JP6709533B2 - Polymer compound, modified product thereof, production method thereof, and polymer material - Google Patents

Description

The present invention relates to a polymer compound, a modified product thereof, a method for producing the same, a compound used in the production method, and a method for producing the compound. The present invention also relates to a polymer material containing a polymer compound and/or a modified product thereof.

It is known that anionic polymerization of styrene proceeds in a living manner to give a polymer having a molecular weight as designed and a narrow molecular weight distribution (for example, Non-Patent Document 1).

Takuhei Nose, Seizo Miyata, Seiichi Nakahama, Graduate School of Polymer Science, Kodansha Scientific, June 10, 1997, P193

However, it is difficult to anionically polymerize a styrene derivative having an acyl group, and there is no known example of successful anionic polymerization of a styrene derivative having an acyl group.

On the other hand, since an acyl group can be converted into various functional groups, a polymer compound containing a structural unit derived from a styrene derivative having an acyl group is considered to be useful as a raw material for a polymer material.

The present invention has been made in view of the above circumstances, and includes a novel polymer compound containing a structural unit derived from a styrene derivative having an acyl group, a modified product of the polymer compound, and a method for producing the polymer compound. The purpose is to provide. Another object of the present invention is to provide a compound used in the method for producing the polymer compound and a method for producing the compound. Another object of the present invention is to provide a polymer material containing at least one of the polymer compound and its modified product.

One aspect of the present invention relates to a polymer compound having a structural unit represented by the following formula (1-1).

[In the formula, R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ]

In one aspect, the polymer compound may be a block copolymer having a block chain having a structural unit represented by the formula (1-1).

In one aspect, the polymer compound may have a structure represented by the following formula (1-2).

[In the formula, R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position, and n represents an integer of 2 or more. ]

In one aspect, the polymer compound may be a block copolymer having a block chain having a structure represented by the formula (1-2).

In one aspect, the polymer compound may be a homopolymer of a compound represented by the following formula (2-1).

[In the formula, R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ]

In one aspect, the polymer compound may have a ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw/Mn) of 2.0 or less.

In one aspect, the hydrocarbon group may be an alkyl group having 4 to 40 carbon atoms.

Another aspect of the present invention relates to a method for producing the polymer compound, which comprises a step of anionically polymerizing a monomer component containing a compound represented by the following formula (2-1).

[In the formula, R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ]

In one aspect, the above step may be a step of performing anionic polymerization using an anionic polymerization initiator having at least one alkali metal element selected from the group consisting of lithium, sodium, potassium and cesium.

Another aspect of the present invention relates to a compound represented by the following formula (2-1).

[In the formula, R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ]

Another aspect of the present invention relates to a method for producing the above compound, which comprises a step of reacting a compound represented by the following formula (3) with a compound represented by the following formula (4).

[In the formula, X ¹ represents a halogen group. ]

[In the formula, R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. X ² represents a halogen group or an acyloxy group. ]

Another aspect of the present invention relates to a modified product of the above-mentioned polymer compound, which is obtained by modifying the acyl group of the above-mentioned polymer compound.

Another aspect of the present invention relates to a polymer material containing the polymer compound and/or the modified product.

According to the present invention, there are provided a novel polymer compound, a modified product of the polymer compound, and a method for producing the polymer compound, which include a structural unit derived from a styrene derivative having an acyl group. Further, according to the present invention, there are provided a compound used in the method for producing the polymer compound and a method for producing the compound. Further, according to the present invention, there is provided a polymer material containing at least one of the polymer compound and a modified product thereof.

It is a figure which shows the < ¹ >H-NMR chart of the compound A used in the Example. Is. It is a figure which shows the < ¹³ >C-NMR chart of the compound A used in the Example. It is a figure which shows the < ¹ >H-NMR chart of the compound B used in the Example. It is a figure which shows the < ¹³ >C-NMR chart of the compound B used in the Example. It is a figure which shows the < ¹ >H-NMR chart of the compound C used in the Example. It is a figure which shows the < ¹³ >C-NMR chart of the compound C used in the Example. It is a figure which shows the < ¹ >H-NMR chart of the compound D used in the Example. It is a figure which shows the < ¹³ >C-NMR chart of the compound D used in the Example. 1 is a view showing a ¹ H-NMR chart of a polymer compound obtained in Example 1. FIG. 9 is a view showing a ¹ H-NMR chart of the polymer compound obtained in Example 8. FIG. FIG. 7 is a diagram showing a ¹ H-NMR chart of the polymer compound obtained in Example 15. FIG. 7 is a diagram showing a ¹ H-NMR chart of a polymer compound obtained in Example 16. FIG. 3 is a diagram showing a ¹ H-NMR chart of a polymer compound obtained in Example 17. FIG. 6 is a view showing a ¹ H-NMR chart of the homopolymer obtained in Example 17. FIG. 5 is a diagram showing GPC measurement results of a polymer compound and a homopolymer obtained in Example 17. 9 is a diagram showing a ¹ H-NMR chart of the polymer compound obtained in Example 18. FIG. FIG. 8 is a diagram showing an FT-IR chart of the polymer compound used in Example 19 and the polymer compound obtained in Example 19.

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

(Polymer compound)
The polymer compound according to this embodiment has a structural unit represented by the following formula (1-1).

In formula (1-1), R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. Here, the hydrocarbon group having no hydrogen atom at the α-position means a hydrocarbon group having no hydrogen atom on the carbon atom adjacent to the carbonyl group.

The hydrocarbon group for R ¹ may be an alkyl group, an alkenyl group, or an aromatic group. The alkyl group for R ¹ is a branched or cyclic alkyl group. The carbon number of the alkyl group may be, for example, 4 to 40, 4 to 30, or 4 to 20. The alkenyl group for R ¹ is a branched or cyclic alkenyl group. The carbon number of the alkenyl group may be, for example, 5 to 40, 5 to 30, or 5 to 20. The aromatic group of R ^{1 is} a group obtained by removing one hydrogen atom from aromatic hydrocarbon. Carbon number of the said aromatic group may be 6-40, may be 6-30, and may be 6-20, for example.

R ¹ may be, for example, an alkyl group represented by the following formula (a).

In formula (a), R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrocarbon group. R ¹⁰ , R ¹¹ and R ¹² may be the same or different.

The hydrocarbon group of R ¹⁰ , R ¹¹ and R ¹² may be, for example, a linear, branched or cyclic alkyl group or an aromatic group. The alkyl group may have, for example, 1 to 10 carbon atoms, 1 to 5 carbon atoms, or 1 to 3 carbon atoms. The carbon number of the aromatic group may be, for example, 6 to 37, 6 to 27, or 6 to 17.

The alkyl group of R ¹⁰ , R ¹¹ and R ¹² is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group. , A cyclohexyl group, etc. The aromatic group of R ¹⁰ , R ¹¹ and R ¹² may be, for example, a phenyl group.

R ¹ may be ^one in which R ¹⁰ and R ¹¹ in formula (a) are bonded to each other to form an alicyclic group, and R ¹⁰ and R ¹¹ and R ¹² are bonded to each other to form an alicyclic group. It may be a cyclic group. The alicyclic group may be a saturated alicyclic group or an unsaturated alicyclic group.

Specific examples of R ¹ include tert-butyl group, 1-adamantyl group, 3-methyladamantyl group, 3,5-dimethyladamantyl group, triethylmethyl group, tripropylmethyl group, tributylmethyl group, phenyl group, toluyl group. , Xylyl group, cumenyl group, mesityl group, naphthyl group, phenanthrenyl group, anthracenyl group, pyrenyl group, methylmethanocyclohexyl group (methylnorbornane group), methylmethanocyclohexenyl group (methylnorbornene group), methyldimethanocyclodecyl group, Examples thereof include a methyldimethanocyclodecenyl group, a methyltrimethanocyclotetradecyl group, and a methyltrimethanocyclotetradecenyl group.

From the viewpoint of improving the heat resistance of the polymer compound, R ¹ is preferably a ¹ -adamantyl group or a methyldimethanocyclodecenyl group.

From the viewpoint of facilitating the preparation of the raw material monomer for the polymer compound, R ¹ is preferably a tert-butyl group, a 1-adamantyl group, a phenyl group or a methyldimethanocyclodecenyl group, and a 1-adamantyl group. More preferably, it is a phenyl group or a methyldimethanocyclodecenyl group.

From the viewpoint of facilitating conversion of the functional group of the carbonyl group of the polymer compound, R ¹ is preferably a tert-butyl group, a 1-adamantyl group, a phenyl group or a methyldimethanocyclodecenyl group, and tert- It is more preferably a butyl group or a phenyl group.

When the polymer compound has a plurality of structural units represented by formula (1-1), a plurality of R ¹ may be the same or different.

The polymer compound may be a polymer compound having a structure in which a plurality of structural units represented by formula (1-1) are linked. That is, the polymer compound may have a structure represented by the following formula (1-2).

In formula (1-2), R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position, n represents an integer of 2 or more, and a plurality of R ¹ may be the same or different. ^{R 1} in formula (1-2) has the same meaning as ^{R 1} in formula (1-1).

N in the formula (1-2) may be, for example, 2 or more, 100 or more, and 1000 or more. Further, n in the formula (1-2) may be 1.0×10 ⁶ or less, 1.0×10 ⁵ or less, and 1.0×10 ⁴ or less.

The number average molecular weight Mn of the polymer compound may be, for example, 500 to 1.0×10 ⁷ , may be 5000 to 1.0×10 ⁶ , and may be 5.0×10 ^{4 to} 1.0×10 ^5. May be

In the polymer compound, the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn may be, for example, 2.0 or less, 1.7 or less, and 1.4 or less. Good. Here, Mw/Mn represents a molecular weight distribution, and a small Mw/Mn means a narrow molecular weight distribution. The lower limit of Mw/Mn is 1.

In the present embodiment, the number average molecular weight Mn indicates a value measured by the RALLS-GPC method (Right Angle Laser Light Scattering GPC). The measurement by the RALLS-GPC method is performed by the method described in the examples.

In the present embodiment, the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn indicates a value calculated from Mn and Mw in terms of polystyrene measured by gel permeation chromatography (GPC). The measurement by GPC is performed by the method described in the examples.

The structural unit represented by the formula (1-1) is as follows, from the viewpoint of facilitating conversion of a carbonyl group into a functional group, advantageous in mechanical properties and thermal properties, and excellent raw material availability. It is preferably a structural unit represented by formula (1-3). When the polymer compound has a plurality of structural units represented by formula (1-1), all of the plurality of structural units may be structural units represented by formula (1-3).

In formula (1-3), R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ^{R 1} in the formula (1-3) has the same meaning as ^{R 1} in formula (1-1).

The structural unit represented by the formula (1-1) can be said to be a structural unit derived from the compound represented by the following formula (2-1).

In formula (2-1), R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ^{R 1} in the formula (2-1) has the same meaning as ^{R 1} in formula (1-1).

The polymer compound may have a group derived from a polymerization initiator or a polymerization terminator at one or both ends of the main chain.

In one aspect, the polymer compound may be a polymer compound composed of only the structural unit represented by the formula (1-1) and a group derived from a polymerization initiator or a polymerization terminator. Examples of such a high molecular compound include a homopolymer of the compound represented by the formula (2-1).

In another aspect, the polymer compound may have a structural unit other than the structural unit represented by the formula (1-1). Such a structural unit can be referred to as a structural unit derived from a polymerizable compound other than the compound represented by the formula (2-1) (hereinafter, sometimes referred to as “other monomer”).

Anionic polymerizable compounds are preferably used as the other monomer. Examples of the anionically polymerizable compound include styrene, α-methylstyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene. , M-bromostyrene, p-bromostyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxy. Styrene compounds such as styrene, m-methoxystyrene, p-methoxystyrene, o-phenylstyrene, m-phenylstyrene, p-phenylstyrene; 1,3-butadiene, isoprene, piperylene, chloroprene, pentadienes, hexadienes, etc. Diene compounds such as; 2-vinylpyridine, vinyl heteroarene compounds such as 4-vinylpyridine; tert-butyl (meth)acrylate, propyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate and the like ( (Meth)acrylic acid ester; acrylamide compounds such as N,N-dialkyl(meth)acrylamide; and acrylonitrile compounds such as (meth)acrylonitrile.

The content of the structural unit represented by formula (1-1) in the polymer compound is not particularly limited, and may be, for example, 10% by mass or more, and 30% by mass or more based on the total amount of the polymer compound. It may be present, may be 50 mass% or more, may be 70 mass% or more, and may be 90 mass% or more.

In still another aspect, the polymer compound may be a block copolymer having a block chain having a structural unit represented by formula (1-1).

In the present embodiment, the block copolymer refers to a linear copolymer in which a plurality of polymer chains are linked as a block. A typical example of the block copolymer is -(AA..AA)-(BB..BB)- in which a block chain A having a structural unit A and a block chain B having a structural unit B are bonded to each other at their ends. It is an AB type diblock polymer having a structure. Further, the polymer compound of this embodiment may be a block copolymer in which three or more types of block chains are bonded. In the case of the triblock polymer, any of ABA type, BAB type, and ABC type may be used. Further, the polymer compound of this embodiment may be a star type block copolymer in which one or more kinds of block chains are radially extended from the center. Further, the polymer compound of this embodiment may be a block copolymer having four or more block chains (for example, (AB)n type, (ABA)n type, etc.).

That is, the polymer compound may have a block chain A having a structural unit represented by the formula (1-1) and a block chain B that is bonded to the block chain A.

The block chain A may have a structural unit other than the structural unit represented by the formula (1-1). For example, the block chain A may further have a structural unit derived from the above-mentioned other monomer.

The content of the structural unit represented by the formula (1-1) in the block chain A is not particularly limited, and may be, for example, 10% by mass or more, and 30% by mass or more based on the total amount of the block chain A. Well, it may be 50 mass% or more, 70 mass% or more, and 90 mass% or more.

The block chain B may be a block chain having a structure different from that of the block chain A. Further, the polymer compound may further have a block chain C different from both the block chain A and the block chain B.

The block chain having a structure different from that of the block chain A (block chain B, block chain C, etc.) may have a structural unit derived from an anionically polymerizable compound, for example. Examples of the anionically polymerizable compound include the compounds represented by the formula (2-1) and the compounds exemplified as the above-mentioned other monomers.

The number average molecular weight Mn _A of the block chain A may be, for example, 500 to 1.0×10 ⁷ , 5,000 to 1.0×10 ⁶ , or 5.0×10 ^{4 to} 1.0×10. It may be ⁵ .

The ratio of the weight average molecular weight Mw _A to the number average molecular weight Mn _A in the block chain _{A (Mw} A / Mn A), for example, may be 2.0 or less, may be 1.7 or less, 1.4 or less May be The lower limit of Mw _A /Mn _A is 1.

The weight average molecular weight and the number average molecular weight of the block chains (block chain B, block chain C, etc.) having a different structure from the block chain A are not particularly limited, but the number average molecular weight is, for example, 500 to 1.0×10 ⁷ . It may be, and may be 5000 to 1.0×10 ⁶ , and 5.0×10 ^{4 to} 1.0×10 ⁵ . The molecular weight distribution (Mw/Mn) may be, for example, 2.0 or less, 1.7 or less, and 1.4 or less.

The polymer compound according to this embodiment has excellent thermal characteristics and mechanical characteristics. Therefore, the polymer material containing the polymer compound according to this embodiment can be suitably used for various applications.

Since the polymer compound according to this embodiment has an acyl group, various modified products can be obtained by converting the acyl group into a functional group.

In the present embodiment, for example, nucleophilic addition reaction, reduction reaction, oxidation reaction, photoreaction, coupling reaction, photocoupling reaction, radical reaction, Wittig reaction, acetalization reaction, etc. The modified product can be obtained by performing imine reaction, esterification reaction, polymerization reaction (radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, etc.). More specifically, for example, a graft polymer (comb polymer, etc.) can be obtained by adding a long-chain alkyl group, a polymer such as polystyrene, etc. to a polymer compound by a nucleophilic addition reaction. Further, for example, a graft polymer (comb polymer etc.) can be obtained by polymerizing a polymerizable compound with an acyl group as a reaction point. Further, when R ¹ in the polymer compound is an aromatic group, that is, when the polymer compound has a benzophenone moiety, the polymer compound in which the benzophenone moiety in the polymer compound is photoreacted intramolecularly or intermolecularly Can be obtained. Such a polymer compound has a benzopinacol site.

The polymer material containing the polymer compound and/or a modified product of the polymer compound according to the present embodiment is, for example, an automobile elastomer, an industrial elastomer, a building elastomer, a miscellaneous goods elastomer, a medical elastomer, a food elastomer. Suitable for use in various thermosetting or thermoplastic elastomers such as resin-modifying elastomers, various adhesives, various sealing (caulking) materials, films, resins, molding materials, paints, rubber, coating materials, etc. You can Automotive elastomers include weather strips, handbrake grip covers, shift knobs, armrests, assist grips, instrument panels, door panels, airbag covers, belt line moldings, roof moldings, glass run channels, engine rooms, boots, tires, etc. Can be used for. Industrial elastomers can be used for applications such as gaskets, cap seals, tubes, sound deadening gears, grips for tools, and the like. The architectural elastomer can be used, for example, in applications such as vibration damping and seismic isolation rubber. The miscellaneous goods elastomer can be used, for example, for grips such as toothbrushes, pens, razors, and cutters, shoe soles, toys, and the like. The medical elastomer can be used for applications such as an infusion bag, an infusion port, and a cap. The food grade elastomer can be used for applications such as a cap liner. The resin-modifying elastomer can be used for applications such as impact resistance improvement of polypropylene and heat resistance improvement of polyethylene.

(Compound)
The compound according to this embodiment is represented by formula (2-1). The compound represented by the formula (2-1) is useful as a monomer component of the polymer compound described above, and can be suitably used in the method for producing the polymer compound. The compound according to this embodiment may be restated as a styrene derivative containing a ketone group.

In formula (2-1), R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ^{R 1} in the formula (2-1) has the same meaning as ^{R 1} in formula (1-1).

The compound represented by the formula (2-1) is preferably a compound represented by the following formula (2-2) from the viewpoint of thermal properties, mechanical properties and raw material availability.

In formula (2-2), R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ^{R 1} in the formula (2-2) has the same meaning as ^{R 1} in formula (1-1).

The compound represented by the formula (2-1) can be obtained, for example, by a production method including a step of reacting a compound represented by the following formula (3) with a compound represented by the following formula (4). ..

In formula (3), X ¹ represents a halogen group. In formula (4), R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position, and X ² represents a halogen group or an acyloxy group. ^{R 1} in the formula (4) has the same meaning as ^{R 1} in formula (1-1).

X ¹ may be a chloro group, a bromo group or an iodo group, and is preferably a chloro group from the viewpoint of stability, reactivity, productivity, raw material availability and cost.

X ² may be a chloro group, a bromo group, an iodo group or an acyloxy group, and is preferably a chloro group from the viewpoints of stability, reactivity, productivity, raw material availability and cost.

The reaction conditions in the above steps may follow the usual Grignard reaction conditions, and can be appropriately selected by those skilled in the art. For example, as the solvent, ethers such as tetrahydrofuran, diethyl ether, diisopropyl ether, dibutyl ether, glyme (glyme), diglyme (diglyme) and triglyme (triglyme), benzene-based solvents such as toluene, xylene and benzene are used, The reaction may be performed at 20 to 100°C for 0.1 to 100 hours. Moreover, you may perform the said process in presence of additives, such as a copper chloride, a nickel catalyst, an alkyl lithium, an iodine, and a 1, 2- dibromo ethane.

(Method for producing polymer compound)
Hereinafter, one aspect of the method for producing the polymer compound will be described in detail.

One aspect of the method for producing the polymer compound includes a step of polymerizing a monomer component containing the compound represented by the formula (2-1) (hereinafter, also referred to as “polymerization step”).

In the polymerization step, the monomer component may be polymerized by anionic polymerization, coordination polymerization, radical polymerization or cationic polymerization.

In the following, when the monomer component is anionically polymerized, that is, the method for producing the polymer compound is a step of anionically polymerizing the monomer component containing the compound represented by the formula (2-1) (hereinafter, “ Also referred to as an anionic polymerization step") will be described in more detail.

In the anionic polymerization step, the active species derived from the compound represented by formula (2-1) may be stably present in the reaction solution. Therefore, anionic polymerization of the compound represented by formula (2-1) proceeds in a living manner. That is, in the above production method, the anionic polymerization of the compound represented by the formula (2-1) is living anionic polymerization. Therefore, according to the above production method, the polymer compound can be obtained with a molecular weight as designed and a narrow molecular weight distribution.

The monomer component may consist of only the compound represented by formula (2-1), and may contain a compound other than the compound represented by formula (2-1). When the monomer component consists only of the compound represented by formula (2-1), a homopolymer of the compound represented by formula (2-1) is obtained.

Examples of the compound other than the compound represented by the formula (2-1) include the compounds exemplified as the above-mentioned other monomers.

In the monomer component, the content of the compound represented by the formula (2-1) may be, for example, 10 mol% or more, and 30 mol% or more based on the total amount of the monomer component. , 50 mol% or more, 70 mol% or more, 90 mol% or more.

In the anionic polymerization step, for example, the monomer component may be anionically polymerized by a method of reacting the monomer component dispersed or dissolved in an organic solvent with an anionic polymerization initiator.

As the organic solvent used in the polymerization step, aliphatic hydrocarbons, aromatic hydrocarbons, ether solvents and the like are suitable, 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, ethylcyclohexane and the like. Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene and the like. Examples of the ether solvent include tetrahydrofuran, diethyl ether, diisopropyl ether, glyme (glyme), diglyme (diglyme), and the like.

In the above production method, an anionic polymerization initiator containing various alkali metals can be used, for example, an anionic polymerization initiator having at least one alkali metal element selected from the group consisting of lithium, sodium, potassium and cesium. Can be used. From the viewpoint that a polymer compound having a narrower molecular weight distribution can be obtained, it is preferable to use an anionic polymerization initiator having at least one alkali metal element selected from the group consisting of sodium, potassium and cesium. The present inventors presume as follows why the polymer compound having a narrower molecular weight distribution can be obtained by using the anionic polymerization initiator having these alkali metal elements. In the following, for convenience, a portion of the anionic polymerization initiator that becomes a nucleophilic species in the reaction with the above-mentioned monomer component is called an anion portion, and a portion that becomes a counter cation is called a cation portion.

In the anionic polymerization of a monomer having an acyl group, a reaction between an anionic polymerization initiator and an acyl group or a reaction between a growth terminal anion and an acyl group may occur as a side reaction. When the ionic radius of the counter cation derived from the cation part of the anionic polymerization initiator is large, it is presumed that the reaction between the anionic polymerization initiator or the growth terminal anion and the acyl group becomes difficult to proceed. At least one alkali metal element selected from the group consisting of sodium, potassium and cesium becomes a counter cation having a large ionic radius in anionic polymerization, and therefore, by using an anionic polymerization initiator having these alkali metal elements, the molecular weight is The present inventors speculate that a polymer compound having a narrower distribution can be obtained.

The anion part of the anionic polymerization initiator is, for example, naphthalene group, benzyl group, diphenylmethyl group, triphenylmethyl group, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, sec-butyl group. , Tert-butyl group and the like. These anion moieties are moderately bulky and weak in nucleophilicity due to resonance stabilization. Therefore, by using a polymerization initiator having these anion moieties, a polymer compound having a designed molecular weight and a narrower molecular weight distribution can be obtained. Tends to be obtained. Among these, a diphenylmethyl group and a triphenylmethyl group are preferable.

Specific examples of the anionic polymerization initiator that can be used in the anionic polymerization step include lithium naphthalene, sodium naphthalene, potassium naphthalene, cesium naphthalene, benzyl lithium, benzyl sodium, benzyl potassium, benzyl cesium, diphenylmethyl lithium, diphenylmethyl. Sodium, diphenylmethyl potassium, diphenylmethyl cesium, triphenylmethyl lithium, triphenyl methyl sodium, triphenyl methyl potassium, triphenyl methyl cesium, methyl lithium, ethyl lithium, normal propyl lithium, isopropyl lithium, normal butyl lithium, isobutyl lithium, Examples thereof include sec-butyllithium and tert-butyllithium.

The amount of the anionic polymerization initiator can be appropriately adjusted according to the molecular weight and the like of the desired polymer compound, and may be, for example, 0.00001 to 100 parts by mass with respect to 100 parts by mass of the monomer component. , 0.001 to 10 parts by mass, or 0.1 to 1 part by mass.

A polymerization terminator may be used in the anionic polymerization step. Examples of the polymerization terminator include alcohols such as methanol, ethanol and isopropyl alcohol; carboxylic acids such as acetic acid; water and the like.

The reaction time of the anionic polymerization can be appropriately adjusted depending on the conversion rate of the monomer components and the like, but may be, for example, 0.1 to 100 hours or 1 to 10 hours. The reaction temperature of the anionic polymerization can be appropriately adjusted according to the conversion rate of the monomer component, the molecular weight distribution of the desired polymer compound, and the like, but may be, for example, -100°C to 100°C, and -50°C to 50°C. It may be in °C.

In one aspect, the polymerization step comprises a step A of polymerizing a monomer component A containing a compound represented by the formula (2-1) to obtain a block chain A and a monomer component B of a block The step B of obtaining the chain B may be included. According to the production method including such a polymerization step, it is possible to produce a block copolymer having a block chain A having a structural unit represented by the formula (1-1).

In the steps A and B, the monomer component may be polymerized by anionic polymerization, coordination polymerization, radical polymerization or cationic polymerization.

The monomer component A may further contain a compound other than the compound represented by formula (2-1). Examples of the compound include the compounds exemplified as the above-mentioned other monomers.

The content of the compound represented by the formula (2-1) in the monomer component A may be, for example, 10 mol% or more, and 30 mol% or more based on the total amount of the monomer component A. It may be 50 mol% or more, 70 mol% or more, 90 mol% or more.

The monomer component B may have a composition different from that of the monomer component A and can form a block chain B having a structure different from that of the block chain A.

The monomer component B preferably contains an anion-polymerizable compound, and examples of the anion-polymerizable compound include compounds represented by the formula (2-1) and the above-mentioned other monomers. Compounds.

In the above manufacturing method, the order of performing the steps A and B is not particularly limited.

For example, in the above-mentioned polymerization step, the monomer component A is anionically polymerized to obtain a block chain A having an active site at the terminal, and the active site of the block chain A and the monomer component B are reacted. And a step B of obtaining a block chain B that binds to the block chain A.

In the polymerization step, step B in which the monomer component B is anionically polymerized to obtain a block chain B having an active site at the terminal, and the active site of the block chain B and the monomer component A are reacted. And the step A of obtaining a block chain A that binds to the block chain B.

Since the compound represented by the formula (2-1) has high electrophilicity, when the monomer components are polymerized by anionic polymerization in the above steps A and B, after step B, step A is performed. By doing so, a polymer compound having a designed molecular weight and a narrower molecular weight distribution tends to be easily obtained.

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

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the examples.

In this example, as a monomer component, a compound (compound A) represented by the following formula (A-1), a compound (compound B) represented by the following formula (B-1), and a following formula (C- The compound (compound C) represented by 1) and the compound (compound D) represented by the following formula (D-1) were used. ¹ H-NMR chart and ¹³ C-NMR chart of the following compound A, compound B, compound C and compound D are shown in FIGS. 1 to 8. In this Example, ¹ H-NMR and ¹³ C-NMR measurements were performed using DPX300 (manufactured by Bruker), and CDCl ₃ was used as a solvent.

[In the formula, Ad represents a 1-adamantyl group. ]

^Wherein, t Bu represents a tert- butyl group. ]

[In the formula, Ph represents a phenyl group. ]

[In the formula, MD represents a methyldimethanocyclodecenyl group. ]

(Example 1)
Anionic polymerization of the compound A was carried out by a break seal method using a Pyrex (registered trademark) reaction vessel.

Specifically, in a Pyrex (registered trademark) reaction container, an ampoule of 2 ml of heptane solution (manufactured by Kanto Chemical Co., Inc.) containing 10.7 mg (0.0615 mmol) of diphenylmethyllithium (Ph ₂ CHLi) sealed by a break seal was used. An ampoule containing 594.0 mg (2.23 mmol) of Compound A and 8 ml of tetrahydrofuran (THF) was welded. Then, the reaction vessel was connected to a high vacuum line (10 ⁻⁶ mmHg), and deaeration and baking were repeated twice under high vacuum to seal the reaction vessel.

Next, the break seal of the container containing the diphenylmethyllithium solution was broken, the diphenylmethyllithium solution was transferred to the reaction container, and then cooled to -78°C. The reaction solution containing the diphenylmethyllithium solution was vigorously stirred, the break seal of the container containing the compound A and THF, which was also cooled to −78° C., was broken, added to the reaction solution, and left to react for 48 hours.

After completion of the polymerization, the reaction vessel was opened, and 2 ml of a polymerization terminator, methanol, was added to terminate the polymerization. When the reaction solution was poured into 100 ml of methanol, a white solid was precipitated. A polymer having a structural unit represented by the following formula (A-2) is obtained by filtering the solid by filtration under reduced pressure using Kiriyama funnel and Kiriyama filter paper, dissolving it in 5 ml of benzene, and performing freeze-drying. 30 mg of the compound (polymer compound 1) was obtained. The ¹ H-NMR chart of the obtained polymer compound 1 is shown in FIG. 9. The conversion rate of the compound A determined from ¹ H-NMR of the obtained polymer compound 1 was 10%. The polymer yield was 5% by mass based on the charged compound A.

[In the formula, Ad represents a 1-adamantyl group. ]

With respect to the obtained polymer compound 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 molecular weight distribution Mw/Mn were measured by the following methods (II) and (III). The results are shown in Table 1.

(I) Calculation of the calculated value of the number average molecular weight Mn The molecular weight of the partial structure derived from the polymerization initiator and the polymerization terminator present at the terminal of the obtained polymer compound, and the amount of the polymerization initiator used (mol) The calculated value of the number average molecular weight Mn is calculated by summing the molecular weight of the polymer chain calculated based on the ratio of the amount of the monomer component used (molar amount) (the amount of the monomer component used/the amount of the polymerization initiator used). did.

(II) Measurement of number average molecular weight Mn The number average molecular weight Mn of the polymer compound 1 was measured using Right 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 detectors is used, the flow rate is 1.0 ml/min, and the column oven is used. The temperature was set to 30° C. and the measurement was performed. THF was used as an outflow solvent, and TOSOH G5000HXL+G4000HXL+G3000HXL was used as an analytical column.

(III) Measurement of ratio (Mw/Mn) Using gel permeation chromatography (GPC), the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn was measured. More specifically, a Viscotek Model 302 Triple Detector Array (manufactured by Asahi Techneion Co., Ltd.) was used.

(Example 2)
Except that the amount of diphenylmethyllithium used was 10.2 mg (0.0584 mmol), the amount of compound A used was 442.2 mg (1.66 mmol), the reaction time was 72 hours, and the reaction temperature was 0°C. Then, anionic polymerization was performed in the same manner as in Example 1 to obtain 389 mg of a polymer compound (polymer compound 2) having a structural unit represented by the formula (A-2). The conversion rate of the compound A determined from ¹ H-NMR of the obtained polymer compound 2 was 100%. The polymer yield was 88% by mass based on the charged compound A.

For the obtained polymer compound 2, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 1.

(Example 3)
Similar to Example 1 except that diphenylmethyl sodium (Ph ₂ CHNa) 10.3 mg (0.0541 mmol) was used instead of diphenylmethyl lithium and the amount of compound A used was 532.8 mg (2.00 mmol). And anionic polymerization was performed to obtain 426 mg of a polymer compound (polymer compound 3) having a structural unit represented by the formula (A-2). The conversion rate of the compound A obtained from ¹ H-NMR of the obtained polymer compound 3 was 89%. The polymer yield was 80% by mass based on the charged compound A.

Regarding the obtained polymer compound 3, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 1.

(Example 4)
In the same manner as in Example 1 except that 8.5 mg (0.0412 mmol) of diphenylmethyl potassium (Ph ₂ CHK) was used instead of diphenylmethyllithium, and the amount of the compound A used was 1251 mg (4.70 mmol). Anion polymerization was performed to obtain 1039 mg of a polymer compound (polymer compound 4) having a structural unit represented by the formula (A-2). The conversion rate of the compound A obtained from ¹ H-NMR of the obtained polymer compound 4 was 100%. The polymer yield was 83% by mass based on the charged compound A.

For the obtained polymer compound 4, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were carried out by the methods (I), (II) and (III). went. The results are shown in Table 1.

The glass transition temperature Tg and the 10 mass% decrease temperature T ₁₀ of the obtained polymer compound 4 were measured by the following method (IV). Tg of 193 ° _{C., T 10} was 430 ° C.. The 10% by mass decrease temperature T ₁₀ means the temperature when the mass of the polymer compound 4 decreases by 10% by mass from the mass at the start of the measurement.

(IV) Measurement of glass transition temperature Tg and 10% by mass decrease temperature T _{10 It} was measured using a DSC apparatus (“DSC6220” manufactured by Seiko Instruments Inc.). For the measurement, the sample was once heated to 100° C., annealed at the same temperature for 10 minutes, and then rapidly cooled to room temperature. Then, the temperature was raised again at 20° C./min, and the glass transition temperature (Tg) and the 10% by mass decrease temperature (T ₁₀ ) were measured.

(Example 5)
In the same manner as in Example 1 except that 13.2 mg (0.0792 mmol) of potassium naphthalene (K-Naph) was used instead of diphenylmethyllithium and the amount of the compound A used was 498.1 mg (1.87 mmol). Anionic polymerization was performed to obtain 443 mg of a polymer compound (polymer compound 5) having a structural unit represented by the formula (A-2). The conversion rate of the compound A obtained from ¹ H-NMR of the obtained polymer compound 5 was 100%. The polymer yield was 89% by mass based on the charged compound A.

For the obtained polymer compound 5, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 1.

(Example 6)
Example 2 was repeated except that 22.4 mg (0.0794 mmol) of triphenylmethyl potassium (Ph ₃ CK) was used instead of diphenylmethyllithium, and the amount of Compound A used was 668.6 mg (2.51 mmol). Anionic polymerization was performed in the same manner to obtain 595 mg of a polymer compound (polymer compound 6) having a structural unit represented by the formula (A-2). The conversion rate of the compound A obtained from ¹ H-NMR of the obtained polymer compound 6 was 95%. The polymer yield was 89% by mass based on the charged compound A.

Regarding the obtained polymer compound 6, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 1.

(Example 7)
Same as Example 1 except that 20.9 mg (0.0697 mmol) of diphenylmethyl cesium (Ph ₂ CHCs) was used instead of diphenylmethyl lithium and the amount of the compound A used was 623.3 mg (2.34 mmol). And anionic polymerization was performed to obtain 530 mg of a polymer compound (polymer compound 7) having a structural unit represented by the formula (A-2). The conversion rate of the compound A obtained from ¹ H-NMR of the obtained polymer compound 7 was 100%. Further, the polymer yield was 85% by mass based on the charged compound A.

Regarding the obtained polymer compound 7, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were carried out by the methods (I), (II) and (III). went. The results are shown in Table 1.

(Example 8)
Anionic polymerization was performed in the same manner as in Example 1 except that 523.4 mg (2.78 mmol) of Compound B was used instead of Compound A and the amount of diphenylmethyllithium used was 9.9 mg (0.0566 mmol). 52 mg of a polymer compound (polymer compound 8) having a structural unit represented by the following formula (B-2) was obtained. The ¹ H-NMR chart of the obtained polymer compound 8 is shown in FIG. The conversion rate of the compound B obtained from ¹ H-NMR of the obtained polymer compound 8 was 16%. Further, the polymer yield was 10% by mass based on the charged compound B.

^Wherein, t Bu represents a tert- butyl group. ]

With respect to the obtained polymer compound 8, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 2. Further, the glass transition temperature (Tg) and the 10 mass% decrease temperature (T ₁₀ ) were measured by the method (IV). Tg of 135 ° _{C., T 10} was 415 ° C..

(Example 9)
Except that the amount of diphenylmethyllithium used was 10.1 mg (0.0581 mmol), the amount of compound B used was 561.0 mg (2.98 mmol), the reaction time was 72 hours, and the reaction temperature was 0°C. Anion polymerization was performed in the same manner as in Example 8 to obtain 476.9 mg of a polymer compound (polymer compound 9) having a structural unit represented by the formula (B-2). The conversion rate of the compound B obtained from ¹ H-NMR of the obtained polymer compound 9 was 100%. Further, the polymer yield was 85% by mass based on the charged compound B.

For the obtained polymer compound 9, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were carried out by the methods (I), (II) and (III). went. The results are shown in Table 2.

(Example 10)
Example 8 except that 9.8 mg (0.0517 mmol) of sodium diphenylmethyl was used instead of diphenylmethyllithium, the amount of compound B used was 564.8 mg (3.00 mmol), and the reaction time was 72 hours. Anion polymerization was performed in the same manner as in, to obtain 441 mg of a polymer compound (polymer compound 10) having a structural unit represented by the formula (B-2). The conversion rate of the compound B obtained from ¹ H-NMR of the obtained polymer compound 10 was 83%. The polymer yield was 78% by mass based on the charged compound B.

With respect to the obtained polymer compound 10, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 2.

(Example 11)
Example 8 except that 8.8 mg (0.0428 mmol) of diphenylmethyl potassium was used instead of diphenylmethyl lithium, the amount of compound B was 431.1 mg (2.29 mmol), and the reaction time was 72 hours. Anionic polymerization was performed in the same manner as in, to obtain 272 mg of a polymer compound (polymer compound 11) having a structural unit represented by the formula (B-2). The conversion rate of the compound B obtained from ¹ H-NMR of the obtained polymer compound 11 was 100%. Further, the polymer yield was 63% by mass based on the charged compound B.

For the obtained polymer compound 11, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were carried out by the methods (I), (II) and (III). went. The results are shown in Table 2.

(Example 12)
Anionic polymerization was performed in the same manner as in Example 8 except that 21.4 mg (0.0757 mmol) of triphenylmethyl potassium was used instead of diphenylmethyl lithium and the amount of the compound B used was 679.7 mg (3.61 mmol). Was performed to obtain 415 mg of a polymer compound (polymer compound 12) having a structural unit represented by the formula (B-2). The conversion rate of the compound B obtained from ¹ H-NMR of the obtained polymer compound 12 was 99%. Further, the polymer yield was 61% by mass based on the charged compound B.

For the obtained polymer compound 12, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were carried out by the methods (I), (II) and (III). went. The results are shown in Table 2.

(Example 13)
Anion polymerization was performed in the same manner as in Example 8 except that 23.3 mg (0.139 mmol) of potassium naphthalene was used instead of diphenylmethyllithium, and the amount of compound B was 625.1 mg (3.32 mmol). , 538 mg of a polymer compound (polymer compound 13) having a structural unit represented by the formula (B-2) was obtained. The conversion rate of the compound B obtained from ¹ H-NMR of the obtained polymer compound 13 was 98%. The polymer yield was 86% by mass based on the charged compound B.

Regarding the obtained polymer compound 13, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 2.

(Example 14)
Anion polymerization was performed in the same manner as in Example 8 except that 19.3 mg (0.0643 mmol) of diphenylmethylcesium was used instead of diphenylmethyllithium, and the amount of the compound B used was 675.9 mg (3.59 mmol). This was performed to obtain 412 mg of a polymer compound (polymer compound 14) having a structural unit represented by the formula (B-2). The conversion rate of the compound B determined from ¹ H-NMR of the obtained polymer compound 14 was 98%. Further, the polymer yield was 61% by mass based on the charged compound B.

For the obtained polymer compound 14, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 2.

(Example 15)
Compound C 556.1 mg (2.67 mmol) was used in place of compound A, triphenylmethyl potassium 16.2 mg (0.0573 mmol) was used in place of diphenylmethyl lithium, the reaction temperature was 0° C., and the reaction time was 24. Anionic polymerization was performed in the same manner as in Example 1 except that the time was changed to obtain 556.1 mg of a polymer compound (polymer compound 15) having a structural unit represented by the following formula (C-2). The ¹ H-NMR chart of the obtained polymer compound 15 is shown in FIG. 11. The conversion rate of the compound C obtained from ¹ H-NMR of the obtained polymer compound 15 was 100%. The polymer yield was 100% by mass based on the charged compound C.

Regarding the obtained polymer compound 15, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were carried out by the methods (I), (II) and (III). went. The results are shown in Table 2. Further, the glass transition temperature (Tg) and the 10 mass% decrease temperature (T ₁₀ ) were measured by the method (IV). Tg of 120 ° _{C., T 10} was 408 ° C..

[In the formula, Ph represents a phenyl group. ]

(Example 16)
Anion was prepared in the same manner as in Example 1 except that compound D (462.7 mg, 1.52 mmol) was used instead of compound A, and diphenylmethyl potassium (8.7 mg, 0.042 mmol) was used instead of diphenylmethyl lithium. Polymerization was performed to obtain 351.7 mg of a polymer compound (polymer compound 16) having a structural unit represented by the following formula (D-2). The ¹ H-NMR chart of the obtained polymer compound 16 is shown in FIG. The conversion rate of the compound C obtained from ¹ H-NMR of the obtained polymer compound 17 was 100%. The polymer yield was 76% by mass based on the charged compound D.

With respect to the obtained polymer compound 16, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The results are shown in Table 2. Further, the glass transition temperature (Tg) and the 10 mass% decrease temperature (T ₁₀ ) were measured by the method (IV). Tg of 172 ° _{C., T 10} was 283 ° C..

[In the formula, MD represents a methyldimethanocyclodecenyl group. ]

(Reference example 1)
Example 1 except that sec-butyllithium (sec-BuLi) 2.69 mg (0.0420 mmol) was used instead of diphenylmethyllithium, and the amount of compound A used was 444.9 mg (1.67 mmol). Anionic polymerization was tried in the same manner, but the anionic polymerization of Compound A did not proceed.

(Reference example 2)
Compound B was used in the same manner as in Example 8 except that sec-butyllithium 1.97 mg (0.0308 mmol) was used instead of diphenylmethyllithium, and the amount of compound B used was 504.6 mg (2.68 mmol). The anionic polymerization of Compound B was attempted, but the anionic polymerization of Compound B did not proceed.

(Reference example 3)
Anionic polymerization of styrene was performed in the same manner as in Example 1 except that 23.3 mg (0.139 mmol) of potassium naphthalene was used instead of diphenylmethyllithium and 13.3 g (128 mmol) of styrene was used instead of Compound A. Then, 13 g of polystyrene was obtained.

With respect to the obtained polystyrene, the number average molecular weight Mn and the molecular weight distribution Mw/Mn were measured by the methods (II), (III) and (IV), and the glass transition temperature (Tg) and the 10 mass% decrease temperature ( T ₁₀ ) was measured. Mn was 96000, Mw/Mn was 1.04, Tg was 104°C and T ₁₀ was 396°C.

(Example 17)
The block copolymerization of the compound A and the compound B was performed by a break seal method using a reaction container made of Pyrex (registered trademark).

Specifically, in a Pyrex (registered trademark) reaction container, an ampoule of 2 ml of a THF solution containing 16.4 mg (0.0796 mmol) of diphenylmethyl potassium sealed by a break seal, and 514.1 mg (1.93 mmol of Compound A). ) And 8 ml of THF were welded to an ampoule containing 487.6 mg (2.59 mmol) of compound B and 6 ml of THF. Then, the reaction vessel was connected to a high vacuum line (10 ⁻⁶ mmHg), and deaeration and baking were repeated twice under high vacuum to seal the reaction vessel.

Then, the break seal containing the diphenylmethyl potassium solution was broken, the diphenylmethyl potassium solution was transferred to the reaction vessel, and then cooled to -78°C. The reaction solution containing the diphenylmethyl potassium solution was vigorously stirred, and a break seal containing Compound A and THF, which was also cooled to −78° C., was broken, added to the reaction solution, and allowed to react for 48 hours as it was. Then, the break seal containing the compound B and THF was broken, added to the reaction solution, and stirred as it was for 48 hours. After the completion of the polymerization, the reaction solution was opened and 2 ml of a polymerization terminator, methanol, was added to terminate the polymerization.

When the reaction solution was poured into 200 ml of methanol, a white solid was precipitated. The solid is filtered by vacuum filtration using a Kiriyama funnel and Kiriyama filter paper, dissolved in 5 ml of benzene, and freeze-dried to obtain the structural unit represented by the formula (A-2) and the formula (B- 881 mg of polymer compound 17 having a structural unit represented by 2) was obtained. The ¹ H-NMR chart of the obtained polymer compound 17 is shown in FIG. 13. The polymer yield was 88% by mass based on the total amount of the compound A and the compound B charged.

With respect to the obtained polymer compound 17, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The calculated value of the number average molecular weight Mn was 14,100, whereas the measured value of the number average molecular weight Mn was 15,000. The molecular weight distribution Mw/Mn was 1.07.

Further, a homopolymer of compound A (block chain A) 48 hours after the start of the reaction was sampled, and ¹ H-NMR of the homopolymer was measured. The ¹ H-NMR chart of the homopolymer is shown in FIG. From the comparison between ¹ H-NMR of the obtained homopolymer and ¹ H-NMR of the polymer compound 17, a block chain having a structural unit represented by the formula (A-2) (block chain A), It was confirmed that the mass ratio (mass of block chain A/mass of block chain B) of the block chain (block chain B) having the structural unit represented by (B-2) was 27/73.

Moreover, the calculation of the number average molecular weight Mn _A of the homopolymer and the measurement of the number average molecular weight Mn _A and the molecular weight distribution Mw _A /Mn _A are performed by the methods (I), (II) and (III). I went. The calculated number average molecular weight Mn _A of the homopolymer was 6500, and the number average molecular weight Mn _A was 6000. The molecular weight distribution Mw _A /Mn _A was 1.08.

From the comparison between the number average molecular weight Mn _A of the homopolymer and the number average molecular weight Mn of the obtained polymer compound 17, it was confirmed that the number average molecular weight Mn of the polymer compound 17 was increased. Further, when the GPC curve of the homopolymer and the GPC curve of the polymer compound 17 were compared, movement of the peak position was confirmed (see FIG. 15). From these results as well, the polymer compound 17 was blocked. It was confirmed to be a copolymer. In addition, when the molecular weight distribution Mw _A /Mn _{A of} the homopolymer and the molecular weight distribution Mw/Mn of the polymer compound 17 were compared, almost no difference was observed in the molecular weight distribution.

(Example 18)
[Synthesis of graft copolymer by living polystyrene]
First, anionic polymerization was performed in the same manner as in Example 1 except that diphenylmethyl potassium was used instead of diphenylmethyl lithium, and a polymer compound having a structural unit represented by the above formula (A-2) (high 61.1 mg of the molecular compound 1′) was obtained. With respect to the obtained polymer compound 1′, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn are performed by the methods (I), (II) and (III). I went. The calculated value of the number average molecular weight Mn was 10400, while the measured value of the number average molecular weight Mn was 11400. The molecular weight distribution Mw/Mn was 1.06.

Then, the obtained polymer compound 1'and polystyrene were graft-polymerized by a break seal method using a Pyrex (registered trademark) reaction container.

Specifically, in a Pyrex (registered trademark) reaction container, an ampoule of 3 ml of a THF solution containing 18.3 mg (0.286 mmol) of sec-butyllithium and sealed with a break seal, and 1.291 g (12.4 mmol) of styrene. ) And 12 ml of THF were welded to an ampoule containing 61.1 mg (2.59 mmol) of polymer compound 1′ and 10 ml of THF. Then, the reaction vessel was connected to a high vacuum line (10 ⁻⁶ mmHg), and deaeration and baking were repeated twice under high vacuum to seal the reaction vessel.

Then, the break seal containing the sec-butyllithium solution was broken, the sec-butyllithium solution was transferred to the reaction vessel, and then cooled to -78°C. The reaction solution containing the sec-butyllithium solution was vigorously stirred, and a break seal containing styrene and THF, which was also cooled to −78° C., was broken, added to the reaction solution, and left to react for 10 minutes. Thereby, polystyrene was synthesized. The measured value of the number average molecular weight Mn was 4,500.

Then, a break seal containing the polymer compound 1'and THF was broken, added to the reaction solution, and stirred as it was for 24 hours. After the completion of the polymerization, the reaction solution was opened and 2 ml of a polymerization terminator, methanol, was added to terminate the polymerization.

When the reaction solution was poured into 200 ml of methanol, a white solid was precipitated. The solid was filtered by vacuum filtration using a Kiriyama funnel and Kiriyama filter paper, and then separated and precipitated by a mixed solution of hexane and cyclohexane to remove excess polystyrene. As a result of separation and purification by fractional precipitation, 0.65 g of a polymer compound having a structural unit represented by the following formula (E) (modified product of polymer compound 1′, polymer compound 18) was obtained. The ¹ H-NMR chart of the obtained polymer compound 18 is shown in FIG. 16. ¹ H-NMR of the polymer compound 18 was almost in agreement with polystyrene, and no signal attributable to the polymer compound 1′ was detected. The polymer yield was 66% by mass with respect to the total amount of the charged polymer compound 1′ and styrene.

[In the formula, Ad represents a 1-adamantyl group, and PS represents polystyrene. ]

With respect to the obtained polymer compound 18, the calculation of the calculated value of the number average molecular weight Mn and the measurement of the number average molecular weight Mn and the molecular weight distribution Mw/Mn were performed by the methods (I), (II) and (III). went. The calculated value of the number average molecular weight Mn was 209,000, while the measured value of the number average molecular weight Mn was 165,000. The molecular weight distribution Mw/Mn was 1.02. Almost no difference was observed in the molecular weight distributions of the polymer compound 1'and the polymer compound 18, and it was confirmed that the graft polymerization proceeded in a living manner.

(Example 19)
[Polymer crosslinking reaction of polymer compound having structural unit represented by formula (C-2) by UV irradiation]
With the content shown below, a crosslinking reaction of a polymer compound having a structural unit represented by the formula (C-2) was performed.

100 mg of the polymer compound 15 (containing 0.48 mmol of carbonyl group) was placed in a vial, and 40 μl (0.52 mmol) of isopropanol and 200 μl of THF were added thereto to dissolve the polymer compound 15. As a result, a solution containing 32% by mass of the polymer compound 15 was prepared. The vial was covered with a cover glass, and UV irradiation was continuously performed for 11 hours using an ultrahigh pressure UV lamp (250w, manufactured by Ushio Inc., trade name: USHIO optical module). After UV irradiation for 11 hours, it was confirmed that the solution lost fluidity and gelled. In addition, it was confirmed that the solution which was colorless and transparent before UV irradiation turned into pale yellow after UV irradiation.

The solution before UV irradiation and the gel obtained after UV irradiation were subjected to FT-IR measurement. In the measurement, a solution before UV irradiation and a gel obtained after UV irradiation were applied on a KBr plate and evaporated to dryness were used. Results are shown in FIG. In FIG. 17, the upper part shows the FT-IR chart of the solution before UV irradiation, and the lower part shows the FT-IR chart of the gel obtained after UV irradiation. In the FT-IR chart shown in FIG. 17, a peak of a hydroxyl group is observed, a carbonyl group of a part of the polymer compound 15 is excited by UV irradiation to cause a crosslinking reaction, and a crosslinked product of the polymer compound 15 is obtained. Was confirmed.

Claims (9)

Have a structural unit represented by the following formula (1-1),
A polymer compound having a ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 2.0 or less .

[In the formula, R ¹ is a hydrocarbon group having no hydrogen atom at the α-position, and is a tert-butyl group, 1-adamantyl group, 3-methyladamantyl group, 3,5-dimethyladamantyl group, triethylmethyl group, triethylmethyl group, triethylmethyl group, Propylmethyl group, tributylmethyl group, phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, naphthyl group, phenanthrenyl group, anthracenyl group, pyrenyl group, methylmethanocyclohexyl group, methylmethanocyclohexenyl group, methyldimethanocyclo A decyl group, a methyldimethanocyclodecenyl group, a methyltrimethanocyclotetradecyl group or a methyltrimethanocyclotetradecenyl group is shown. ] The polymer compound according to claim 1, which is a block copolymer having a block chain having the structural unit represented by the formula (1-1). The polymer compound according to claim 1, which has a structure represented by the following formula (1-2).

[In the formula, R ¹ is a hydrocarbon group having no hydrogen atom at the α-position, and is a tert-butyl group, 1-adamantyl group, 3-methyladamantyl group, 3,5-dimethyladamantyl group, triethylmethyl group, triethylmethyl group, triethylmethyl group, Propylmethyl group, tributylmethyl group, phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, naphthyl group, phenanthrenyl group, anthracenyl group, pyrenyl group, methylmethanocyclohexyl group, methylmethanocyclohexenyl group, methyldimethanocyclo A decyl group, a methyldimethanocyclodecenyl group, a methyltrimethanocyclotetradecyl group or a methyltrimethanocyclotetradecenyl group is shown, and n is an integer of 2 or more. ] The polymer compound according to claim 3, which is a block copolymer having a block chain having a structure represented by the formula (1-2). The polymer compound according to claim 1, which is a homopolymer of a compound represented by the following formula (2-1).

[In the formula, R ¹ is a hydrocarbon group having no hydrogen atom at the α-position, and is a tert-butyl group, 1-adamantyl group, 3-methyladamantyl group, 3,5-dimethyladamantyl group, triethylmethyl group, triethylmethyl group, triethylmethyl group, Propylmethyl group, tributylmethyl group, phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, naphthyl group, phenanthrenyl group, anthracenyl group, pyrenyl group, methylmethanocyclohexyl group, methylmethanocyclohexenyl group, methyldimethanocyclo A decyl group, a methyldimethanocyclodecenyl group, a methyltrimethanocyclotetradecyl group or a methyltrimethanocyclotetradecenyl group is shown. ] A method for producing a polymer compound according to any one of claims 1 to 5
A production method comprising a step of anionically polymerizing a monomer component containing a compound represented by the following formula (2-1).

[In the formula, R ¹ is a hydrocarbon group having no hydrogen atom at the α-position, and is a tert-butyl group, 1-adamantyl group, 3-methyladamantyl group, 3,5-dimethyladamantyl group, triethylmethyl group, triethylmethyl group, triethylmethyl group, Propylmethyl group, tributylmethyl group, phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, naphthyl group, phenanthrenyl group, anthracenyl group, pyrenyl group, methylmethanocyclohexyl group, methylmethanocyclohexenyl group, methyldimethanocyclo A decyl group, a methyldimethanocyclodecenyl group, a methyltrimethanocyclotetradecyl group or a methyltrimethanocyclotetradecenyl group is shown. ] The production method according to claim 6 , wherein in the step, an anionic polymerization initiator having at least one alkali metal element selected from the group consisting of lithium, sodium, potassium and cesium is used. Made by modifying the acyl groups of the polymer compound according to any one of claims 1 to 5 modified product of the polymer compound. Containing modified products according to the polymer compound and / or claim 8 as claimed in any one of claims 1 to 5 polymer material.