JP2015086267A - Indene-based copolymer, hydrogenated indene-based copolymer, thermoplastic resin composition and manufacturing method of indene-based copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel indene-based copolymer excellent in heat resistance, a hydrogenated indene-based copolymer, a thermoplastic resin composition and a manufacturing method of the indene-based copolymer.SOLUTION: There is provided an indene-based copolymer having a first structural unit represented by the following formula (1-1) and a second structural unit derived from a conjugated diene monomer, or a hydrogenated indene copolymer by hydrogenating at least a part of an olefin bond of the copolymer. In the formula (1-1), Rto Rare each independently H, an alkyl group or an aryl group, Rand R, Rand R, Rand R, Rand R, and Rand Rmay each bind together to form a ring.

Description

  The present invention relates to an indene copolymer, a hydrogenated indene copolymer, a thermoplastic resin composition, and a method for producing an indene copolymer.

  Conventionally, thermoplastic elastomers are used in various applications such as adhesives and resin modification. As a thermoplastic elastomer, for example, Patent Document 1 describes a cyclic diene thermoplastic elastomer having a specific structure.

JP-A-10-259221

  An object of the present invention is to provide a novel indene copolymer, a hydrogenated indene copolymer, a thermoplastic resin composition, and a method for producing an indene copolymer that are excellent in heat resistance.

［式（１−１）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、アルキル基又はアリール基を示す。Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６、Ｒ^６とＲ^７、及び、Ｒ^７とＲ^８は、それぞれ互いに結合して環を形成していてもよい。］

［式（２−１）中、Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ独立に、水素原子又はアルキル基を示す。Ｒ^１１とＲ^１３は、互いに結合して環を形成していてもよい。］ The present invention provides an indene copolymer having a first structural unit represented by the following formula (1-1) and a second structural unit represented by the following formula (2-1). .

[In Formula (1-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. ]

[In Formula (2-1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group. R ¹¹ and R ¹³ may be bonded to each other to form a ring. ]

  The indene-based copolymer of the present invention has a specific structure in which an indene skeleton and a conjugated diene skeleton are incorporated in the main chain, and thus has a high glass transition temperature. Therefore, the indene-based copolymer of the present invention can be suitably used in the fields of automobile parts, electric / electronic parts, industrial parts and the like that require heat resistance.

［式（１−２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、アルキル基又はアリール基を示す。Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６、Ｒ^６とＲ^７、及び、Ｒ^７とＲ^８は、それぞれ互いに結合して環を形成していてもよい。］

［式（２−２）中、Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ独立に、水素原子又はアルキル基を示す。Ｒ^１１とＲ^１３は、互いに結合して環を形成していてもよい。］ The indene copolymer of the present invention further has a third structural unit represented by the following formula (1-2) and a fourth structural unit represented by the following formula (2-2). May be.

[In formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. ]

[In Formula (2-2), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group. R ¹¹ and R ¹³ may be bonded to each other to form a ring. ]

  The indene-based copolymer of the present invention may be a block copolymer having the segment A containing the first structural unit and the segment B containing the second structural unit.

［式（１−２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、アルキル基又はアリール基を示す。Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６、Ｒ^６とＲ^７、及び、Ｒ^７とＲ^８は、それぞれ互いに結合して環を形成していてもよい。］

［式（２−２）中、Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ独立に、水素原子又はアルキル基を示す。Ｒ^１１とＲ^１３は、互いに結合して環を形成していてもよい。］ The segment A may further include a structural unit represented by the following formula (1-2), and the segment B may further include a structural unit represented by the following formula (2-2).

[In formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. ]

[In Formula (2-2), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group. R ¹¹ and R ¹³ may be bonded to each other to form a ring. ]

  The present invention also provides a hydrogenated indene copolymer obtained by hydrogenating at least a part of the olefinic bonds of the indene copolymer.

  The present invention also provides a thermoplastic resin composition containing the indene-based copolymer or the hydrogenated indene-based copolymer.

［式（３）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、アルキル基又はアリール基を示す。Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６、Ｒ^６とＲ^７、及び、Ｒ^７とＲ^８は、それぞれ互いに結合して環を形成していてもよい。］

［式（４）中、Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ独立に、水素原子又はアルキル基を示す。Ｒ^１１とＲ^１３は、互いに結合して環を形成していてもよい。］ The present invention also provides a process for obtaining the indene-based copolymer of the present invention by living polymerization of the first monomer represented by the following formula (3) and the second monomer represented by the following formula (4). A method for producing an indene copolymer is provided.

[In Formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. ]

[In Formula (4), R < ¹¹ >, R < ¹² > and R < ¹³ > show a hydrogen atom or an alkyl group each independently. R ¹¹ and R ¹³ may be bonded to each other to form a ring. ]

  According to the method for producing an indene copolymer of the present invention, a novel indene copolymer having a specific structure in which an indene skeleton and a conjugated diene skeleton are incorporated in the main chain can be easily obtained.

  The living polymerization may be living anionic polymerization.

  ADVANTAGE OF THE INVENTION According to this invention, the novel indene-type copolymer excellent in heat resistance, a hydrogenated indene-type copolymer, a thermoplastic resin composition, and the manufacturing method of an indene-type copolymer are provided.

1 is a diagram showing a GPC chart of an indene copolymer obtained in Example 1. FIG. 1 is a diagram showing a DSC spectrum of an indene copolymer obtained in Example 1. FIG. 2 is a diagram showing a TGA curve of the indene copolymer obtained in Example 1. FIG. 1 is a diagram showing a ¹ H-NMR spectrum of an indene copolymer obtained in Example 1. FIG.

  A preferred embodiment of the indene copolymer of the present invention will be described below.

(Indene copolymer)
The indene copolymer according to the present embodiment has a first structural unit represented by the following formula (1-1) (hereinafter referred to as “structural unit 1-1” in some cases).

In formula (1-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring.

  The alkyl group may be linear, branched or cyclic. As an alkyl group, a C1-C10 alkyl group is preferable. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. , Neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.

  The aryl group is a group formed by removing one hydrogen atom bonded to the carbon atom constituting the aromatic ring of the arene. The arene is a hydrocarbon compound having an aromatic ring, and examples thereof include benzene, toluene, xylene, mesitylene, cumene, naphthalene, anthracene, and phenanthrene.

  The aryl group preferably has 6 to 15 carbon atoms. Examples of the aryl group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,6-xylyl group, mesityl group, 1 -A naphthyl group, 2-naphthyl group, anthracenyl group is mentioned.

R ¹ and R ² are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Further, the structural unit 1-1, it is preferable that at least one of R ¹ and R ² are hydrogen atoms, and more preferably R ¹ and R ² are both hydrogen atoms.

R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Further, the structural unit 1-1, it is preferable that at least one of R ³ and R ⁴ are hydrogen atoms, more preferably R ³ and R ⁴ are both hydrogen atoms.

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. It is more preferable that

The indene-based copolymer may further have a third structural unit represented by the following formula (1-2) (hereinafter sometimes referred to as “structural unit 1-2”). In addition, R < ¹ >, R < ² >, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, R < ⁷ > and R < ⁸ > in the formula (1-2) are respectively R < ¹ >, R < ² >, R < ³ > in the formula (1-1). , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ .

  The structural unit 1-1 and the structural unit 1-2 are both structural units that can be formed from the first monomer represented by the formula (3) to be described later. The unit 1-2 is collectively referred to as “structural unit 1-A”.

In the indene-based copolymer having the structural unit 1-1 and the structural unit 1-2, the total molar amount C _1-1 of the structural unit 1-1 in the indene-based copolymer, the C _1-1, and the structural unit 1 The ratio C _1-1 / (C _1-1 + C _1-2 ) with the sum of the total molar amounts C _1-2 of -2 (that is, the total molar amount of the structural unit 1-A) is 0.1 or more. Preferably, it is 0.2 or more, and more preferably 0.3 or more. According to such an indene copolymer, an indene copolymer having a higher glass transition temperature can be obtained.

Moreover, ratio _C1-1 / ( _C1-1 + _C1-2 ) may be 1.0 or less, may be 0.7 or less, and may be 0.5 or less.

The above-mentioned suitable ratio _C1-1 / ( _C1-1 + _C1-2 ) can be realized, for example, by living anionic polymerization of the first monomer represented by the formula (3) described later.

  The indene copolymer further has a second structural unit represented by the following formula (2-1) (hereinafter sometimes referred to as “structural unit 2-1”).

In formula (2-1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group. R ¹¹ and R ¹³ may be bonded to each other to form a ring.

  In addition, in this specification, the wavy line in a formula shows that the stereoconfiguration of the substituent in the double bond which a wavy line couple | bonds is not limited. That is, the second structural unit represented by the formula (2-1) is a structural unit represented by the following formula (2-1-a) and a structural unit represented by the following formula (2-1-b). Any of the geometric isomers may be used. Further, the indene copolymer may have only one of the structural unit represented by the formula (2-1-a) and the structural unit represented by the formula (2-1-b). You may have.

  Examples of the alkyl group in formula (2-1) include the same alkyl groups as described above. Moreover, as an alkyl group in Formula (2-1), a C1-C10 alkyl group is preferable and a methyl group is more preferable.

R ¹¹ and R ¹³ are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom. R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

The indene copolymer may further have a fourth structural unit represented by the following formula (2-2) (hereinafter, referred to as “structural unit 2-2” in some cases). In addition, R < ¹¹ >, R < ¹² > and R < ¹³ > in Formula (2-2) are synonymous with R < ¹¹ >, R < ¹² > and R < ¹³ > in Formula (2-1), respectively.

  As described above, the wavy line in the formula indicates that the configuration of the substituent in the double bond is not limited, and the fourth structural unit represented by the formula (2-2) is represented by the following formula (2-2-2). Any geometric isomer of the structural unit represented by a) and the structural unit represented by the following formula (2-2b) may be used.

  The structural unit 2-1 and the structural unit 2-2 are both structural units that can be formed from the second monomer represented by the formula (4) described later. The unit 2-2 is collectively referred to as “structural unit 2-A”.

In the indene-based copolymer having the structural unit 2-1 and the structural unit 2-2, the total molar amount C _2-1 of the structural unit 2-1 in the indene-based copolymer, C _2-1 and the structural unit 2 -2 to the sum of the total molar amount C _2-2 (that is, the total molar amount of the structural unit 2-A) C _2-1 / (C _2-1 + C _2-2 ) is 0.05 or more Preferably, it is 0.1 or more, more preferably 0.2 or more. According to such an indene copolymer, an indene copolymer having excellent properties such as tensile elongation, low strain, and high resilience required for a thermoplastic elastomer can be obtained.

Moreover, ratio _C2-1 / ( _C2-1 + _C2-2 ) may be 1.0 or less, 0.9 or less, and 0.8 or less.

The above-mentioned suitable ratio _C2-1 / ( _C2-1 + _C2-2 ) can be realized, for example, by living anionic polymerization of the second monomer represented by the formula (4) described later.

In the indene-based copolymer, the total molar amount of the structural unit 1-1 and the structural unit 1-2 (that is, the total molar amount of the structural unit 1-A) is C _1-A , the structural unit 2-1 and the structural unit 2 -2 (ie, the total molar amount of the structural unit 2-A) is C _2-A , the ratio C _1-A / (C _1-A + C _{2 -A} ) is the structural unit 1- From the viewpoint that the hard segment formed from A works as a crosslinking point and further heat resistance is obtained, it is preferably 0.02 or more, and more preferably 0.06 or more. Further, the ratio C _1-A / (C _1-A + C _{2 -A} ) is from the viewpoint of more effectively obtaining properties such as tensile elongation, low strain, and high resilience required for the thermoplastic elastomer. It is preferably 44 or less, and more preferably 0.35 or less.

  The indene copolymer may have a structural unit other than the above. Examples of the structural unit other than the above include structural units derived from compounds other than the compound represented by Formula (3) and the compound represented by Formula (4) among the polymerizable monomers described below.

  The indene copolymer may have a group derived from a polymerization initiator or a group derived from a polymerization terminator at both ends.

  The total amount of the structural unit 1-A and the structural unit 2-A in the indene copolymer is, for example, preferably 80% by mass or more based on the total amount of the indene copolymer, and is 90% by mass or more. It is more preferable that That is, the amount of structural units other than the structural unit 1-A and the structural unit 2-A in the indene-based copolymer is preferably 20% by mass or less, and more preferably 10% by mass or less.

  The weight average molecular weight Mw of the indene copolymer can be, for example, 2000 or more, or 2500 or more. In addition, the weight average molecular weight Mw of the indene-based copolymer may be, for example, 750000 or less and may be 300000 or less.

  The number average molecular weight Mn of the indene copolymer may be 2000 or more, and may be 2500 or more. Further, the number average molecular weight Mn of the indene copolymer may be, for example, 500,000 or less, or 200,000 or less.

  The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in the indene copolymer can be, for example, 1.5 or less. Moreover, it is good also as 1.3 or less. Here, the ratio Mw / Mn represents a molecular weight distribution, and a small ratio Mw / Mn indicates a narrow molecular weight distribution.

  In the present embodiment, the weight average molecular weight Mw and the number average molecular weight Mn indicate values measured by the RALLS-GPC method (Right Angle Laser Light Scattering GPC). In addition, even if the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution (Mw / Mn) measured by a method other than the above are out of the above numerical range, the value measured by the above method is within the above numerical range. If it is in. In addition, as RALLS-GPC method, the method as described in an Example is suitable.

  The indene copolymer may be a block copolymer having the segment A having the structural unit 1-A and the segment B having the structural unit 2-A.

  In this embodiment, the block copolymer refers to a linear copolymer in which a plurality of homopolymer chains are bonded as a block. A typical example of a block copolymer is-(AA ·· AA)-(BB ·· BB)-, in which an A block chain having a repeating unit A and a B block chain having a repeating unit B are bonded to each other at the ends. It is an AB type diblock polymer having a structure. You may use the block copolymer which 3 or more types of polymer chains couple | bonded. In the case of a triblock polymer, any of ABA type, BAB type, and ABC type may be used. A star-type block copolymer in which one or a plurality of types of block chains extend radially from the center may be used. A block copolymer such as (A-B) n type or (ABA) n type having four or more block chains may be used.

  The segment A includes at least the structural unit 1-1 and may further include the structural unit 1-2. The segment B includes the structural unit 2-1, and may further include the structural unit 2-2.

When the total mass of segment A in the indene-based copolymer is C _A and the total mass of segment B is C _B , the ratio C _A / (C _A + C _B ) indicates that segment A, which is a hard segment, has a crosslinking point. It is preferable that it is 0.03 or more from a viewpoint which works and the further heat resistance is acquired, and it is more preferable that it is 0.1 or more. Further, the ratio C _A / (C _A + C _B ) may be 0.6 or less from the viewpoint of more effectively obtaining properties such as tensile elongation, low strain, and high resilience required for the thermoplastic elastomer. Preferably, it is 0.5 or less.

  In one embodiment of the present invention, the indene copolymer may be an ABA type block copolymer in which the segment A is bonded to both ends of the segment B. Such an ABA type block copolymer is composed of potassium naphthalenide, 1,4-bis (1-phenylvinyl) benzene or 1,3-bis (1-phenylvinyl) benzene and alkyllithium. Living polymerization of the second monomer represented by the formula (4) described later using an initiator such as a prepared dianion species is performed to obtain a segment B having active species at both ends, and then both segments B It can be obtained by conducting living polymerization of the first monomer represented by the formula (3) using the terminal active species as a starting point.

  In such an ABA type block copolymer, the weight average molecular weight Mw of the segment B can be 1000-700000, for example, and 1500-300000 may be sufficient as it. Moreover, the weight average molecular weight of the segment A can be 500-2500, for example, and 1000-200000 may be sufficient.

(Indene copolymer production method)
The indene copolymer according to the present embodiment can be obtained, for example, by the production method shown below.

The indene copolymer can be produced by polymerizing a first monomer represented by the following formula (3) and a second monomer represented by the following formula (4). Incidentally, ^R 1 in the formula ^{(3), R 2, R} 3, R 4, R 5, R 6, R 7 and ^{R 8, R} 1 in each formula ^{(1-1), R 2, R} 3, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are synonymous. Also, ^{R 11, R 12} and ^{R 13} in Formula (4) has the same meaning as ^{R 11, R 12} and ^{R 13} in each formula (2-1).

  As described above, the wavy line in the formula indicates that the configuration of substituents in the double bond is not limited. That is, the second monomer represented by the formula (4) may be any geometric isomer or a mixture of geometric isomers.

  Examples of the first monomer represented by the formula (3) include benzofulvene, 1-ethylideneindene, 1-propylideneindene, 1-butylideneindene, 1-pentylideneindene, 1-hexylideneindene, 6, Examples include 6-dimethyl-1,2-benzofulvene, 6,6-diethyl-1,2-benzofulvene, 6,6-dipropyl-1,2-benzofulvene, and 1- (1-methylpropylidene) indene. It is done.

  Examples of the second monomer represented by the formula (4) include isoprene, butadiene, cyclopentadiene, cyclohexadiene, piperylene, 1,3-cyclohexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,2- Examples include dimethyl-1,3-butadiene.

  The polymerization method is not particularly limited, and examples thereof include anionic polymerization, cationic polymerization, radical polymerization, living polymerization, and living anion polymerization. Among these, living polymerization is preferable and living anion polymerization is more preferable.

  The indene copolymer can be produced, for example, by anionic polymerization of a polymerizable monomer containing a first monomer represented by the formula (3) and a second monomer represented by the formula (4).

According to the anionic polymerization, an indene copolymer having a ratio C _1-1 / (C _1-1 + C _1-2 ) within the above-described preferred range can be easily obtained.

  The anionic polymerization can be performed, for example, by reacting a polymerizable monomer dispersed or dissolved in an organic solvent with an anionic polymerization initiator.

  As the organic solvent used in the anionic polymerization, aliphatic hydrocarbons, aromatic hydrocarbons, ether solvents and the like are preferably used, and these can be used alone or in admixture of two or more.

  Examples of the aliphatic hydrocarbon include propane, butane, isobutane, pentane, neopentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene and the like.

  Examples of the ether solvent include tetrahydrofuran, diethyl ether, diisopropyl ether, diglyme and the like.

  As an anionic polymerization initiator, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, lithium naphthalenide, sodium naphthalenide, potassium naphthalenide, cesium naphthalenide, phenylmagnesium chloride (PhMgCl) ), Phenylmagnesium bromide (PhMgBr), benzylmagnesium chloride, benzylmagnesium bromide, diphenylmethyllithium, diphenylmethylsodium, diphenylmethylpotassium, diphenylmethylcesium, triphenylmethyllithium, triphenylmethylsodium, triphenylmethylpotassium, triphenyl Methyl cesium, lithium diisopropylamide, sodium methoxide, sodium ethoxide, potassium te t- butoxide, 1,4-bis (1-phenylvinyl) benzene or 1,3-bis (1-phenylvinyl) dianion species or the like which is prepared from benzene and alkyl lithium.

  Among these, living anionic polymerization initiators such as sec-butyllithium, lithium naphthalene, and potassium naphthalene are preferable. According to such a polymerization initiator, an indene copolymer can be produced by living anionic polymerization.

  The polymerizable monomer may contain a compound other than the first monomer represented by formula (3) and the second monomer represented by formula (4). When the indene copolymer is produced by anionic polymerization, the polymerizable monomer is selected from methacrylate compounds such as methyl methacrylate, ethyl methacrylate and tert-butyl methacrylate; acrylate compounds such as tert-butyl acrylate; styrene, α-methylstyrene, 2 -Vinyl compounds such as vinylpyridine and 4-vinylpyridine; N, N-dialkylacrylamide compounds such as N, N-dimethylacrylamide and N, N-diethylacrylamide; In addition, copolymerization with anionic ring-opening polymerizable monomers such as hexamethylcyclotrisiloxane (D3), lactide, and ε-caprolactone is also possible.

  In the anionic polymerization, after the first monomer represented by the formula (3) is polymerized, the second monomer represented by the formula (4) is added to the reaction solution, or the formula (4) After polymerizing the second monomer represented by formula (3), the block monomer can be produced by adding the second monomer represented by formula (3) to the reaction solution. Alternatively, the first monomer represented by the formula (3) and the second monomer represented by the formula (4) can be simultaneously supplied to the reaction solution to produce a random copolymer.

  The indene copolymer can also be produced by cationic polymerization of a polymerizable monomer containing the first monomer represented by the formula (3) and the second monomer represented by the formula (4).

  The cationic polymerization can be performed, for example, by reacting a polymerizable monomer dispersed or dissolved in an organic solvent in the presence of a Lewis acid catalyst.

  As the organic solvent used in the cationic polymerization, halogenated hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons and the like are suitably used, and these can be used alone or in admixture of two or more. Here, examples of the aliphatic hydrocarbon and the aromatic hydrocarbon include the same compounds as described above.

  Examples of halogenated hydrocarbons include chloroform, methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, 1-chloropropane, 1-chloro-2-methylpropane, and 1-chlorobutane. 1-chloro-2-methylbutane, 1-chloro-3-methylbutane, 1-chloro-2,2-dimethylbutane, 1-chloro-3,3-dimethylbutane, 1-chloro-2,3-dimethylbutane, 1-chloropentane, 1-chloro-2-methylpentane, 1-chloro-3-methylpentane, 1-chloro-4-methylpentane, 1-chlorohexane, 1-chloro-2-methylhexane, 1-chloro- 3-methylhexane, 1-chloro-4-methylhexane, 1-chloro-5-methylhexane, 1-chlorohept Down, 1-chloro octane, 2-chloropropane, 2-chlorobutane, 2-chloro-pentane, 2-chloro-hexane, 2-chloro-heptane, 2-chloro octane, chlorobenzene, and the like.

As the Lewis acid catalyst, a known Lewis acid used as a catalyst for cationic polymerization can be used. Examples of Lewis acid catalysts include boron halide compounds such as boron trichloride, boron trifluoride, diethyl ether complex of boron trifluoride, methanol complex of boron trifluoride (BF ₃ .MeOH); titanium tetrachloride, Titanium halide compounds such as titanium tetrabromide and titanium tetraiodide; Halogen compounds such as tin tetrachloride, tin tetrabromide and tin tetraiodide; Halogens such as aluminum trichloride, alkyldichloroaluminum and dialkylchloroaluminum Aluminum halide compounds; antimony halide compounds such as antimony pentachloride and antimony pentafluoride; tungsten halide compounds such as tungsten pentachloride; molybdenum halide compounds such as molybdenum pentachloride; tantalum halide compounds such as tantalum pentachloride; tetra Metal Al such as alkoxy titanium Examples include coxide.

  Of these, as the Lewis acid catalyst, diethyl ether complex of boron trifluoride, tin tetrachloride, titanium tetrachloride, antimony pentachloride, alkyldichloroaluminum, and the like are preferably used.

  The polymerizable monomer may contain a compound other than the first monomer and the second monomer. For example, when an indene copolymer is produced by cationic polymerization, the polymerizable monomer may contain an aromatic vinyl compound, an olefin having 4 to 12 carbon atoms, vinyl ether, vinyl silanes, allyl silanes, and the like. Specifically, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, Isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane , Divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, Contains ylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, etc. You may go out.

  In cationic polymerization, after the first monomer represented by the formula (3) is polymerized, the second monomer represented by the formula (4) is added to the reaction solution, or the formula (4) After polymerizing the second monomer represented by formula (3), the block monomer can also be produced by adding the first monomer represented by formula (3) to the reaction solution. Alternatively, the first monomer represented by the formula (3) and the second monomer represented by the formula (4) can be simultaneously supplied to the reaction solution to produce a random copolymer.

  The indene copolymer can also be produced by radical polymerization of a polymerizable monomer containing the first monomer represented by the formula (3) and the second monomer represented by the formula (4).

  The radical polymerization can be performed, for example, by reacting a polymerizable monomer dispersed or dissolved in an organic solvent with a radical polymerization initiator.

  Examples of the organic solvent used in radical polymerization include aromatic hydrocarbons such as toluene and xylene; alcohol solvents such as methanol, ethanol, propyl alcohol, and butyl alcohol; cyclohexane, dioxane, tetrahydrofuran, acetone methyl ethyl ketone, dimethylformamide, isopropyl acetate, Methylene chloride, 1,2-dichloroethane and the like are preferably used, and these can be used alone or in admixture of two or more.

  Examples of radical polymerization initiators include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxyacetate, and tert-butyl perbutyl pyridine. Organic peroxides such as barate and tert-butylperoxypivalate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1, And azo initiators such as 1′-azobis (cyclohexane-1-carbonitrile) and dimethyl-2,2′-azobisisobutyrate;

  The polymerizable monomer may contain a compound other than the first monomer and the second monomer. When the indene-based copolymer is produced by radical polymerization, the polymerizable monomer contains alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, and tert-butyl methacrylate; aromatic vinyl compound such as styrene and divinylbenzene; Also good.

  In radical polymerization, after the first monomer represented by the formula (3) is polymerized, the second monomer represented by the formula (4) is added to the reaction solution, or the formula (4) After polymerizing the second monomer represented by formula (3), the block monomer can also be produced by adding the first monomer represented by formula (3) to the reaction solution. Alternatively, the first monomer represented by the formula (3) and the second monomer represented by the formula (4) can be simultaneously supplied to the reaction solution to produce a random copolymer.

(Hydrogenated indene copolymer)
The hydrogenated indene-based copolymer can be obtained by hydrogenating at least a part of the olefin bonds of the indene-based copolymer.

The hydrogenated indene copolymer has, for example, a structural unit represented by the following formula (5-1) and a structural unit represented by the following formula (6-1). Incidentally, ^R 1 in the formula ^{(5-1), R 2, R} 3, R 4, R 5, R 6, R 7 and ^{R 8, R} 1 in each formula ^{(1-1), R 2, R} 3 , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ . Moreover, R < ¹¹ >, R < ¹² > and R < ¹³ > in Formula (6-1) are synonymous with R < ¹¹ >, R < ¹² > and R < ¹³ > in Formula (2-1), respectively.

Moreover, the hydrogenated indene-based copolymer may further have, for example, a structural unit represented by the following formula (5-2), and further includes a structural unit represented by the following formula (6-2). You may have. Incidentally, ^R 1 in the formula ^{(5-2), R 2, R} 3, R 4, R 5, R 6, R 7 and ^{R 8, R} 1 in each formula ^{(1-1), R 2, R} 3 , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ . Moreover, R < ¹¹ >, R < ¹² > and R < ¹³ > in Formula (6-2) are synonymous with R < ¹¹ >, R < ¹² > and R < ¹³ > in Formula (2-1), respectively.

  The hydrogenation reaction can be performed, for example, by reacting an indene copolymer dispersed or dissolved in an organic solvent in a hydrogen atmosphere in the presence of a hydrogenation catalyst.

  Examples of the organic solvent used in the hydrogenation reaction include aliphatic hydrocarbons; aromatic hydrocarbons; alcohol solvents such as methanol, ethanol and propanol; ether solvents such as tetrahydrofuran, diethyl ether, diisopropyl ether and diglyme; , Halogenated hydrocarbons such as dichloroethane, chloroform, etc. can be suitably used. Here, examples of the aliphatic hydrocarbon, aromatic hydrocarbon, ether solvent, and halogenated hydrocarbon include the same compounds as described above.

Examples of the hydrogenation catalyst include palladium supported on activated carbon, rhodium supported on activated carbon, ruthenium supported on activated carbon, palladium supported on aluminum oxide, rhodium supported on aluminum oxide, Ruthenium supported on aluminum oxide, ruthenium dichlorotris (triphenylphosphine) complex (RuCl ₂ (PPh ₃ ) ₃ ), tris (triphenylphosphine) ruthenium hydrochloride complex (RuHCl (PPh ₃ ) ₃ ), ruthenium dihydride And tetrakistriphenylphosphine complex (RuH ₂ (PPh ₃ ) ₄ ).

  The hydrogenation reaction can be carried out, for example, at a reaction temperature of 0 to 200 ° C., and preferably from 80 to 180 ° C., more preferably from 100 to 170 ° C. from the viewpoint of the conversion rate of the reaction and the polymer yield.

  The reaction time of the hydrogenation reaction can be 15 minutes to 10 hours, preferably 30 minutes to 9 hours, more preferably 2 hours to 8 hours, from the viewpoint of the conversion rate of the reaction.

  The hydrogen pressure in the hydrogenation reaction can be set to 1 to 20 MPa, and is preferably 2 to 15 MPa and more preferably 3 to 12 MPa from the viewpoint of the conversion rate of the reaction and the ease of operation.

  The amount of catalyst added in the hydrogenation reaction can be 0.0001 to 25% by mass with respect to the total amount of polymerizable monomers, and is preferably 0.001 to 20% by mass from the viewpoint of reaction rate and economy. 0.005 to 15% by mass is more preferable.

  The amount of the solvent used in the hydrogenation reaction can be 1 to 300 g with respect to 1 g of the polymerizable monomer, and is preferably 5 to 250 g from the viewpoint of the conversion rate of the reaction, the reaction rate, and the solubility of the reaction raw material. -230g is more preferable.

(Thermoplastic resin composition)
Since the indene copolymer and the hydrogenated indene copolymer have excellent heat resistance, they can be suitably used as a thermoplastic resin. That is, the thermoplastic resin composition according to the present embodiment includes the indene copolymer and / or the hydrogenated indene copolymer.

  The thermoplastic resin composition according to the present embodiment may contain an additive other than the indene copolymer and the hydrogenated indene copolymer. Examples of the additive include polyolefin polymers such as ethylene polymers and propylene polymers; poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4- Phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1, Polyphenylene polymers such as 4-phenylene ether) and poly (2-ethyl-6-propyl-1,4-phenylene ether); process oil or extender oil used for softening, increasing volume, improving processability of rubber, etc. Mineral oil rubber softeners called calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, Inorganic additives such as barium acid, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide, carbon black; reinforcing resins such as poly α-methylstyrene; flame retardants; antioxidants; heat stabilizers; A light stabilizer, an antistatic agent, a release agent, a foaming agent, a pigment, a dye, and a brightening agent.

  The thermoplastic resin composition according to this embodiment can be suitably used for applications such as automotive parts, electrical / electronic parts, and industrial parts.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.

(Example 1: Production of indene copolymer 1)
To 3.1 ml of a tetrahydrofuran (THF) solution containing potassium naphthalenide (0.153 mmol), 10.7 ml of a THF solution containing 2.0 ml of isoprene (12.8 mmol) and heptane was added while cooling to -78 ° C. The reaction was performed at −78 ° C. for 4 hours. After part of the reaction solution was divided into side tubes, 11.3 ml of a THF solution containing benzofulvene (6.18 mmol) was added to the remaining reaction solution while cooling to −78 ° C. and allowed to react for 20 minutes. When a THF solution containing benzofulvene was added to the reaction solution, the color of the solution changed to yellow instantly.

  After completion of the polymerization, 2.0 ml of methanol as a polymerization terminator was added to terminate the polymerization. When the reaction solution was poured into 200 ml of methanol, a white solid precipitated. The solid was filtered by vacuum filtration using Kiriyama funnel and Kiriyama filter paper, dissolved in 10 ml of benzene, and freeze-dried to obtain 1.56 g of a white powdery indene copolymer. The polymer yield was 98% by mass based on the charged benzofulvene.

For the indene copolymer 1 obtained in Example 1, the calculated value of the number average molecular weight Mn was calculated by the method (I) below. Further, the number average molecular weight Mn and the weight average molecular weight Mw were measured by the method (II) below, and the molecular weight distribution Mw / Mn was determined by the method (III) below. Further, the glass transition temperature T ₁ on the low temperature side and the glass transition temperature T ₂ on the high temperature side of the indene copolymer obtained in Example 1 were measured by the following method (IV). The results were as shown in Table 1. Moreover, the GPC chart of the indene copolymer obtained in Example 1 is shown in FIG. 1, and the DSC spectrum is shown in FIG.

  Moreover, about the indene-type copolymer 1 obtained in Example 1, the thermal decomposition start temperature and the 10% thermogravimetric decrease temperature were measured. The 10% thermogravimetric decrease temperature is 10% of the initial mass when the sample is heated from 30 ° C. to 600 ° C. at 20 ° C./min with a thermogravimetric measuring device (“TG / DTA6200” manufactured by Seiko Denshi). This is the temperature when the mass is reduced by mass%. The indene copolymer 1 of Example 1 had a thermal decomposition starting temperature of about 250 ° C. and a 10% thermogravimetric temperature reduction temperature of 328 ° C. The TGA curve of the indene copolymer obtained in Example 1 is shown in FIG.

Further, when the ¹ H NMR spectrum of the indene copolymer 1 obtained in Example 1 was measured using GPLU (300 MHz) manufactured by BLUKER, the structure represented by the following formula (A-1) (hereinafter, "Structure A-1"), a structure represented by the following formula (A-2) (hereinafter referred to as "structure A-2"), a structure represented by the following formula (B-1) ( Hereinafter, the structure is represented by “Structure B-1”, the structure represented by the following formula (B-2) (hereinafter, referred to as “Structure B-2”), and the following formula (B-3). Signals corresponding to the structures (hereinafter referred to as “structure B-3”) were observed. The ¹ H-NMR spectrum of the indene copolymer obtained in Example 1 is shown in FIG.

The content of the structure A-1 with respect to the total amount of the structure A-1 and the structure A-2 was calculated from the area ratio of the signals corresponding to the structures A-1 and A-2 in the ¹ H NMR spectrum, respectively, and 38% It was 62% when content of structure A-2 was computed. In addition, inclusion of structure B-1 with respect to the total amount of structure B-1, structure B-2, and structure B-3 based on the area ratio of signals corresponding to structure B-1, structure B-2, and structure B-3, respectively The amount was calculated to be 25%, the content of structure B-2 was calculated to be 53%, and the content of structure B-3 was calculated to be 22%. Further, the ratio of the total amount of the structure A-1 and the structure A-2 to the total molar amount of the structure A-1, the structure A-2, the structure B-1, the structure B-2, and the structure B-3 is 0. 42.

(I) Calculation of Calculated Value of Number Average Molecular Weight Mn Molecular Weight of Partial Structure Derived from Polymerization Initiator and Polymerization Terminator Present at Terminal of Inden Copolymer Obtained, and Amount of Use of Polymerization Initiator (mol) The molecular weight of the polymer chain calculated based on the ratio of the amount of monomer used (mol) to the amount of monomer (the amount of monomer used / the amount of polymerization initiator used) was added to obtain the calculated value of the number average molecular weight Mn.

(II) Measurement of weight average molecular weight Mw and number average molecular weight Mn The weight average molecular weight Mw and the number average molecular weight Mn of the indene-based copolymer were measured using Light Angle Laser Light Scattering GPC (RALLS-GPC). More specifically, a Viscotek Model 302 Triple Detector Array (manufactured by Asahi Techneion Co., Ltd.) having a refractometer, a scattering intensity meter, and a viscometer as a detector is used, and the flow rate is 1.0 ml / min. The measurement was performed with the temperature set at 30 ° C. The effluent solvent was THF, and the analytical column was TOSOH G5000HXL + G4000 HXL + G3000 HXL.

(III) Calculation of molecular weight distribution Mw / Mn The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained by the above (II) was used as a value indicating the molecular weight distribution.

(IV) Measurement of glass transition temperature Tg It measured using the DSC apparatus ("DSC6220" by Seiko Denshi KK). In the measurement, the sample was once heated to 150 ° C., annealed at the same temperature for 5 minutes, and then rapidly cooled to −196 ° C. Thereafter, the temperature was raised again at 20 ° C./min, and the glass transition temperature (Tg) was measured.

  The indene-based copolymer of the present invention is useful as a resin for use in automotive parts, electrical / electronic parts, industrial parts and the like that require heat resistance.

Claims (8)

An indene-based copolymer having a first structural unit represented by the following formula (1-1) and a second structural unit represented by the following formula (2-1).

[In Formula (1-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. ]

[In Formula (2-1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group. R ¹¹ and R ¹³ may be bonded to each other to form a ring. ] The indene-based copolymer according to claim 1, further comprising a third structural unit represented by the following formula (1-2) and a fourth structural unit represented by the following formula (2-2). .

[In formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. ]

[In Formula (2-2), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group. R ¹¹ and R ¹³ may be bonded to each other to form a ring. ]   The indene-based copolymer according to claim 1 or 2, which is a block copolymer having a segment A containing the first structural unit and a segment B containing the second structural unit. The segment A further includes a structural unit represented by the following formula (1-2),
The indene-based copolymer according to claim 3, wherein the segment B further contains a structural unit represented by the following formula (2-2).

[In formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. ]

[In Formula (2-2), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group. R ¹¹ and R ¹³ may be bonded to each other to form a ring. ]   A hydrogenated indene copolymer obtained by hydrogenating at least part of the olefinic bonds of the indene copolymer according to any one of claims 1 to 4.   The thermoplastic resin composition containing the indene-type copolymer as described in any one of Claims 1-4, or the hydrogenated indene-type copolymer of Claim 5. The indene-based copolymer according to any one of claims 1 to 4, by living polymerization of a first monomer represented by the following formula (3) and a second monomer represented by the following formula (4). A method for producing an indene copolymer, comprising a step of obtaining a polymer.

[In Formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. ]

[In Formula (4), R < ¹¹ >, R < ¹² > and R < ¹³ > show a hydrogen atom or an alkyl group each independently. R ¹¹ and R ¹³ may be bonded to each other to form a ring. ]   The manufacturing method of the indene-type copolymer of Claim 7 whose said living polymerization is living anion polymerization.

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