyst was press-fitted with nitrogen to initiate copolymerization.
After polymerizing for 30 minutes, the reaction was stopped by cooling and depressurizing. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, which was then collected by filtration and washing, and further dried under reduced pressure until the amount became constant. The results are shown in Table 1.

(Comparative Example 1)
A water contact angle test was conducted using a low-density polyethylene resin (manufactured by Japan Polyethylene Corporation, trade name: Kernel KF260) polymerized using a metallocene catalyst.
(Comparative Example 2)
A water contact angle test was conducted using a linear low-density polyethylene resin (manufactured by Japan Polyethylene Corporation, trade name: Harmorex NF444N) polymerized using a metallocene catalyst.
(Comparative Example 3)
A water contact angle test was conducted using a high-density polyethylene resin (manufactured by Japan Polyethylene Corporation, trade name: Novatec HD HS430P) polymerized using a Ziegler-based catalyst.

(Evaluation of the results of Examples and Comparative Examples)
From Tables 1 and 2, the copolymers of Examples 1 to 5 satisfying the provisions of claim 1 of the present invention have a contact angle of more than 100 °, which is superior to that of polyethylene of 95 to 100 ° and that of fluororesin. It shows a value close to PTFE (114 °), demonstrating that the copolymer of the present invention has very good water repellency. In Comparative Examples 1 to 3, the contact angle is about 94 to 98 °, and the water repellency is equivalent to that of polyethylene.
Further, since the comonomer content of Example 3 is higher than that of Examples 1 and 2, the contact angle is higher than that of Examples 1 and 2, and the contact angle of Example 4 is larger than that of Example 5 because the number of fluorine atoms is larger. Is higher than in Example 5.
Furthermore, the number of methyl branches calculated by ¹³ C-NMR of the copolymer of the present invention is 1.0 or less, demonstrating that the copolymer has excellent mechanical strength.
Therefore, it has been clarified that the constitution of the present invention has significance, rationality, usefulness, and excellence over the prior art.

According to the present invention, the water repellency and mechanical properties of a fluorine-containing copolymer of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a polar group-containing olefin are improved, so that the polar group-containing olefin can be used together. The copolymer becomes very useful industrially and has high industrial availability.

Claims (5)

It is composed of ethylene and / or α-olefin having 3 to 20 carbon atoms and a polar group-containing olefin monomer selected from the monomer group represented by the general formula (1), contains a fluorine atom, and is calculated by ¹³ C-NMR. An olefin copolymer characterized in that the number of methyl branches formed is 5 or less per 1,000 carbons.

[In the formula, T ¹ , T ² , T ³ and T ⁴ are substituents independently selected from ester groups having 2 to 20 carbon atoms having a hydrogen atom, a hydrocarbon group and a fluorine atom, and T. Any one or more of ^{1 to} T ⁴ is a substituent containing a hydrogen atom, and the number of fluorine atoms is any number of 1 or more. In a ^further, any one or more of T 1 through T ⁴ is an ester group having 2 to 20 carbon atoms having a fluorine atom ^and, T ^1, T 2, ^{T 3} and ^{T 4} are bonded to each other to form a ring May be formed. ] The olefin copolymer according to claim 1, wherein T ¹ and T ² are hydrogen atoms and T ³ is a hydrogen atom or a methyl group. The olefin copolymer according to claim 1 or 2, wherein the olefin copolymer 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. Method of manufacturing coalescence. The method for producing an olefin copolymer according to claim 3, wherein the transition metal catalyst is a metal catalyst of Group 10 of the periodic table. The method for producing an olefin copolymer according to claim 4, wherein the transition metal catalyst is a nickel or palladium metal catalyst.