KR20170126965A - Polymer compound and method for producing polymer compound - Google Patents

Abstract

It is an object of the present invention to provide a novel polymer compound having a fat chain and an aromatic ring in the main chain. The polymer compound comprising at least one repeating structure represented by the following formulas (A-1) to (A-4) and (B-1) to (B-3) to be.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer compound and a polymer compound,

TECHNICAL FIELD The present invention relates to a method for producing a polymer compound and a polymer compound, and more particularly, to a novel polymer compound having an alkoxyalene structure and a pyridine structure, and a process for producing a polymer compound.

Polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) having a flexible fat chain and a bulky aromatic ring in the main chain are excellent in balance of molding processability, heat resistance, mechanical properties and electrical characteristics, It is considered one of the engineering plastics.

Similarly, a so-called " semi-aromatic polyamide ", in which an aromatic ring is introduced into the main chain, has also been developed as one of engineering plastics, and is known to have excellent heat resistance as compared with a polyamide composed of fatty chain chains.

On the other hand, it is also known that polyester and polyamide are synthesized by a polycondensation reaction using a heteroatom, and thus have a difficult point derived from the obtained structure. For example, polybutylene terephthalate has been reported to have a problem in durability under hot and humid atmospheres, because carboxyl groups at the terminals are deteriorated in hydrolysis resistance (see Patent Document 1).

In recent years, polymerization reactions using a half sandwich type metallocene complex having scandium as a central metal have been reported. For example, Patent Document 2 discloses a copolymerization reaction of an aromatic vinyl compound such as styrene with a conjugated polyene such as 1,3-butadiene, and a neutral metallocene complex is changed to a cationic alkyl complex by an ionic compound And functions as a polymerization catalyst.

Patent Document 1: JP-A-9-316183 Patent Document 2: JP-A No. 2011-084641

A polymer compound having an aliphatic chain and an aromatic ring in the main chain can be a material having excellent properties such as moldability and heat resistance and can be said to be a compound having high applicability.

An object of the present invention is to provide a novel polymer compound having a fat chain and an aromatic ring in the main chain.

As a result of intensive investigations to solve the above problems, the present inventors have found that, by using a specific metallocene complex, the carbon-hydrogen bond (C-H bond) of an alkoxyalene structure or a pyridine structure is activated, -Carbon double bond in the middle part of the reaction, so that a novel polymer compound having an aliphatic chain and an aromatic ring in the main chain can be easily produced, thereby completing the present invention.

That is, the present invention is as follows.

<1> A polymer compound comprising at least one repeating structure represented by the following formulas (A-1) to (A-4) and (B-1) to (B-3)

[Chemical Formula 1]

(In the formulas (A-1) to (A-4) and (B-1) to (B-3), R ¹ independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ² independently represents a halogen atom , Or a hydrocarbon group of 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, R ³ represents a single bond or a nitrogen atom, an oxygen atom, a sulfur atom , And a halogen atom, and R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one kind of atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom , R ^a is independently a single bond or a group capable of containing at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, A bivalent hydrocarbon group having 1 to 20 carbon atoms, R ^b is independently a number A hydrocarbon group having 1 to 6 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, and m independently represents an integer of 0 to 3. However, if the R ² is a hydrocarbon group, the hydrocarbon group R ² connectors and other hydrocarbons of the hydrocarbon group and / or R ² of R ¹ may form a cyclic (環狀) structure. in addition, R ^b is a hydrocarbon group case, the hydrocarbon group of R ^b is connected to the other group R ^a hydrocarbon group of the hydrocarbon group and / or R ^b can form a cyclic structure.)

(2) A polymer compound comprising at least one repeating structure represented by the following formulas (E) and (F).

(2)

(In the formulas (E) and (F), R ¹ independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ² independently represents a halogen atom or a group selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom group having 1 to 20 hydrocarbon group, which can contain atoms of at least one, R ^a includes at least one kind of atoms, each independently represent a single bond, or a nitrogen atom, an oxygen atom, selected from sulfur atom, and a halogen atom And R ^b each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, a hydrocarbon group of ~ 6, m are each independently an integer of 0 to 3. However, R ² is, if a hydrocarbon group, the R ² hydrocarbon groups connectors and a hydrocarbon group and / or other hydrocarbon R ² of R ¹ The annular structure It can be formed. In addition, R ^b is a hydrocarbon group when, in R ^b hydrocarbon group connectors and other hydrocarbons of the hydrocarbon group R ^a and / or R ^b can form a cyclic structure.)

&Lt; 3 &gt; The polymer compound according to &lt; 1 &gt; or &lt; 2 &gt;, which does not contain a hetero atom other than the oxygen atom of the alkoxy group of the alkoxyarylene structure and the nitrogen atom of the pyridine structure in the main chain.

<4> The number-average molecular weight (M _n) of 700 - 100,000, the polymer compound according to any one of <1> to <3>.

<5> The polymer compound according to any one of <1> to <4>, wherein the molecular weight distribution (M _w / M _n ) is 1.5 to 4.0.

<6> Polymerization which produces a polymer compound by reacting alkoxyallenes and / or pyridines with a diene in the presence of a metallocene complex represented by the following formula (D) and an ionic compound comprising a nonpolar anion and a cation &Lt; / RTI &gt;

(3)

(Wherein M represents a scandium atom, a yttrium atom, a samarium atom, a gadolinium atom, or a lutetium atom, and R represents an atom selected from a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, Q ¹ and Q ² each independently represent an anionic coordination site in a monoanionic ligand or a multidentate ligand; L is independently an anionic coordination site in a neutral Lewis base, Or n is an integer of 0 to 5 and w is an integer of 0 to 3. When n is an integer of 2 or more, the hydrocarbon group of R may be any other hydrocarbon group of R So that the annular structure can be formed.

In the presence of a metallocene complex represented by the following formula (D), and an ionic compound comprising a non-coordinating anion and a cation, a compound having both an alkoxy arylene structure and / or a pyridine structure and an aliphatic carbon- A method for producing a polymer compound comprising a polymerization step of polymerizing a compound to produce a polymer compound.

[Chemical Formula 4]

(Wherein M represents a scandium atom, a yttrium atom, a samarium atom, a gadolinium atom, or a lutetium atom, and R represents an atom selected from a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, Q ¹ and Q ² each independently represent an anionic coordination site in a monoanionic ligand or a multidentate ligand; L is independently an anionic coordination site in a neutral Lewis base, Or n is an integer of 0 to 5 and w is an integer of 0 to 3. When n is an integer of 2 or more, the hydrocarbon group of R may be any other hydrocarbon group of R So that the annular structure can be formed.

According to the present invention, a novel polymer compound having high applicability can be provided.

In describing the present invention in detail, a specific example will be described, but the present invention is not limited to the following contents, and can be appropriately changed without departing from the gist of the present invention.

<Polymer Compound 1>

(A-1) to (A-4), and (B-1) to (A-4), which are one type of the present invention (hereinafter sometimes referred to as "polymer compound 1 of the present invention" And a repeating structure represented by the following formula (B-3).

[Chemical Formula 5]

(In the formulas (A-1) to (A-4) and (B-1) to (B-3), R ¹ independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ² independently represents a halogen atom , Or a hydrocarbon group of 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, R ³ represents a single bond or a nitrogen atom, an oxygen atom, a sulfur atom , And a halogen atom, and R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one kind of atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom , R ^a is independently a single bond or a group capable of containing at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, A bivalent hydrocarbon group having 1 to 20 carbon atoms, R ^b is independently a number A hydrocarbon group having 1 to 6 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, and m independently represents an integer of 0 to 3. However, the R ² is, if a hydrocarbon group, the R ² hydrocarbon groups connectors and a hydrocarbon group and / or other hydrocarbon R ² of R ¹ may form a cyclic structure. when addition, R ^b is a hydrocarbon group, R ^b May be bonded to the hydrocarbon group of R &lt; ^a & gt ^; and / or other hydrocarbon groups of R &lt; ^b &gt; to form a cyclic structure.

The present inventors have found that by activating cyclic carbon-hydrogen bonds (C-H bonds) of alkoxyallenes or pyridines by using specific metallocene complexes (details will be described later), addition reaction to alkenes It is clear that it is possible to push forward. Further, it has been found that by using a diene having two carbon-carbon double bonds as an alkene, the polymerization reaction progresses and the polymer compound can be efficiently produced. The following formula shows the reaction mechanism when "1,4-dimethoxybenzene" is used as the "alkoxyallenes" and "1,4-divinylbenzene" is used as the "dienes" , 4-dimethoxybenzene is added to 1,4-divinylbenzene at the 2-position, but since the position to which the alkoxylarene is added can be controlled by a substituent or the like, the polymer compound of the present invention It is not limited to the combination).

[Chemical Formula 6]

Further, when alkoxyallenes or pyridines having a methyl group (-CH ₃ ) at position 2 (o-position) are used, the carbon-hydrogen bond of the methyl group is activated and the addition reaction from the methyl group position to the alkene proceeds The inventors of the present invention disclose. The following formula shows the reaction mechanism when "2,6-lutidine" is used as the "pyridine" and "2,5-norbornadine" is used as the "diene".

(7)

That is, it is possible to easily produce a useful polymer compound having an aromatic ring derived from alkoxyallenes or pyridines and an aliphatic chain derived from dienes in the main chain by the central-valence reaction formed by the carbon-carbon bond (C-C bond) It is.

Further, the formula (A-4) represents a repeating structure formed as the polymerization progresses three-dimensionally. In the formula (A-4), &quot; Means that the end repeats the structure derived from an alkoxyallene and the structure derived from a diene.

[Chemical Formula 8]

Hereinafter, the "repeating structure represented by formulas (A-1) to (A-4) and (B-1) to (B-3)" will be described in detail.

R ¹ each independently represents a "hydrocarbon group having 1 to 6 carbon atoms", but the "hydrocarbon group" is not limited to a straight-chain saturated hydrocarbon group and may have a carbon-carbon unsaturated bond, a branched structure, .

The number of carbon atoms of the hydrocarbon group of R ¹ is preferably 4 or less, more preferably 3 or less, further preferably 2 or less.

As R ^1, a methyl group (-CH _3), ethyl group (-C ₂ H _5), n- propyl group (- C ₃ H ₇ ^n), i- propyl _{^{(- i C 3 H 7)}} , n- butyl ( ^-N C ₄ H ₉ ), a t-butyl group ( ^-t C ₄ H ₉ ), and a phenyl group (-C ₆ H ₅ ).

R ² each independently represents a "halogen atom" or a "hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom". However, May contain at least one kind of atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom "may include a functional group including a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom and the like , It means that a linking group including a nitrogen atom, an oxygen atom, a sulfur atom and the like can be included in the interior or terminal of the carbon skeleton. The "hydrocarbon group" has the same meaning as described above. Accordingly, the hydrocarbon group which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom includes, for example, an ether group such as -CH ₂ -O-CH ₃ , A hydrocarbon group having 2 carbon atoms contained in the interior of the carbon skeleton, and a hydrocarbon group having 2 carbon atoms including an ether group such as -O-CH ₂ -CH _{3 in} the terminal of the carbon skeleton.

When R ² is a hydrocarbon group, the number of carbon atoms of the hydrocarbon group of R ² is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 18 or less, more preferably 16 or less, More preferably 14 or less.

When R ² is a hydrocarbon group, examples of the functional group and the linking group contained in R ² include an amide group (-NHCO-), an ether group (-O-), a thioether group (-S-), a fluorine group (-F) (-Cl), a bromo group (-Br), an iodo group (-I), and a dimethylamino group (-N (CH ₃ ) ₂ ).

Examples of R ^2, fluoride group (-F), chloro group (-Cl), bromo (-Br), iodine group (-I), a methyl group (-CH _3), ethyl group (-C ₂ H _5), n- a propyl group (- C ₃ H ₇ ^n), i- propyl _{^{(- i C 3 H 7)}} , n- butyl _{^{(- n C 4 H 9)}} , t- butyl _{^{(- t C 4 H 9)}} , (-C ₆ H ₅ ), a naphthyl group (-C ₁₀ H ₇ ), a methoxyphenyl group (-C ₆ H ₄ OCH ₃ ), a pyridyl group (-C ₅ H ₄ N), a methoxy group (-OCH ₃ ) , Ethoxy group (-OC ₂ H ₅ ), phenoxy group (-OC ₆ H ₅ ), methoxyphenoxy group (-OC ₆ H ₄ OCH ₃ ), and the like. In addition, the following formula is a methoxyphenyl group, a pyridyl group, or a methoxyphenoxy group.

[Chemical Formula 9]

When R ² is a hydrocarbon group, the hydrocarbon group of R ^{2 may be connected to} the hydrocarbon group of R ¹ and / or other hydrocarbon groups of R ² to form a cyclic structure. In the state where a cyclic structure is formed, An example is what appears.

[Chemical formula 10]

When the hydrocarbon group of R ² is connected to the hydrocarbon group of R ¹ and / or the other hydrocarbon group of R ² to form a cyclic structure, it is considered that the total number of carbon atoms of the hydrocarbon group is 20 or less.

R ³ represents a "single bond" or a "bivalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom" Bivalent hydrocarbon group "means a hydrocarbon group having two bonding sites and is not limited to a straight chain saturated hydrocarbon group but means that it can have each of a carbon-carbon unsaturated bond, a branched structure and a cyclic structure. Quot; may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom &quot; has the same meaning as described above. In addition, in the case where R ³ is a single bond, those represented by the following formulas can be mentioned.

(11)

When R ³ is a hydrocarbon group, the number of carbon atoms of the hydrocarbon group of R ³ is preferably 18 or less, more preferably 16 or less, still more preferably 14 or less, particularly preferably 8 or less.

When R ³ is a hydrocarbon group, examples of the functional group and the linking group contained in R ³ include an amide group (-NH-), an amide group (-NHCO-), an ether group (-O-), a carbonyl group (-CO-) combining (-COOC _n H _2n -), thioether group (-S-), fluorine group (-F), chloro group (-Cl), bromo (-Br), iodine group (-I), dimethylamino group ( -N can be cited (CH _{3) 2)} or the like. In view of the chemical stability of the polymer compound, it is preferable that R ³ does not contain a hetero atom as a main chain, and more specifically, an amide group (-NHCO-), an ether group (-O-), a thioether group (-S-). Details of the &quot; main chain &quot; will be described later.

As R ^3, a single bond, a methylene group (-CH ₂ -), ethylene group _{(-C 2 H 4 -),} n- propylene group _{(-C 3 H 6 -),} i- propylene group (-CH (CH ₃ ) CH ₂ -), and a phenylene group (-C ₆ H ₄ -).

R ⁴ represents a "trivalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one kind of atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom", but "a trivalent hydrocarbon group" Means a hydrocarbon group having three bonding sites and is not limited to a straight chain saturated hydrocarbon group but means that it can have each of a carbon-carbon unsaturated bond, a branched structure and a cyclic structure. Quot; may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom &quot; has the same meaning as described above.

The carbon number of the hydrocarbon group of R ⁴ is preferably 18 or less, more preferably 16 or less, still more preferably 14 or less, particularly preferably 8 or less.

Examples of R ⁴ include a methine group (> CH-), a methylmethine group (> C (CH ₃ ) -), and those represented by the following formulas.

[Chemical Formula 12]

R ^a each independently represents a "single bond" or a "bivalent hydrocarbon group of 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom" However, the "bivalent hydrocarbon group" and the "may contain at least one kind of atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom" have the same meanings as described above. In addition, examples of the state where R ^a is a single bond include those represented by the following formulas.

[Chemical Formula 13]

When R ^a is ^a hydrocarbon group, the number of carbon atoms of the hydrocarbon group of R ^a is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, preferably 18 or less, more preferably 16 or less, More preferably 14 or less.

When R ^a is a hydrocarbon group, examples of the functional group and the linking group contained in R ^a include an amide group (-NHCO-), an ether group (-O-), a thioether group (-S-), a fluoro group (-F) (-Cl), a bromo group (-Br), an iodo group (-I), and a dimethylamino group (-N (CH ₃ ) ₂ ). In view of the chemical stability of the polymer compound, it is preferable that R ^a does not contain a hetero atom as ^a main chain, and more specifically, an amide group (-NHCO-), an ether group (-O-), a thioether group (-S-). Details of the &quot; main chain &quot; will be described later.

Examples of R ^a, single bond, a methylene group (-CH ₂ -), ethylene group _{(-C 2 H 4 -),} n- propylene group _{(-C 3 H 6 -),} i- propylene group (-CH (CH ₃ -CH ₂ -), a phenylene group (-C ₆ H ₄ -), a naphthylene group (-C ₁₀ H ₆ -) and a diphenylene group (-C ₆ H ₄ C ₆ H ₄ -).

R ^b each independently represents a "hydrogen atom" or a "hydrocarbon group of 1 to 6 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom". However, Quot; may include at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom &quot; is the same as that described above.

When R ^b is a hydrocarbon group, examples of the functional group and the linking group contained in R ^b include an amide group (-NHCO-), an ether group (-O-), a thioether group (-S-), a fluorine group (-F) (-Cl), a bromo group (-Br), an iodo group (-I), and a dimethylamino group (-N (CH ₃ ) ₂ ).

Examples of R ^b, hydrogen atom, a methyl group (-CH _3), ethyl group (-C ₂ H _5), n- propyl group (- C ₃ H ₇ ^n), i- propyl _{^{(- i C 3 H 7)}} , n -Butyl group ( ^-n C ₄ H ₉ ), t-butyl group ( ^-t C ₄ H ₉ ), and the like.

R ^b is, if a hydrocarbon group, R ^b of the hydrocarbon group R ^a hydrocarbon group and / or R ^b of the other is a hydrocarbon connecting group and may form a cyclic structure. However, the hydrocarbons of the R ^b groups R ^a hydrocarbon group and / or Examples of the state of connecting with other hydrocarbon groups of R ^b to form a cyclic structure include those represented by the following formulas.

[Chemical Formula 14]

Further, the hydrocarbon group of R ^b groups connectors and other hydrocarbon R ^a hydrocarbon group and / or R ^b carbon atoms of the hydrocarbon group if it can form a cyclic structure, R ^a and the carbon number of the hydrocarbon group of R ^b I think that the sum is less than 20.

m each independently represent an integer of 0 to 3, but is preferably 2 or less, more preferably 1 or less.

Examples of the repeating structure represented by the formula (A-1) include those represented by any one of the following formulas (A-1-1) to (A-1-6).

[Chemical Formula 15]

(In the formulas (A-1-1) to (A-1-6), R ¹ independently represents a hydrocarbon group of 1 to 6 carbon atoms.)

Examples of the repeating structure represented by the formula (A-2) include those represented by any one of the following formulas (A-2-1) to (A-2-9).

[Chemical Formula 16]

(In the formulas (A-2-1) to (A-2-9), R ¹ independently represents a hydrocarbon group of 1 to 6 carbon atoms.)

Examples of the repeating structure represented by the formula (A-3) include those represented by any one of the following formulas (A-3-1) to (A-3-3).

[Chemical Formula 17]

(In the formulas (A-3-1) to (A-3-3), R ¹ independently represents a hydrocarbon group of 1 to 6 carbon atoms.)

Examples of the repeating structure represented by the formula (A-4) include those represented by the following formulas (A-4-1) to (A-4-2).

[Chemical Formula 18]

(In the formulas (A-4-1) to (A-4-2), each R ¹ independently represents a hydrocarbon group of 1 to 6 carbon atoms.)

Examples of the repeating structure represented by the formula (B-1) include those represented by any one of the following formulas (B-1-1) to (B-1-27).

[Chemical Formula 19]

(In the formulas (B-1-1) to (B-1-9), X represents a halogen atom.)

Examples of the repeating structure represented by the formula (B-2) include those represented by any one of the following formulas (B-2-1) to (B-2-9).

[Chemical Formula 20]

(In the formulas (B-2-1) to (B-2-9), X represents a halogen atom.)

Examples of the repeating structure represented by the formula (B-3) include those represented by any one of the following formulas (B-3-1) to (B-3-3).

[Chemical Formula 21]

&Lt; Polymer compound 2 &gt;

The polymer compound (hereinafter abbreviated as &quot; polymer compound 2 of the present invention &quot; in some cases) which is another type of the present invention is a polymer compound having at least one kind selected from repeating structures represented by the following formulas (E) .

[Chemical Formula 22]

(In the formulas (E) and (F), R ¹ independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ² independently represents a halogen atom or a group selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom group having 1 to 20 hydrocarbon group, which can contain atoms of at least one, R ^a includes at least one kind of atoms, each independently represent a single bond, or a nitrogen atom, an oxygen atom, selected from sulfur atom, and a halogen atom And R ^b each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, a hydrocarbon group of ~ 6, m are each independently an integer of 0 to 3. However, R ² is, if a hydrocarbon group, the R ² hydrocarbon groups connectors and a hydrocarbon group and / or other hydrocarbon R ² of R ¹ The annular structure It can be formed. In addition, R ^b is a hydrocarbon group when, in R ^b hydrocarbon group connectors and other hydrocarbons of the hydrocarbon group R ^a and / or R ^b can form a cyclic structure.)

The inventors of the present invention have also found that by using a compound having both an alkoxyalene structure and / or a pyridine structure and an aliphatic carbon-carbon double bond, the polymerization reaction can be carried out singly to thereby efficiently produce a polymer compound will be. The following formula shows the reaction mechanism in the case of using &quot; 4-allyl anisole &quot; as the &quot; compound having both an alkoxy arylene structure and / or a pyridine structure and an aliphatic carbon-carbon double bond &quot;.

(23)

R ¹ , R ² , R ^a , R ^b and m in the repeating structure represented by the formulas (E) and (F) have the same meanings as described above.

The repeating structure represented by the formula (E) includes those represented by any one of the following formulas (E-1) to (E-4).

&Lt; EMI ID =

(In the formulas (E-1) to (E-4), R ¹ independently represents a hydrocarbon group of 1 to 6 carbon atoms.)

The repeating structure represented by the formula (F) includes those represented by any one of the following formulas (F-1) to (F-4).

(25)

It is preferable that the polymer compound 1 of the present invention and the polymer compound 2 of the present invention do not contain a hetero atom other than the oxygen atom of the alkoxy group of the alkoxyarylene structure and the nitrogen atom of the pyridine structure in the main chain. The "main chain" means a stem (skeleton) of a polymer compound having a maximum carbon number, and more specifically, a stem (skeleton) in which the molecular weight of the polymer compound is reduced by half when the bond is cleaved . For example, in the case of the repeating structure represented by the following formula, the stem (skeleton) represented by the bold line is referred to as &quot; main chain &quot;, and such a polymer compound does not contain a hetero atom other than the nitrogen atom of the pyridine structure in the main chain . Since the main chain does not contain a hetero atom, it is possible to eliminate the difficulty arising from the structure.

(26)

The polymeric compound 1 of the present invention and the polymeric compound 2 of the present invention may have a structure other than the repeating structure represented by the formulas (A-1) to (A-3) and (B-1) , Presence or absence of a crosslinked structure, and the like are not particularly limited.

Hereinafter, the molecular weight and the like of the polymer compound 1 of the present invention and the polymer compound 2 of the present invention will be described in detail.

(A-1) to (A-3) and (B-1) to (B-3) in the polymer compound 1 of the present invention and the polymer compound 2 of the present invention, Is preferably 20% or more, more preferably 40% or more, more preferably 60% or more, in terms of the amount of the material, and the content ratio of the repeating structure represented by the formula (F) , Preferably 80% or more, and particularly preferably 100%.

Polymer compound 1, and an average molecular weight (M _n) number of the polymer 2 of the present invention of the present invention is usually not less than 500, preferably not less than 600, more preferably 700 or more and usually 200,000 or less, preferably 150,000 or less , And more preferably not more than 100,000.

Polymer Compound 1, and the weight average molecular weight (M _w) of the polymer 2 of the present invention of the present invention is usually not less than 600, preferably 700, more preferably at least 800, usually 200,000 or less, preferably 170,000 or less , More preferably not more than 150,000.

The molecular weight distribution (M _w / M _n ) of the polymer compound 1 of the present invention and the polymer compound 2 of the present invention is usually 1.1 or more, preferably 1.3 or more, more preferably 1.5 or more, and usually 5 or less, 4.5 or less, more preferably 4 or less.

Within this range, the polymer compound can be easily used for various purposes.

The average molecular weight of the polymer compound 1 and the polymer compound 2 of the present invention can be measured by a known method using gel permeation chromatography (GPC).

The polymer compound 1 of the present invention and the polymer compound 2 of the present invention may be either crystalline or amorphous, but are preferably crystalline polymer compounds. If it is a crystalline polymer compound, it can be easily used for various purposes.

The melting point ( _Tm ) of the polymer compound 1 of the present invention and the polymer compound 2 of the present invention is generally 10 ° C or higher, preferably 20 ° C or higher, more preferably 30 ° C or higher, usually 350 ° C or lower, 330 ° C or less, and more preferably 300 ° C or less.

A glass transition point (T _g) of the polymer compound of the present invention, is usually more than 30 ℃, preferably at least 40 ℃, more preferably not less than 50 ℃, usually more preferably 350 ℃, preferably up to 330 ℃, Or less.

Within this range, the polymer compound can be easily used for various purposes. The melting point or glass transition point of the polymer compound can be measured by a known method using a differential scanning calorimeter (DSC).

The use of the polymeric compound 1 of the present invention and the polymeric compound 2 of the present invention is not particularly limited and can be appropriately selected according to the characteristics of the polymer compound. Examples thereof include insulating materials, functional films for optical, magnetic tapes, Film, container, automobile parts, and the like.

The method for producing the polymeric compound 1 of the present invention and the polymeric compound 2 of the present invention are not particularly limited and those produced by a known polymerization method such as cross-linking polymerization may be mentioned. However, the specific metallocene complex and the ionic compound A method of reacting alkoxyallenes and / or pyridines with a diene, or a method of polymerizing a compound having both an alkoxy alene structure and / or a pyridine structure and an aliphatic carbon-carbon double bond . These methods are described in detail in &quot; Polymer Compound Production Method 1 &quot; and &quot; Polymer Compound Production Method 2 &quot;.

&Lt; Process 1 for producing polymer &

The polymer compound 1 of the present invention can be produced by, for example, reacting alkoxyallenes and / or pyridines with a diene in the presence of a metallocene complex represented by the formula (D) and an ionic compound comprising a non-coordinating anion and a cation . Is changed to a cationic complex in which the "metallocene complex represented by the formula (D)" is active by the "ionic compound composed of nonpolar anions and cations", and the "alkoxyallenes" and "pyridines" Hydrogen bond of the diene and activates the carbon-hydrogen bond of the diene. Such a reaction is a very useful reaction that can form a carbon-carbon bond (C-C bond) which is a main chain without using a hetero atom.

In addition, a polymerization process for producing a polymer compound by reacting alkoxyallenes and / or pyridines with a diene in the presence of a metallocene complex represented by the following formula (D) and an ionic compound comprising a non-coordinating anion and a cation (Hereinafter may be abbreviated as &quot; polymerization process 1 &quot; in some cases) is a kind of the present invention.

(27)

(Wherein M represents a scandium atom, a yttrium atom, a samarium atom, a gadolinium atom, or a lutetium atom, and R represents an atom selected from a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, Q ¹ and Q ² each independently represent an anionic coordination site in a monoanionic ligand or a multidentate ligand; L is independently an anionic coordination site in a neutral Lewis base, Or n is an integer of 0 to 5 and w is an integer of 0 to 3. When n is an integer of 2 or more, the hydrocarbon group of R may be replaced with another hydrocarbon group of R Can be connected to form a cyclic structure.)

Hereinafter, the metallocene complex represented by the formula (D), the ionic compound comprising the nonpolar anion and the cation, the alkoxyallenes, the pyridines and the dienes will be described in detail.

(Metallocene complex represented by the formula (D)).

(28)

The carbon number of the hydrocarbon group of R is preferably 18 or less, more preferably 16 or less, further preferably 14 or less.

As the functional group or linking group contained in R, fluorine groups (-F), chloro group (-Cl), bromo (-Br), iodine group (-I), phosphino group (-PR _'2), an alkoxy group ( -OR '), an aryloxy group (-OAr), a trialkylsilyl group (-SiR' ₃ ), and a phosphine oxide group (-P (= O) R ' ₂ ).

As R, a methyl group (-CH _3), ethyl group (-C ₂ H _5), n- propyl group (- C ₃ H ₇ ^n), i- propyl ^{_{(- i C 3 H 7)}} , n- butyl ( - ⁿ C ₄ H ₉ ), a t-butyl group ( ^-t C ₄ H ₉ ), a phenyl group (-C ₆ H ₅ ), and a naphthyl group (-C ₁₀ H ₇ ).

When n is an integer of 2 or more, the hydrocarbon group of R may be connected to other hydrocarbon groups of R to form a cyclic structure. In the state of forming a cyclic structure, an indane ring, an octahydrofluorenyl ring , And a fluorenyl ring.

[Chemical Formula 29]

Examples of the metallocene ligand include those represented by the following formulas.

(30)

Q ¹ and Q ² each independently represent an anionic coordination site in a monoanion ligand or a multistage ligand. However, the "anionic coordination site in a multistage ligand" is a ligand coordinating to M in the multidentate ligand, Means that the ligand has, in addition to the anionic coordination site Q ¹ , another anionic coordination site Q ² or a neutral Lewis basic coordination site L.

Examples of the monoanionic ligands include 1) a hydride, 2) a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and an arsenic atom, 3) An amide group, and 4) a phosphino group.

Examples of the anionic coordination site include a methylene anion (-CH ₂ -) and a phenyl anion (-C ₆ H ₅ -).

Examples of the hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and an arsenic atom include a methyl group, an ethyl group, a propyl group, a butyl group, An alkyl group such as a methyl group, an ethyl group, an isopropyl group, an ethyl group, an isopropyl group, an isopropyl group, an isopropyl group, an isobutyl group, an isobutyl group, an isobutyl group, an isobutyl group, a heptyl group, ). &Lt; / RTI &gt;

侶³ -C ₃ R ^x ₅ (x)

(In the formula (x), R "each independently represents a hydrogen atom or an alkyl group.)

^{_{CH 2 C 6 R y1 4 ER}} y2 n -o (y)

(Wherein R ^y1 represents, independently of each other, a hydrogen or an alkyl group, E represents N, P, As, O or S, R ^y2 each independently represents an alkyl group or an aryl group, .

Examples of the amide group include a dimethyl amide group, a diethyl amide group, a methyl ethyl amide group, a dit-butyl amide group, a diisopropyl amide group, and a diphenyl amide group.

The phosphino group includes a diphenylphosphino group, a dicyclohexylphosphino group, a diethylphosphino group, and a dimethylphosphino group.

L each independently represent a neutral Lewis base or a neutral Lewis basic site in a multistage ligand. However, the &quot; neutral Lewis basic site in a multistage ligand &quot; is a multistage ligand coordinated to M, Means that the ligand has a neutral Lewis basic coordination site L or anionic coordination site Q ¹ , Q ² other than the neutral Lewis basic coordination site L.

Examples of the neutral Lewis base include diethyl ether, tetrahydrofuran, dimethylaniline, trimethylphosphine, lithium chloride and the like.

The coordination site of the neutral Lewis basic group includes an amino group.

Examples of the metallocene complex represented by the formula (D) include (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ , (C ₅ Me ₅ ) Y (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ can be given to the.

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Examples of the metallocene complex represented by the formula (D) include (1) Li, X .; Nishiura, M .; Mori, K .; Mashiko, T., Hou, Z. Chem. Commun. 4313, (2007). Or (2) Shima, T .; Nishiura, M., Hou, Z. Organometallics 30, 2513, (2011). Can be synthesized according to the method described in &quot;

The amount of the metallocene complex represented by the formula (D) in the polymerization process is not particularly limited and may be appropriately selected in accordance with the intended use. It is usually 0.0005 mol or more, preferably 1 mol or more per mol of the alkoxyallenes and / or pyridines Is not less than 0.001 mol, more preferably not less than 0.002 mol, and usually not more than 0.2 mol, preferably not more than 0.15 mol, more preferably not more than 0.1 mol. Within the above range, the polymer compound can be easily produced at an excellent yield.

(An ionic compound composed of nonpolar anions and cations)

The &quot; ionic compound comprising nonpolar anions and cations &quot; means an ionic compound formed by arbitrary nonpolar anions and cations, and specific types of nonpolar anions and cations are not particularly limited.

The non-coordinating anion is preferably a tetravalent boron anion, for example, tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (Tetrafluorophenyl) borate, tetra (trilyl) borate, tetra (xylyl) borate, (triphenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis Tetravalent boron anions such as tris (pentafluorophenyl) borate, tris (pentafluorophenyl), phenyl] borate and tridecahydride-7,8-dicarbal undecaborate. Among them, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ) is particularly preferable.

Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.

Examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation and tri-substituted phenylcarbonium cation. Examples of tri-substituted phenylcarbonium cations include tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation.

Examples of the ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation and di (n-octadecyl) methylammonium cation, N, N-dialkyl anilinium cations such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation, di ) Ammonium cation, and a dialkylammonium cation such as a dicyclohexylammonium cation.

Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation. Among them, anilinium cation and carbonium cation are preferable, and triphenylcarbonium cation ([Ph ₃ C] ⁺ ), di (n-octadecyl) methylammonium cation and N, N-dimethylanilinium cation are particularly preferable Do.

Examples of the ionic compound composed of nonpolar anions and cations include triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, and di (n-octadecyl) methylammonium tetrakis (pentafluorophenyl) borate. Among them, preferred are triphenylcarbomonium tetrakis (pentafluorophenyl) borate, di (n-octadecyl) methylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ) Borate is preferred.

The amount of the ionic compound consisting of the non-coordinating anion and the cation in the polymerization step is usually 1 equivalent to the metallocene complex.

(Alkoxyalenes)

Refers to an organic compound having a structure in which an alkoxy group is bonded to an aromatic ring, and other structures and the like are not particularly limited, but a compound represented by any one of the following formulas (a-1) to (a-4) .

(32)

(In the formulas (a-1) to (a-4), each R ¹ independently represents a hydrocarbon group having 1 to 6 carbon atoms; each R ² independently represents a halogen atom or a nitrogen atom, an oxygen atom, a sulfur atom, R ³ is a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, And R ⁴ is a trivalent hydrocarbon having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, an, m are each independently an integer of 0 to 3. However, R ² is, if a hydrocarbon group, the R ² hydrocarbon groups connectors and a hydrocarbon group and / or other hydrocarbon R ² of R ¹ to form a cyclic structure can do.)

Details of R ¹ , R ² , R ³ , R ⁴ and m are as described above.

The alkoxyalenes include those represented by the following formulas.

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(Pyridines)

The term &quot; pyridine &quot; means an organic compound having a pyridine structure, and other structures and the like are not particularly limited, but include compounds represented by any one of the following formulas (b-1) to (b-3).

(34)

(In the formulas (b-1) to (b-3), R ² is each independently a halogen atom or a group capable of containing at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom R ³ is a single bond or a divalent hydrocarbon group of 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, m are each independently an integer of 0 to 3. However, if the R ² is a hydrocarbon group, the hydrocarbon group R ² connectors and other hydrocarbon R ² may form a cyclic structure.)

Details of R ² , R ³ , and m are as described above.

Examples of the pyridines include those represented by the following formulas.

(35)

(Dienes)

The term &quot; diene &quot; means an organic compound having two carbon-carbon double bonds, and the other structures and the like are not particularly limited, but include compounds represented by the following formula (c).

(36)

(In the formula (c), R ^a independently represents a single bond or a divalent hydrocarbon having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom And R ^b each independently represents a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, provided that R ^b when the hydrocarbon group, the hydrocarbon group of R ^b is connected to the other group R ^a hydrocarbon group of the hydrocarbon group and / or R ^b can form a cyclic structure.)

The details of R ^a and R ^b are as described above.

The dienes include those represented by the following formulas.

(37)

&Lt; Polymer Compound Production Method 2 &

The polymer compound 2 of the present invention can also be produced by reacting an alkoxyalene structure and / or a pyridine structure with an aliphatic carbon-carbon (C) complex in the presence of, for example, a metallocene complex represented by the formula (D) and an ionic compound comprising a non- Linking group and a double bond.

Further, a compound having both an alkoxyalene structure and / or a pyridine structure and an aliphatic carbon-carbon double bond in the presence of a metallocene complex represented by the following formula (D) and an ionic compound comprising a non-coordinating anion and a cation (Hereinafter abbreviated as &quot; the production process 2 of the present invention &quot; hereinafter) containing a polymerization process for producing a polymer compound by polymerization (hereinafter sometimes abbreviated as "polymerization process 2" ) Is also a form of the invention.

(38)

(Wherein M represents a scandium atom, a yttrium atom, a samarium atom, a gadolinium atom, or a lutetium atom, and R represents an atom selected from a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, Q ¹ and Q ² each independently represent an anionic coordination site in a monoanionic ligand or a multidentate ligand; L is independently an anionic coordination site in a neutral Lewis base, Or n is an integer of 0 to 5 and w is an integer of 0 to 3. When n is an integer of 2 or more, the hydrocarbon group of R may be any other hydrocarbon group of R So that the annular structure can be formed.

The &quot; metallocene complex represented by the formula (D) &quot; and the &quot; ionic compound comprising a nonpolar anion and a cation &quot;

(A compound having both an alkoxyalene structure and / or a pyridine structure and an aliphatic carbon-carbon double bond)

The &quot; compound having both an alkoxyalene structure and / or a pyridine structure and an aliphatic carbon-carbon double bond &quot; means a compound having both an alkoxyarylene structure and / or a pyridine structure in which an alkoxy group is bonded to an aromatic ring, , There are no particular limitations on the other structures and the like, but include compounds represented by any one of the following formulas (e-1) to (f-1).

[Chemical Formula 39]

(In the formulas (e-1) and (f-1), R ¹ independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ² independently represents a halogen atom or a nitrogen atom, an oxygen atom, a sulfur atom, A hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of ^a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom; R ^a is independently a single bond, And R ^b each independently represents a hydrogen atom or a group selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, and R ^b is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms, a hydrocarbon group of 1 to 6 that, m each independently represents an integer of 0 to 3. However, when R ² is a hydrocarbon group, R ² of the hydrocarbon groups R ¹ or other of the hydrocarbon group and / or R ² Linked with a hydrocarbon group, It is possible to form the tank. In addition, R ^b is a hydrocarbon group when, in R ^b hydrocarbon group connectors and other hydrocarbons of the hydrocarbon group R ^a and / or R ^b can form a cyclic structure.)

Details of R ¹ , R ² , R ^a , R ^b , and m are as described above.

Examples of the compound having both an alkoxyalene structure and / or a pyridine structure and an aliphatic carbon-carbon double bond include those represented by the following formulas.

(40)

The amount of the alkoxyallenes and / or pyridines and the dienes used in the polymerization step 1 is not particularly limited and may be appropriately selected according to the purpose, but is usually 0.8 mol or more per mol of the alkoxyallenes and / or pyridines , Preferably not less than 0.9 mol, more preferably not less than 1 mol, usually not more than 2 mol, preferably not more than 1.8 mol, more preferably not more than 1.5 mol. Within the above range, the polymer compound can be easily produced at an excellent yield.

The operating procedure and the reaction conditions of the polymerization step 1 and the polymerization step 2 are not particularly limited, and known methods and conditions can be suitably employed. In a reactor packed with an inert gas such as nitrogen gas, A method in which a metallocene complex, alkoxyallenes and / or pyridines, a diene, a solvent and the like are added and heated to a predetermined reaction temperature.

Examples of the solvent include hydrocarbon solvents such as hexane, benzene and toluene; ether solvents such as diethyl ether, 1,4-dioxane and tetrahydrofuran (THF); halogen solvents such as 1,2-dichloroethane and chloroform; , Protonic polar solvents such as ethanol, ethylene glycol and glycerin, and the like.

The reaction temperature is usually 25 ° C or higher, preferably 30 ° C or higher, more preferably 35 ° C or higher, and usually 150 ° C or lower, preferably 140 ° C or lower, more preferably 130 ° C or lower.

The reaction time is usually 1 hour or more, preferably 2 hours or more, more preferably 3 hours or more, and usually 100 hours or less, preferably 90 hours or less, more preferably 80 hours or less.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not to be construed as being limited by the specific examples described below.

< ¹ H-NMR measurement>

The ¹ H-NMR measurement of the polymer compound obtained in the examples was carried out using the "ECX400P type" nuclear magnetic resonance apparatus manufactured by Nihon Denshi under the following conditions.

Cumulative count: 16

Repetition time: 3.3sec

Solvent: 1,1,2,2-tetrachloroethane-d ₂

Sample concentration: 25 g / L

Measuring temperature: 25-120 DEG C

< ¹³ C-NMR Measurement>

The ¹³ C-NMR measurement of the polymer compound obtained in the examples was also conducted under the following conditions using an &quot; ECX400P type &quot; nuclear magnetic resonance apparatus manufactured by JEOL Ltd.

Cumulative count: 200-1000 times

Pulse repetition time: 5.5 seconds

Solvent: 1,1,2,2-tetrachloroethane-d ₂

Sample concentration: 25 g / L

Measuring temperature: 25-120 DEG C

<Measurement of molecular weight>

The molecular weight of the polymer compound obtained in the examples was measured by gel permeation chromatography (GPC, Tosoh HLC-8221 GPCHT, Column GMHHR-H HT 3) under the following conditions.

Eluent: 1,2-Dichlorobenzene

Column temperature: 145 DEG C

Standard material: Standard polystyrene

&Lt; Measurement of melting point ( _Tm ) and glass transition point (Tg) &_gt;

The melting point (T _m ) and the glass transition point (T _g ) of the polymer compound obtained in the examples were measured by differential scanning calorimetry (DSC) DSC240 manufactured by Seikodensa under the following conditions.

About 5-10 mg of the sample was heated to 300 DEG C under a nitrogen atmosphere (10 mL / min), maintained at 300 DEG C for 3 minutes, and then cooled to -100 DEG C at 10 DEG C / min. Then, the temperature was maintained at -100 ° C for 3 minutes, and then the temperature was raised to 300 ° C at 10 ° C / minute. The melting point (T _m ) and the heat of fusion (? H) determined by the glass transition point (T _g ) and the peak temperature of the crystal melting peak were calculated from the chart at the second heating.

<Preparation of reagents>

2,5-Norbornadine: purchased from Kanto Kagaku Co., Ltd.

· 1,4-divinylbenzene: Prepared from terephthalaldehyde using Biithir reagent.

4,4'-Dimethoxybiphenyl: Prepared from 4,4'-biphenyldicarboxyaldehyde using a Biothy reagent.

1,4-Dimethoxybenzene: purchased from Tokyo Kasei Kogyo Co., Ltd.

4,4'-Dimethoxybiphenyl: purchased from Tokyo Kasei Kogyo Co., Ltd.

[Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]: purchased from Strem Chemical Inc.

(C ₅ Me ₅ ) Y (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ , (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ : Chem.Commun., 2007, 4137; Organometallics 30, 2513, (2011).

· 4-allyl isole: purchased from Kanto Kagaku Co., Ltd.

· 3-allyl isole: Preparations based on Org. Chem., 2004, 69, 2859.

· 4-p-nonylbutene: Am. Chem. Soc., 2013, 135, 7831.

5-p-anilylpentene: Angew.Chem., Int. Ed. Preparation based on 2015, 54, 5451.

[Example 1: Copolymerization of 1,4-dimethoxybenzene and 1,4-divinylbenzene]

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(1) A toluene solution (toluene: 1 mL) of (C ₅ Me ₅ ) Y (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (12.3 mg, 0.025 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (23.0 mg, 0.025 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 1,4-dimethoxybenzene (0.069 g, 0.5 mmol) was added.

(3) After further stirring for 5 minutes, 1,4-divinylbenzene (0.065 g, 0.5 mmol) was added.

(4) A sealed Schlick tube was taken out from the glove box, heated to 70 DEG C and stirred for 24 hours.

(5) After returning to room temperature, methanol was added to quench the polymerization reaction.

(6) The polymerization product was separated by filtration, washed with methanol, and dried under vacuum at 60 캜 to obtain a polymer compound (0.110 g, yield 82.0%).

The results of measurement of ¹ H-NMR, ¹³ C-NMR, average molecular weight, and glass transition point (T _g ) of the obtained polymer compound are shown below.

^{1 H-NMR: d = 3.00} (s, 8H), 3.83 (s, 6H), 6.73 (s, 2H), 7. 22 (s, 4H)

¹³ C-NMR: d = 32.10, 36.01, 56.56, 114.08, 128.27, 128.34, 128.37, 151.84.

M _n = 1.2 kg mol ^-1 , M _w / M _n = 1.82

T _g = 31.6 ℃

[Example 2: copolymerization of 1,4-dimethoxybenzene and 4,4'-divinylbiphenyl]

(42)

(1) A toluene solution (toluene: 1 mL) of (C ₅ Me ₅ ) Y (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (12.3 mg, 0.025 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (23.0 mg, 0.025 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 1,4-dimethoxybenzene (0.069 g, 0.5 mmol) was added.

(3) After further stirring for 5 minutes, 4,4'-divinylbiphenyl (0.103 g, 0.5 mmol) was added.

(4) A sealed Schlick tube was taken out from the glove box, heated to 70 DEG C and stirred for 24 hours.

(5) After returning to room temperature, methanol was added to effect polymerization reaction.

(6) The polymerization product was filtered off, washed with methanol, and vacuum-dried at 60 ° C to obtain a polymer compound (0.055 g, yield: 31.9%).

The results of measurement of ¹ H-NMR, ¹³ C-NMR, average molecular weight, and glass transition point (T _g ) of the obtained polymer compound are shown below.

^{1 H-NMR: d = 3.05} (s, 8H), 3.82 (s, 6H), 6.72 (s, 2H), 7.33 (d, J = 7.5Hz, 4H), 7.58 (d, J = 7.5Hz, 4H ).

¹³ C-NMR: d = 31.96, 36.13, 56.61, 114.19, 126.

77, 128.89, 128.97, 129.09, 138.79, 141.38, 151.92.

M _n = 0.79 kg mol ^-1 , M _w / M _n = 1.86

T _g = 69.0 ℃

[Example 3: copolymerization of 1,4-dimethoxybenzene and 2,5-norbornadine]

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(1) A toluene solution (toluene: 1 mL) of (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (11.2 mg, 0.025 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (23.0 mg, 0.025 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 1,4-dimethoxybenzene (0.138 g, 1.0 mmol) was added.

(3) After further stirring for 5 minutes, 2,5-norbornadiene (0.092 g, 1.0 mmol) was added.

(4) A sealed Schlick tube was taken out from the glove box, heated to 70 DEG C and stirred for 24 hours.

(5) After returning to room temperature, methanol was added to effect polymerization reaction.

(6) The polymerization product was filtered off, washed with methanol, and vacuum-dried at 60 캜 to obtain a polymer compound (0.229 g, yield 99%).

The results of measurement of ¹ H-NMR, ¹³ C-NMR, average molecular weight and melting point (T _m ) of the obtained polymer compound are shown below.

^{1 H-NMR: d = 1.5-2.0} (m, 9H), 2.16 (br s, 2H), 2.34 (br s, 2H), 2.72 (br s, 4H), 3.47 (br s, 2H), 3.61 ( br s, 2H), 3.95 (br s, 6H), 4.02 (br s, 6H), 6.90-7.14 (m, 4H).

¹³ C-NMR: d = 34.50, 35.07, 37.63, 38.17, 40.01, 40.40, 41.64, 42.44, 47.77, 56.07, 109.44, 109.84, 133.06, 133.16, 133.36, 133.46, 151.34, 151.41, 151.46.

M _n = 13.1 kgmol ^-1 , M _w / M _n = 2.46

T _m = 231.6

[Example 4: copolymerization of 4,4'-dimethoxybiphenyl and 2,5-norbornanine]

(44)

(1) A toluene solution (toluene: 1 mL) of (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (11.2 mg, 0.025 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (23.0 mg, 0.025 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 4,4'-dimethoxybiphenyl (0.214 g, 1.0 mmol) was added.

(3) After further stirring for 5 minutes, 2,5-norbornadiene (0.092 g, 1.0 mmol) was added.

(4) The sealed shrink tube was taken out from the glove box, heated to 70 DEG C and stirred for 24 hours.

(5) After returning to room temperature, methanol was added to effect polymerization reaction.

(6) The polymerization product was filtered, washed with methanol, and vacuum-dried at 60 캜 to obtain a polymer compound (0.303 g, yield 99%).

The results of measurement of ¹ H-NMR, ¹³ C-NMR, average molecular weight, and glass transition point (T _g ) of the obtained polymer compound are shown below.

^{1 H-NMR: d = 1.2-1.9} (m, 10H), 2.03 (br s, 2H), 2.15 (br s, 2H), 2.66 (br s, 3H), 3.47 (br s, 2H), 3.26 ( 2H), 3.36 (br s, 2H), 3.95 (br s, 12H), 6.97 (br s, 4H), 7.24-7.69 (m, 8H).

¹³ C-NMR d = 34.28, 34.67, 37.48, 37.92, 39.34, 40.34, 41.44, 41.50, 41.84, 55.50, 55.68, 110.52, 114.18, 124.49, 124.78, 128.40, 133.44, 135.66, 135.89, 135.96, 156.51, 156.66 , 158.41.

M _n = 0.80 kg mol ^-1 , M _w / M _n = 2.01

T _g = 157.8 ℃

[Example 5: copolymerization of 2,6-lutidine and 2,5-norbornadine]

[Chemical Formula 45]

(1) A toluene solution (toluene: 1 mL) of (C ₅ H ₅ ) Y (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (8.4 mg, 0.02 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (18.6 mg, 0.02 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 2,6-lutidine (0.054 g, 0.5 mmol) was added.

(3) After further stirring for 5 minutes, 2,5-norbornadiene (0.046 g, 0.5 mmol) was added.

(4) The sealed shrink tube was taken out from the glove box, heated to 70 DEG C, and stirred for 72 hours.

(5) After returning to room temperature, methanol was added to effect polymerization reaction.

(6) The polymerization product was filtered off, washed with methanol, and vacuum-dried at 60 ° C to obtain a polymer compound (0.066 g, yield 66.3%).

The results of measurement of ¹ H-NMR, ¹³ C-NMR, average molecular weight, and glass transition point (T _g ) of the obtained polymer compound are shown below.

^{1 H-NMR: d = 1.2-1.5} (m, 5H), 1.75-2.01 (m, 4H), 2.24 (br s, 1H), 2.38-2.71 (m, 4H), 6.89 (s, 2H), 7.43 (s, 1 H).

¹³ C-NMR: d = 31.19, 32.46, 32.62, 36.79, 36.95, 37.17, 37.41, 38.00, 39.76, 40.67, 41.38, 41.68, 42.80, 44.70, 45.00, 45.21, 120.16, 128.42, 129.24, 136.12, 160.72.

M _n = 20.3 kgmol ^-1 , M _w / M _n = 1.70

T _g = 35.3 ℃

[Example 6: Polymerization of 4-allyl anisole]

(46)

(1) A toluene solution (toluene: 1 mL) of (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (9.0 mg, 0.02 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (18.4 mg, 0.02 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 4-allyl anisole (0.148 g, 1.0 mmol) was added, and the mixture was further stirred for 5 minutes.

(3) The sealed shrink tube was taken out from the glove box, heated to 80 DEG C and stirred for 72 hours.

(4) After returning to room temperature, methanol was added to effect polymerization reaction.

(5) The polymerization product was filtered off, washed with methanol, and vacuum-dried at 60 캜 to obtain a polymer compound (0.131 g, yield: 89.0%).

The results of measurement of ¹ H-NMR, ¹³ C-NMR, average molecular weight, and glass transition point (T _g ) of the obtained polymer compound are shown below.

^{1 H-NMR: d = 1.20} (br s, 3H), 2.63 (br s, 1H), 2.90 (br s, 1H), 3.41 (br s, 1H), 3.78 (br s, 3H), 6.76 (d , ³ J = 7.8 Hz, 1 H), 6.96 (d, ³ J = 7.8 Hz, 1 H), 7.08 (br s, 1 H).

¹³ C-NMR: d = 19.65, 34.37, 43.07, 55.65, 110.35, 127.20, 127.86, 133.58, 135.05, 155.14.

M _n = 2.0 kg mol ^-1 , M _w / M _n = 1.30

T _g = 45 ° C

[Example 7: Polymerization of 3-allyl anisole]

(47)

(1) A toluene solution (toluene: 1 mL) of (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (9.0 mg, 0.02 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (18.4 mg, 0.02 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 3-allyl anisole (0.148 g, 1.0 mmol) was added, and the mixture was further stirred for 5 minutes.

(3) The sealed shrink tube was taken out from the glove box, heated to 80 DEG C and stirred for 72 hours.

(4) After returning to room temperature, methanol was added to effect polymerization reaction.

(5) The polymerization product was filtered off, washed with methanol, and vacuum-dried at 60 캜 to obtain a polymer compound (0.031 g, yield 20.0%).

The results of measurement of ¹ H-NMR, average molecular weight and glass transition point (T _g ) of the obtained polymer compound are shown below.

^{1 H-NMR: d = 1.10-1.22} (m, 3H), 2.52-2.60 (m, 1H), 2.80-2.99 (m, 1H), 3.31-3.49 (m, 1H), 3.60-3.78 (m, 3H ), 6.56 (s, 1 H), 6.66 - 6.78 (m, 1 H), 7.00 - 7.11 (m, 1 H).

M _n = 1.1 kgmol ^-1 , M _w / M _n = 1.32

[Example 8: Polymerization of 4-p-anilbutene]

(48)

(1) A toluene solution (toluene: 1 mL) of (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (9.0 mg, 0.02 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (18.4 mg, 0.02 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 4-p-anisylbutene (0.162 g, 1.0 mmol) was added and the mixture was further stirred for 5 minutes.

(3) The sealed shrink tube was taken out from the glove box, heated to 80 DEG C and stirred for 72 hours.

(4) After returning to room temperature, methanol was added to effect polymerization reaction.

(5) The polymerization product was separated, washed with methanol, and vacuum-dried at 60 캜 to obtain a polymer compound (0.151 g, yield 93.0%).

The results of measurement of ¹ H-NMR, ¹³ C-NMR, average molecular weight, and glass transition point (T _g ) of the obtained polymer compound are shown below.

^{1 H-NMR: d = 1.31} (br s, 3H), 1.89 (br s, 1H), 2.02 (br s, 1H), 2.54 (br s, 1H), 2.61 (br s, 1H), 3.28 (br (s, 1H), 3.83 (br s, 3H), 6.82 (br s, 1H), 7.01 (br s, 1H), 7.07

¹³ C-NMR: d = 18.68, 29.64, 31.11, 36.76, 53.14, 108.10, 123.76, 124.64, 132.58, 132.97, 152.74.

M _n = 2.8 kgmol ^-1 , M _w / M _n = 1.59

T _g = 31 ° C

[Example 9: Polymerization of 5-p-anilylpentene]

(49)

(1) A toluene solution (toluene: 1 mL) of (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (9.0 mg, 0.02 mmol) was added in a glove box filled with nitrogen gas A toluene solution (toluene: 2 mL) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (18.4 mg, 0.02 mmol) was added to the shrink tube while stirring.

(2) After 5 minutes, 5-p-anilylpentene (0.176 g, 1.0 mmol) was added and the mixture was further stirred for 5 minutes.

(3) The sealed shrink tube was taken out from the glove box, heated to 80 DEG C and stirred for 72 hours.

(4) After returning to room temperature, methanol was added to effect polymerization reaction.

(5) The polymerization product was filtered off, washed with methanol, and dried under vacuum at 60 캜 to obtain a polymer compound (0.165 g, yield 94.0%).

The results of ¹ H-NMR, ¹³ C-NMR and measurement of the average molecular weight of the obtained polymer compound are shown below.

^{1 H-NMR: d = 1.19} (br s, 3H), 1.40-1.70 (m, 4H), 2.45-2.60 (m, 2H), 3.15-3.25 (m, 1H), 3.78 (br s, 3H), 6.74 (d, ³ J = 8.2 Hz, 1H), 6.88-7.00 (m, 2H).

¹³ C-NMR: d = 18.65, 27.48, 29.27, 32.99, 34.54, 53.18, 108.03, 123.61, 124.58, 132.49, 133.28, 152.66.

M _n = 2.0 kg mol ^-1 , M _w / M _n = 1.78

The polymer compound 1 of the present invention and the polymer compound 2 of the present invention can be used as an insulating material, a functional film for optical, a magnetic tape, a photographic film, a packaging film, a container, an automobile part and the like.

Claims (7)

A polymer compound comprising at least one repeating structure represented by the following formulas (A-1) to (A-4) and (B-1) to (B-3)
[Chemical Formula 1]

(In the formulas (A-1) to (A-4) and (B-1) to (B-3), R ¹ independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ² independently represents a halogen atom , Or a hydrocarbon group of 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, R ³ represents a single bond or a nitrogen atom, an oxygen atom, a sulfur atom , And a halogen atom, and R ⁴ represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one kind of atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom , R ^a is independently a single bond or a group capable of containing at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, A bivalent hydrocarbon group having 1 to 20 carbon atoms, R ^b is independently a number A hydrocarbon group having 1 to 6 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, and m independently represents an integer of 0 to 3. However, the R ² is, if a hydrocarbon group, the R ² hydrocarbon groups connectors and a hydrocarbon group and / or other hydrocarbon R ² of R ¹ may form a cyclic structure. when addition, R ^b is a hydrocarbon group, R ^b May be bonded to the hydrocarbon group of R &lt; ^a & gt ^; and / or other hydrocarbon groups of R &lt; ^b &gt; to form a cyclic structure. And at least one repeating structure represented by the following formulas (E) and (F).
(2)

(In the formulas (E) and (F), R ¹ independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ² independently represents a halogen atom or a group selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom group having 1 to 20 hydrocarbon group, which can contain atoms of at least one, R ^a includes at least one kind of atoms, each independently represent a single bond, or a nitrogen atom, an oxygen atom, selected from sulfur atom, and a halogen atom And R ^b each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, a hydrocarbon group of ~ 6, m are each independently an integer of 0 to 3. However, R ² is, if a hydrocarbon group, the R ² hydrocarbon groups connectors and a hydrocarbon group and / or other hydrocarbon R ² of R ¹ The annular structure It can be formed. In addition, R ^b is a hydrocarbon group when, in R ^b hydrocarbon group connectors and other hydrocarbons of the hydrocarbon group R ^a and / or R ^b can form a cyclic structure.) 3. The method according to claim 1 or 2,
And does not contain a hetero atom other than the oxygen atom of the alkoxy group of the alkoxyarylene structure and the nitrogen atom of the pyridine structure in the main chain. 4. The method according to any one of claims 1 to 3,
The number average molecular weight (M _n) of 700 ~ 100,000 high molecular weight compound. 5. The method according to any one of claims 1 to 4,
And a molecular weight distribution (M _w / M _n ) of 1.5 to 4.0. A polymerization process in which a macromolecule compound is produced by reacting alkoxyallenes and / or pyridines with a diene in the presence of a metallocene complex represented by the following formula (D) and an ionic compound comprising a non-coordinating anion and a cation Wherein the polymer is a polymer.
(3)

(Wherein M represents a scandium atom, a yttrium atom, a samarium atom, a gadolinium atom, or a lutetium atom, and R represents an atom selected from a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, Q ¹ and Q ² each independently represent an anionic coordination site in a monoanionic ligand or a multidentate ligand; L is independently an anionic coordination site in a neutral Lewis base, Or n is an integer of 0 to 5 and w is an integer of 0 to 3. When n is an integer of 2 or more, the hydrocarbon group of R may be any other hydrocarbon group of R So that the annular structure can be formed. A compound having both an alkoxy alene structure and / or a pyridine structure and an aliphatic carbon-carbon double bond in the presence of a metallocene complex represented by the following formula (D) and an ionic compound comprising a non-coordinating anion and a cation To produce a polymer compound.
[Chemical Formula 4]

(Wherein M represents a scandium atom, a yttrium atom, a samarium atom, a gadolinium atom, or a lutetium atom, and R represents an atom selected from a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, Q1 and Q2 each independently represent an anionic coordination site in a monoanionic ligand or a multidentate ligand; L represents an anionic coordination site independently of a neutral Lewis base or a multidentate ligand; Where n is an integer of 0 to 5 and w is an integer of 0 to 3. When n is an integer of 2 or more, the hydrocarbon group of R is linked to other hydrocarbon groups of R So that a cyclic structure can be formed.)