JP2016222911A - Olefin copolymer containing fluorine atom and polar group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide fluorine-based olefin copolymer excellent in moldability, good in mechanical physical property, sufficient in water repellency and containing a polar group.SOLUTION: There is provided an F-containing olefin copolymer constituted by ethylene and/or C3 to 20 α-olefin, a polar group-containing olefin monomer (1), where Tto Tare each independently H, a hydrocarbon group, a hydrocarbon group having F substituted/unsubstituted with a hetero atom-containing substituent, the substituent is an ester group having F, an alkoxy group having F, a substituted amino group having F, or a substituted silyl group having F, one or more of Tto Tis a substituent containing F, one or more of Tto Tis a polar group other than F, and Tto Tmay bind to form a ring.SELECTED DRAWING: None

Description

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

  In general, olefin-based resins have high mechanical properties, excellent long-term durability, chemical resistance, corrosion resistance, etc., are inexpensive, have good moldability, and are compatible with environmental issues and resource reusability. Therefore, it is heavily used as an industrial material, and is formed into a film, a laminate, a container, a blow bottle, etc. by, for example, injection molding, extrusion molding, blow molding, etc., and used for a wide range of applications.

  Since olefin polymers are generally nonpolar, have the disadvantages of low adhesion strength to different materials and poor printability, ethylene and a polar group-containing monomer are copolymerized to form a polar group-containing olefin copolymer. A method for obtaining a polymer is widely used.

In addition, in order to improve the heat resistance and water repellency of an olefin polymer, it is also well known to introduce a halogen atom such as a fluorine atom. However, such a polymer is poor in moldability and mechanical. The inherent strength is inferior.
For example, Patent Document 1 proposes a fluorine-containing ethylene copolymer such as a radical polymer of ethylene and acrylate containing fluorine atoms, but has low moldability and is insufficient for practical use. Patent Document 2 proposes a fluorinated ethylene-based acrylate copolymer, but has a large number of Me branches and insufficient mechanical strength. Patent Document 3 proposes a fluorine-containing ethylene copolymer with improved water repellency, but water repellency and moldability are not sufficient.

  Therefore, for polar group-containing fluorine-based olefin resins, resin materials having excellent moldability, good mechanical properties, and sufficient water repellency are desired.

JP 2005-519174 A JP 2005-307218 A Republished 2006-22122

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

In order to solve the above-mentioned problems, the present inventors have selected a polar group and a polymerization catalyst, a molecular structure of the polar group-containing olefin copolymer, and further, a structure and water repellency of the copolymer. Examining and examining various correlations of adhesive performance, etc., and as a result, found a fluorine-based olefin resin having excellent moldability, good mechanical properties, sufficient water repellency, and also containing polar groups. That led to the creation of the present invention.
That is, the fluorinated 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 an olefin monomer containing ethylene and / or an α-olefin having 3 to 20 carbon atoms and a polar group selected from the monomer group represented by the general formula (1). This is a fluorinated olefin copolymer characterized in that it is a basic invention.

[Wherein T ¹ , T ² , T ³ and T ⁴ are each independently a hydrogen atom, a hydrocarbon group, a C 2-20 having a fluorine atom which may be substituted with a hetero atom-containing substituent. 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 is a substituent selected from 1 to 18 substituted silyl group, any one of T ¹ through T ⁴ is a substituent containing a fluorine atom, the number of fluorine atoms is any number of 1 or more. Furthermore, any one or more of T ^{1 to} T ⁴ is a polar group other than a fluorine atom, and T ¹ , T ² , T ³ and T ⁴ may be bonded to each other to form a ring. . ]

In contrast to the basic invention described above (the invention of the independent claim of claim 1), T ^{1 to} T ⁴ are specified as the accompanying embodiment inventions (each invention of the dependent claims) (claim 2). To 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 to 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 correlative action of these components, the moldability and mechanical strength are good, and the water repellency is particularly excellent. Such specific and novel configurations and performances are insignificant from the prior art literature.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described in general. Here, the overall configuration of the present invention will be summarized and summarized in the following [1]. ] To [9].
Here, the olefin copolymer in [1] is configured as the basic invention [1], and [2] each of the following inventions adds an additional requirement to the basic invention or indicates an embodiment thereof. It 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 contains a fluorine atom. Olefin copolymer.

[Wherein T ¹ , T ² , T ³ and T ⁴ are each independently a hydrogen atom, a hydrocarbon group, a C 2-20 having a fluorine atom which may be substituted with a hetero atom-containing substituent. 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 1 to 18 substituted silyl groups, 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 an arbitrary number of 1 or more. . Furthermore, any one or more of T ^{1 to} T ⁴ is a polar group other than a fluorine atom, 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 having a fluorine atom, wherein T ⁴ is substituted with a fluoroalkyl group having 2 to 15 carbon atoms, a fluoroaryl group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms 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 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 having a polar group other than a fluorine atom The olefin copolymer according to [1] or [2], wherein the olefin copolymer is good.
[4] T ⁴ is a C 2-15 fluoroalkyl group having a polar group other than a fluorine atom, a C 6-15 fluoroaryl group, a C 2-15 ester group having a fluorine atom, 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 carbon atoms.
[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 carbon atoms.

[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] ] The olefin copolymer in any one of [6].
[8] The olefin copolymer according to [7], wherein the transition metal catalyst is a metal catalyst belonging to 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.

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 an α-olefin having 3 to 20 carbon atoms and a polar group-containing olefin monomer. Due to these correlations, the moldability and mechanical strength are good, and the water repellency is particularly excellent.
Further, the copolymer in the present invention has a methyl branch number calculated by ¹³ C-NMR of 50 or less per 1,000 C. When the methyl branch satisfies this value, the elastic modulus is high, and the mechanical strength of the molded product Can be expected to be higher.

  In the following, the olefin copolymer containing a fluorine atom and a polar group of the present invention, its structure and characteristics, each monomer and its production method, and the transition metal catalyst used for its production, for each item This will be described specifically 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 a basic invention in the present invention, is selected from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a monomer group represented by the general formula (1). An olefin copolymer comprising a polar group-containing olefin monomer and containing a fluorine atom, and in particular, a random copolymer in which the monomer units are randomly copolymerized.

[Wherein T ¹ , T ² , T ³ and T ⁴ are each independently a hydrogen atom, a hydrocarbon group, a C 2-20 having a fluorine atom which may be substituted with a hetero atom-containing substituent. 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 1 to 18 substituted silyl groups, 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 an arbitrary number of 1 or more. . Furthermore, any one or more of T ^{1 to} T ⁴ is a polar group other than a fluorine atom, and T ¹ , T ² , T ³ and T ⁴ may be bonded to each other to form a ring. . ]

  In addition, although the polar group containing olefin copolymer obtained by copolymerizing ethylene and / or a C3-C20 alpha olefin and a polar group containing olefin monomer is a well-known thing, this invention 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 particularly excellent in water repellency. It is significantly different from the above 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 used together with ethylene and used for polymerization or α having 3 to 20 carbon atoms. -The olefin may be used alone, but two or more types 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. Or may have a branch). More preferably, it is an α-olefin having 3 to 12 carbon atoms, and more preferably, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, An α-olefin selected from 4-methyl-1-pentene, 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).

[Wherein T ¹ , T ² , T ³ and T ⁴ are each independently a hydrogen atom, a hydrocarbon group, a C 2-20 having a fluorine atom which may be substituted with a hetero atom-containing substituent. 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 1 to 18 substituted silyl groups, 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 an arbitrary number of 1 or more. . Furthermore, any one or more of T ^{1 to} T ⁴ is a polar group other than a fluorine atom, 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 the hydrocarbon group having 2 to 20 carbon atoms, the alkyl group, an ethyl group, 1-propyl, 1-butyl group, 1-pentyl, 1 -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, methyl Cyclohexyl group, tricyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2.2] Examples include octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, and 5-decyl group.
Among these, preferred substituents are ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, -A decyl group.

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

T ¹ , T ² , T ³ , and T ⁴ may be linked to form a cyclic structure. A preferred specific example is a cyclic norbornene structure, and specific examples 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 group having 2 to 20 carbon atoms having a fluorine atom that may be substituted with a heteroatom-containing substituent includes oxygen, It may have a substituent containing a hetero atom such as nitrogen or silicon, and is a hydrocarbon group having 2 to 20 carbon atoms having a fluorine atom.

In T ¹ , T ² , T ³ and T ⁴ , preferred specific examples of the ester group having 2 to 20 carbon atoms having a fluorine atom include a methoxycarbonyl group, an ethoxycarbonyl group and an n-propoxy group each having a fluorine atom. Carbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, n-hexoxycarbonyl group, n-heptoxycarbonyl group, n-octoxycarbonyl group, n- Nonoxycarbonyl group and n-decoxycarbonyl group can be mentioned.
Among these, preferable substituents include a fluorine atom-containing n-hexoxycarbonyl group, n-heptoxycarbonyl group, n-octoxycarbonyl group, n-nonoxycarbonyl group, and n-decoxycarbonyl group. It is.

In T ¹ , T ² , T ³ and T ⁴ , preferred specific examples of the C 1-20 alkoxy group having a fluorine atom include a methoxy group, an ethoxy group, an 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 preferred 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 group having 1 to 12 carbon atoms having a fluorine atom include monomethylamino group, dimethylamino group and monoethyl 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. Of these, more preferred 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 ^{3 to} 18 carbon atoms having a fluorine atom include a trimethylsilyl group and a (dimethyl) (phenyl) silyl group having a fluorine atom in each group. , (Diphenyl) (methyl) silyl group, and 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 that T ¹ and T ² are hydrogen atoms, and T ³ is a hydrogen atom or a methyl group.
More preferable specific examples are 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, a polar group other than a fluorine atom, and a fluorine atom. A hydrocarbon group having 2 to 15 carbon atoms, an ester group having 2 to 10 carbon atoms and 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 These are 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.
More preferable specific examples are that 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, or a C 2 to 15 carbon atom having a fluorine atom. An ester group and a C1-C10 alkoxy group having a fluorine atom.

(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 express moldability, mechanical properties and water repellency in a balanced manner. Preferably, it is 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 of the polar group-containing olefin monomers is usually 0.001 to 20 mol%, preferably 0.01 to 15 mol%, more preferably 0.02 to 10 mol%, and more. It is preferable to select from a 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 using a ¹ H-NMR spectrum. ¹ H-NMR spectrum was measured by the following method.
200-250 mg of a sample having an inner diameter of 10 mmφ together with 2.4 ml of o-dichlorobenzene / deuterated benzene bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane which is a chemical shift reference material The sample was placed in an NMR sample tube, purged with nitrogen, sealed, heated and dissolved, and subjected to NMR measurement as a uniform solution. The NMR measurement was performed at 120 ° C. using a Bruker BioSpin Corporation AV400M NMR apparatus equipped with a 10 mmφ cryoprobe. ¹ H-NMR was measured at a pulse angle of 4.5 °, a pulse interval of 2.0 seconds, and the number of integrations of 512 or more. The chemical shift was set so that the peak of methyl proton of hexamethyldisiloxane was 0.088 ppm, and the chemical shift of the peak due to other protons was based on this. ¹³ C-NMR was measured by a proton complete decoupling method with a pulse angle of 90 °, a pulse interval of 20 seconds, and a cumulative number of 256 times or more. The chemical shift was set such that the methyl carbon peak of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shifts of peaks due to other carbons were based on this.

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 ) × 100 / (I _FHA + I _E )
I _M = 0.5 × (I _{4.8 to 4.0} −I _V × 2),
I _V = 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 indicates the integrated intensity of the proton signal detected between 4.8 ppm and 4.0 ppm. I _total is ½ of the integral intensity of the proton signal detected from 0.5 ppm to 6 ppm.

(5) Molecular Weight of Copolymer In the copolymer of ethylene and / or α-olefin and polar group-containing olefin of the present invention, the weight average molecular weight (Mw) is usually 10,000 to 1,000,000, The range is preferably 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 the molding process becomes difficult. If it is less than 10,000, moldability is insufficient.

  In the copolymer of ethylene and / or α-olefin and polar group-containing olefin of the present invention, the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) is usually 1.5-3. 0.5, preferably 1.6 to 3.3, and more preferably 1.7 to 3.0. If Mw / Mn is less than 1.5, various workability tends to be insufficient, whereas if Mw / Mn exceeds 3.5, performance such as adhesion tends to be insufficient. Mw / Mn may be expressed as a molecular weight distribution parameter.

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

[II] Characteristics in Olefin Copolymer (1) Water Repellency Specific characteristics of the olefin copolymer containing a fluorine atom and a polar group of the present invention include water repellency, that is, the olefin copolymer is It is excellent in water repellency and exhibits water repellency close to that of PTFE (polytetrafluoroethylene) as a fluororesin, exceeding polyethylene.
The water repellency is a property with respect to hydrophilicity, and is a performance of repelling water on the surface of an object. The water repellency is quantified by a contact angle at which a water droplet is in contact with the surface of the object. For polyethylene, the contact angle is 95 to 100 ° (degrees) on the surface of the molded body, and 114 ° for PTFE of fluororesin. In the olefin copolymer of the present invention, 2- (part An example of a copolymer of (fluorobutyl) ethyl acrylate, which is about 98 to 106 °, depending on the comonomer content.

(2) Number of methyl branches Specific characteristics of the olefin copolymer containing a fluorine atom and a polar group of the present invention include the number of methyl branches calculated by ¹³ C-NMR, and the number of methyl branches is the polymer chain. The number of methyl branches per 1,000 carbon atoms is quantified. The smaller the number of methyl branches, the better the copolymer is in mechanical strength.
In the olefin copolymer of the present invention, the number of methyl branches is small. Particularly, when copolymerization is performed using the transition metal catalyst of the present invention (so-called SHOP catalyst), the number of methyl branches can be reduced to 50 or less, more preferably 5 or less. In the olefin copolymer of the present invention, in the example of a copolymer of 2- (perfluorobutyl) ethyl acrylate in Examples described later, the number of methyl branches is 1.0 or less.

The number of methyl branches is measured as follows. 2～60Ppm, normalized sum I _total integrated intensity of the peak due to carbon of 170~180ppm 1,000, of 20ppm methyl branch signals due to methyl carbon of the integrated intensity and 33ppm signal with methyl branch methine carbon in the integral The number of methyl branches per 1,000 carbons in total was calculated using the following formula using the value I _B1 obtained by dividing the sum of the intensity and the integrated intensity of the signal by methylene carbon of 37 ppm methyl branches by 4.
Number of methyl branches (pieces / total 1000C) = I _B1 × 1000 / I _total
The chemical shift was set such that the methyl carbon peak of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shifts of peaks due to other carbons were based on this.

[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, a fluorine atom and a polar group. It can be obtained by copolymerizing the contained olefin monomer using a transition metal catalyst.

(2) Polymerization catalyst for olefin copolymer The type of the polymerization catalyst according to the present invention is a copolymer of ethylene and / or an α-olefin having 3 to 20 carbon atoms and an olefin monomer containing a fluorine atom and a polar group. However, there is no particular limitation as long as it is possible, for example, a method of polymerizing using a transition metal compound of Group 5 to 11 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 the arylphosphine or arylarsine compound is more coordinated even if it has a substituent. Transition metal catalysts are more preferred.

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

  Examples of the metal catalyst in which these arylphosphine compounds and the like are coordinated include the catalyst of the following general formula (2).

(Y is phosphorus or arsenic, Z is —SO ₃ — or —CO ₂ —. R ^{1 to} R ¹³ each independently represents a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms. A hydrogen group, a C1-C20 hydrocarbon group substituted with a halogen atom, a C2-C20 hydrocarbon group substituted with an alkoxy group, a C1-C20 alkoxy group, a C6-C20 R ¹⁴ represents 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, and R ¹⁴ is either a carbon atom, a silicon atom, or an oxygen atom. And a substituent having 1 to 20 carbon atoms bonded to an aromatic ring.
M represents a metal atom selected from the group consisting of group 8-10 transition metals, and A represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or 1 carbon atom substituted with a halogen atom. Hydrocarbon group having 1 to 30 carbon atoms, hydrocarbon group having 1 to 30 carbon atoms substituted with alkoxy group, hydrocarbon group having 1 to 30 carbon atoms substituted with aryloxy group, alkoxy group having 1 to 30 carbon atoms, or carbon The substituent selected from the group which consists of a number 1-30 aryloxy group is shown. B represents any ligand coordinated to M. A and B may be bonded to each other to form a ring. )

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

Wherein, R ³ represents a hydrogen atom or a heteroatom hydrocarbon group which may contain 1 to 20 carbon atoms. L ¹ represents a ligand coordinated to nickel. 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 each independently a hydrocarbon group optionally containing a hetero atom having 1 to 40 carbon atoms, and at least one of R ⁴ and R ⁵ includes two or more hetero atoms. This represents a hydrocarbon group to be contained. R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group optionally containing a C 1-30 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 ) ₂ M ′ or an epoxy-containing group (where R ¹ is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms) represents a hydrogen radical, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, M 'is an alkali metal, alkaline earth metal, a Moniumu represents quaternary ammonium or phosphonium, M "represents an alkaline earth metal, x is an integer of 0 to 3, y is 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 connected to each other, and a heterocycle selected from an alicyclic ring, an aromatic ring, oxygen, nitrogen or sulfur You may form the heterocyclic ring containing an atom, and the number of ring members is 5-8 at this time, and it may or may not have a substituent on this ring. ]

In the compound represented by the general formula (3) of the present invention, X ¹ in the formula is preferably oxygen from the viewpoint of polymerization activity.

In the present invention, R ³ represents hydrogen or a hydrocarbon group that may contain a heteroatom having 1 to 20 carbon atoms. The copolymerization reaction in the present invention is considered to be initiated by inserting the ethylene and / or α-olefin or polar group-containing olefin in the present invention into the bond between nickel and R ³ . Therefore, when the number of carbon atoms in R ³ is excessively large, this initiation reaction tends to be inhibited. For this reason, as preferable R < ³ >, it is C1-C16, More preferably, it is C1-C10.

Specific examples of R ³ include hydride group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, 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 ligand coordinated to nickel. The ligand L ¹ in the present invention is a hydrocarbon compound having 1 to 20 carbon atoms having oxygen, nitrogen, and sulfur as atoms capable of coordination bonding. Further, as L ¹ , a hydrocarbon compound having a carbon-carbon unsaturated bond that can be coordinated to a transition metal (which may contain a hetero atom) can also be used. Preferably, L1 has ¹ to 16 carbon atoms, more preferably 1 to 10 carbon atoms. As the L ¹ to the general formula (3) Nickel coordinate bonds in the compound having no charge is preferable.
L ¹ forms a coordinate bond with nickel, but in the present invention, in order to proceed polymerization of ethylene and / or α-olefin and copolymerization of ethylene and / or α-olefin and polar group-containing olefin, L 1 There is no need to use a compound (scavenger) that removes ¹ from nickel.

In the so-called SHOP-based metal complex, a complex similar to that of the present invention can be synthesized by using phosphine, for example, trimethylphosphine or triphenylphosphine, instead of L ^{1 in} the present invention. However, when such a ligand is used, it is known that the use of a scavenger that removes the ligand from M is essential for the expression of olefin polymerization ability.

Preferred L ¹ in the present invention includes pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitrile derivatives, aryl nitrile derivatives, alcohols, amides, aliphatic esters. , Aromatic esters, amines, cyclic unsaturated hydrocarbons and the like.
More preferred L ¹ includes pyridines, cyclic ethers, aliphatic esters, aromatic esters and cyclic olefins, and particularly preferred 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).
R ³ and L ¹ may be bonded to each other to form a ring. Examples of such include a cyclooct-1-enyl group, which is also a preferred embodiment in the present invention.

In the general formula (3) of the present invention, R ⁴ and R ⁵ are each independently a hydrocarbon group optionally containing a hetero atom having 1 to 40 carbon atoms, and at least one of 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, R ⁴ and R ⁵ are preferably bulky. R ⁴ and R ⁵ preferably have 3 to 40 carbon atoms, more preferably 6 to 20 carbon atoms.

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 heteroatom-containing group containing these heteroatoms include an oxygen group, an alkoxy group, an aryloxy group, an acyl group, an aroyl group, and a carboxylate group, and a nitrogen-containing group includes an amino group and an amide group. Sulfur-containing groups include thioalkoxy groups and thioaryloxy groups, phosphorus-containing substituents include phosphino groups, selenium-containing groups include selenyl groups, and silicon-containing groups. Includes a trialkylsilyl group, a dialkylarylsilyl group, and an alkyldiarylsilyl group. Examples of the fluorine-containing group include a fluoroalkyl group and a fluoroaryl group. Examples of the boron-containing group include an alkylboron group and an arylboron group. Is mentioned.
Of these heteroatom-containing groups, an alkoxy group or an aryloxy group is most preferable.

As the hetero atom contained in the hetero atom-containing group described above, one capable of coordinating with a transition metal is preferable.
Specific examples of the hetero atom-containing group containing a hetero atom capable of coordinating with such a transition metal include the following.
That is, as an oxygen-containing group, 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, and a cyclohexylamino group.
Examples of the sulfur-containing group 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- A methoxythiophenoxy group etc. can be mentioned.
Examples of the phosphorus-containing substituent include dimethylphosphino group, diethylphosphino group, di-n-propylphosphino group, cyclohexylphosphino group and the like.
Examples of the selenium-containing group include a methylselenyl group, an ethylselenyl group, an n-propylselenyl group, an n-butylselenyl group, a t-butylselenyl group, and a phenylselenyl group.

In R ⁴ and R ^5, either one of R ⁴ or R ⁵ may have a two or more heteroatom-containing groups, but in particular, R ⁴ and R ⁵ are both two or more hetero Those containing an atom-containing group are preferred.

In the present invention, R ⁴ and R ⁵ are each independently a hydrocarbon group optionally containing a hetero atom having 1 to 40 carbon atoms. More specifically, R ⁴ and R ⁵ contain hydrogen or a hetero atom. A linear hydrocarbon group which may contain, a branched hydrocarbon group which may contain a hetero atom, an alicyclic hydrocarbon group which may contain a hetero atom, a hetero atom A good aryl group is mentioned.
As described above, R ⁴ and R ⁵ are preferably bulky. Therefore, among these, an alicyclic hydrocarbon group which may contain a hetero atom or an aryl group which may contain a hetero atom is preferable, and an aryl group which may contain a hetero atom is most preferred. preferable. Examples of such an aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

In R ⁴ and R ⁵ of the present invention, when the hetero atom-containing group described above is bonded to the aromatic skeleton of these aryl groups, the bonding mode may be that the hetero atom-containing group is directly bonded to the aromatic skeleton. , It may be bonded to the aromatic skeleton through a spacer such as a methylene group.
When the heteroatom-containing group is bonded to the aromatic skeleton via a methylene group, the number of methylene groups is preferably one. Moreover, as a substitution position, among the aromatic skeletons in R ⁴ and R ⁵ , an ortho position with respect to carbon bonded to phosphorus is preferable. By doing so, it is possible to take a spatial arrangement so that the heteroatoms in R ⁴ and R ⁵ interact with nickel.

Specific examples of preferable R ⁴ and R ⁵ include 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- Examples thereof include a t-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. Among these, R ¹³ is preferably bulky because it tends to give a high molecular weight polymer. R ¹³ has 1 to 30 carbon atoms, preferably 3 to 30 carbon atoms.
Specific examples of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ include hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl. Group, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 4-t-butylphenyl group, 2,4-di-t-butylphenyl group, A 9-fluorenyl group, a cyclohexyl group, etc., as a hetero atom-containing hydrocarbon group, a trifluoromethyl group, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triphenylsilyl group, a 2,6-difluorophenyl group 2,4,6-trifluorophenyl group, pentafluorophenyl group, cyclohexylamino group, etc. .
Among these, particularly preferred R ¹³ is t-butyl group, trimethylsilyl group, phenyl group, 9-anthracenyl group, 4-t-butylphenyl group, 2,4-di-t-butylphenyl group, pentafluorophenyl group. Is mentioned.

If necessary, the metal catalyst according to the present invention can be used in combination with an activator, a carrier and the like. Examples of the activator include alkylalumoxane and boron-containing compounds, which are promoters 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.

Moreover, as a support | carrier, unless the main point of this invention is spoiled, arbitrary support | carriers can be used. In general, inorganic oxides and polymer carriers can be preferably used. Specific examples include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a mixture 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, inorganic silicate, polyethylene carrier, polypropylene carrier, A polystyrene carrier, polyacrylic acid carrier, polymethacrylic acid carrier, polyacrylic acid ester carrier, polyester carrier, polyamide carrier, polyimide carrier and the like can be used. These carriers are not particularly limited in particle size, particle size distribution, pore volume, specific surface area, etc., and any one can be used.

As the inorganic silicate, silica, alumina, clay, clay mineral, zeolite, diatomaceous earth, or the like can be used. A synthetic product may be used for these, and the mineral produced naturally may be used.
Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite and other vermiculite minerals, illite, sericite and sea chlorite and other mica minerals, attapulgite, sepiolite, pigolite, bentonite, wood Examples include knot clay, gyrome clay, hysingelite, pyrophyllite, and ryokdee stones. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

  Among these specific examples, preferably, kaolins such as dickite, nacrite, kaolinite, anorcite, halosites such as metahalosite, halosite, serpentine such as chrysotile, lizardite, antigolite, montmorillonite, Examples include smectites, such as sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and sea chlorite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite. Particularly preferred are montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and other smectite groups, vermiculite minerals such as vermiculite, synthetic mica and synthetic hectorite. Synthetic saponite, synthetic taeniolite.

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

(3) Production method of copolymer In the present invention, there is no particular limitation on the polymerization type. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization carried out in the vaporized monomer, or 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. Living polymerization may be used, or polymerization may be performed while simultaneously performing chain transfer.

  There are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges. 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, more preferably 1 minute to 6 hours.

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

  The method for 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 take a technique in which a predetermined amount of polar monomer is supplied to a copolymerization reactor in advance, an organometallic compound is added, a contact catalyst is formed, and then copolymerization is performed. is there. In this case, an additional monomer or an additional catalyst may be supplied to the copolymerization reactor. In the case of continuous polymerization, a predetermined amount of monomer and organometallic compound are added and contacted, and then the contacted catalyst is continuously or intermittently supplied to the copolymerization reactor to carry out the copolymerization reaction continuously. The technique can be taken.

  Regarding the control of the composition of the copolymer, a method of controlling the copolymer 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 for controlling the copolymer composition by utilizing the difference in the monomer reactivity ratio due to the difference in the structure of the catalyst, and a method for controlling the copolymer composition by utilizing the dependency of the monomer reactivity ratio on the polymerization temperature. Can be mentioned.

A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, a method for controlling the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and a molecular structure by controlling the ligand structure in the metal catalyst. Control.
When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used. In addition, when the polar group-containing olefin itself is 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 molecular weight by controlling the ligand structure in the metal catalyst, a bulky substituent is arranged around the transition metal M, or an aryl group or hetero atom that may have a substituent on the transition metal M It can arrange | position so that electron donor groups, such as a containing substituent, can interact.

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

1. Evaluation method (1) Tm
It calculated | required by the following DSC measurements. Using “EXSTAR6000” manufactured by Seiko Denshi Kogyo Co., Ltd., isothermally maintained at 40 ° C. for 1 minute, heated to 40-160 ° C. at 10 ° C./minute, maintained isothermal at 10 ° C. for 10 minutes, 160-160 at 10 ° C./minute The temperature was lowered to 10 ° C., maintained at 10 ° C. for 5 minutes, and then determined by measurement at 10 ° C./min to 10 to 160 ° C.

(2) Mw / Mn: measured by GPC.
Apparatus: Alliance GPCV2000 manufactured by Nippon Waters
Detector: Differential refractometer detector with built-in GPCV2000
Sample preparation: Weigh 3 mg of sample and 3 mL of orthodichlorobenzene (containing 0.1 mg / mL 1,2,4-trimethylphenol) in a 4 mL vial, and use a resin scoop cap and a Teflon (registered trademark) septum. After capping, dissolution was performed for 2 hours using a SSC-9300 type high-temperature shaker manufactured by Senshu Kagaku set at a temperature of 150 ° C. After dissolution, it was visually confirmed that there were no insoluble components.
Column: Showex Denko Shodex HT-806M x 2 + HT-G
Preparation of calibration curve: Four 4 mL glass bottles are prepared, and 0.2 mg each of monodisperse polystyrene standard samples or n-alkanes in combination (i) to (iv) below are weighed, followed by orthodichlorobenzene ( Made by Senshu Kagaku, which weighed 3 mL (containing 0.1 mg / mL 1,2,4-trimethylphenol), capped with a resin screw cap and a Teflon (registered trademark) septum, and set the temperature to 150 ° C. It melt | dissolved for 2 hours using the SSC-9300 type | mold 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
The vial containing the sample solution was set in the apparatus, measured under the above-mentioned conditions, and a chromatogram (retention data and differential refractometer detector response data set) was 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 molecular weight. Here, the molecular weights of n-eicosane and n-tetracontane were 600 and 1,200, respectively. A nonlinear least square method was applied to this plot, and the obtained quartic curve was used as a calibration curve.

Calculation of molecular weight: Measurement was performed under the above-mentioned conditions, and a chromatogram was 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 average molecular weight values (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 from Microsoft) on a PC on which Microsoft OS / Windows (registered trademark) / XP was installed. .
In addition, the following formula was used for the molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 × 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) Sample preparation method for water contact angle test The polar group-containing olefin copolymer is placed in a hot press mold having dimensions of 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. Thereafter, the resin was melted by repeating pressurization and decompression, and the residual gas in the molten resin was deaerated, and further pressurized at 4.9 MPa and held for 5 minutes. Thereafter, the plate was gradually cooled at a rate of 10 ° C./min with a pressure of 4.9 MPa applied, and the molded plate was taken out of the mold when the temperature dropped to near room temperature. The obtained molded plate was conditioned 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 pieces, the water contact angle was measured with distilled water with reference to the still liquid method of JIS R 3257-1999. The only difference from JIS R 3257-1999 is the test piece. Regarding other measurement conditions, etc., the test was carried out by a method according to JIS R 3257-1999.
・ Measuring device: manufactured by Kyowa Interface Science Co., Ltd., contact angle meter DM-501 ・ Measurement atmosphere: temperature 23 ± 2 ° C., humidity 50 ± 5% ・ Water droplet volume: 1-4 μL ・ Contact angle calculation method: θ / 2 Law

2. Metal Catalyst A metal catalyst was synthesized as a B-27DM / Ni complex according to the synthesis example described in JP2013-038771A, and a ligand B-27DM represented by the following chemical formula was used. Also, International Publication in accordance with Example of JP WO2010 / 050256, using bis-1,5-cyclooctadiene nickel _{(0) (Ni (COD)} 2 is referred to as a), B-27DM and Ni _{(COD) 2} A nickel complex in which 1 and 1 reacted with each other was synthesized.

(Example 1) Copolymer of 2- (perfluorobutyl) ethyl acrylate Copolymerization of ethylene and acrylic acid 1H, 1H, 2H, 2H-nonafluorohexyl (FHA; manufactured by Daikin Industries, Ltd., trade name: R1420) :
In an autoclave equipped with a stirring blade having an internal volume of 2.4 liters, dry toluene (1.0 liter), tri-n-octylaluminum (TNOA) 36.6 mg (0.1 mmol) and predetermined amounts 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. while stirring and nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave and the pressure was adjusted to 3.0 MPa. After completion of the adjustment, 12 ml (120 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization.
After polymerization for 90 minutes, the reaction was stopped by cooling and depressurization. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, and then collected by filtration and washing, and further dried under reduced pressure until a constant weight was obtained. 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 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-hexafluoroisopropyl acrylate Ethylene and 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFiPA; Daikin Industries, Ltd.) Copolymerization with product name: R7210):
In an autoclave with a stirring blade having an internal volume of 2.4 liters, dry toluene (1.0 liter), tri-n-octylaluminum (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. while stirring and nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave and the pressure was adjusted to 3.0 MPa. After completion of the adjustment, 24 ml (240 μmol) of B-27DM / Ni catalyst was injected with nitrogen to start copolymerization.
After polymerization for 30 minutes, the reaction was stopped by cooling and depressurization. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, and then collected by filtration and washing, and further dried under reduced pressure until a constant weight was obtained. The results are shown in Table 1.

(Example 5) Copolymer of 2,2,2-trifluoroethyl acrylate Copolymerization of ethylene and 2,2,2-trifluoroethyl acrylate (TFEA; manufactured by Daikin Industries, Ltd., trade name: R1110):
In an autoclave with a stirring blade having an internal volume of 2.4 liters, dry toluene (1.0 liter), tri-n-octylaluminum (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. while stirring and nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave and the pressure was adjusted to 3.0 MPa. After completion of the adjustment, 12 ml (120 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization.
After polymerization for 30 minutes, the reaction was stopped by cooling and depressurization. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, and then collected by filtration and washing, and further dried under reduced pressure until a constant weight was obtained. 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 Nippon Polyethylene Co., Ltd., 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 (trade name: Harmolex NF444N, manufactured by Nippon Polyethylene Co., Ltd.) polymerized using a metallocene catalyst.
(Comparative Example 3)
A water contact angle test was conducted using a high-density polyethylene resin (trade name: Novatec HD HS430P, manufactured by Nippon Polyethylene Co., Ltd.) polymerized using a Ziegler-based catalyst.

(Evaluation of results of Examples and Comparative Examples)
From Tables 1 and 2, in the copolymers of Examples 1 to 5 that satisfy the provisions of claim 1 of the present invention, the contact angle exceeds 100 °, which is superior to that of polyethylene of 95 to 100 °, The value is close to PTFE (114 °), and it is demonstrated that the water repellency of the copolymer of the present invention is very good. In Comparative Examples 1 to 3, the contact angle is about 94 to 98 °, which is the same water repellency as polyethylene.
In addition, since Example 3 has a higher comonomer content than Examples 1 and 2, the contact angle is higher than Examples 1 and 2, and Example 4 has a larger number of fluorine atoms than Example 5, so that the contact angle is higher. Is higher than 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, and it has been demonstrated that the mechanical strength is excellent.
Thus, it has been clarified that the configuration of the present invention has significance, rationality and usefulness, and superiority over the prior art.

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

Claims (9)

An olefin copolymer comprising 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 formula (1) and containing a fluorine atom. Polymer.

[Wherein T ¹ , T ² , T ³ and T ⁴ are each independently a hydrogen atom, a hydrocarbon group, a C 2-20 having a fluorine atom which may be substituted with a hetero atom-containing substituent. 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 1 to 18 substituted silyl groups, 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 an arbitrary number of 1 or more. . Furthermore, any one or more of T ^{1 to} T ⁴ is a polar group other than a fluorine atom, and T ¹ , T ² , T ³ and T ⁴ may be bonded to each other to form a ring. . ] 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. T ⁴ is a C 2-15 fluoroalkyl group, a C 6-15 fluoroaryl group, a C 1-10 alkoxy group substituted with a fluorine atom and a C 2-15 hydrocarbon group, carbon 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, an alkoxy group having 1 to 10 carbon atoms having a fluorine atom, It is a substituent selected from 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 may have a polar group other than a fluorine atom The olefin copolymer according to claim 1 or 2, wherein 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, or a carbon having a fluorine atom. The olefin copolymer according to any one of claims 1 to 3, wherein the olefin copolymer is a substituent selected from an alkoxy group of formulas 1 to 10. 5. The olefin copolymer according to claim 1, wherein the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbon atoms. 6. The olefin copolymer according to claim 5, wherein the number of methyl branches calculated by ¹³ C-NMR is 5 or less per 1,000 carbon atoms. The olefin copolymer is a copolymer polymerized in the presence of a transition metal catalyst of a group 5-11 metal of a periodic table having a chelating ligand. The olefin copolymer of any one of these. The olefin copolymer according to claim 7, wherein the transition metal catalyst is a metal catalyst of Group 10 of the periodic table. The olefin copolymer according to claim 8, wherein the transition metal catalyst is a metal catalyst of nickel or palladium.