JP2016210965A - Polymer compound, modified product thereof and production method therefor, compound used for the production method and method for producing the same, and polymer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polymer compound comprising a structural unit derived from a styrene derivative having an acyl group.SOLUTION: The present invention provides a polymer compound having a structural unit represented by the following formula (1-1) [where Ris a hydrocarbon group having no hydrogen atom in α-position].SELECTED DRAWING: None

Description

  The present invention relates to a polymer compound, a modified product thereof, a production method thereof, a compound used in the production method and a production method thereof. The present invention also relates to a polymer material containing at least one of a polymer compound and 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, Kiyozo Miyata, Seiichi Nakahama, Graduate School of Polymer Science, Kodansha Scientific, June 10, 1997, P193

  However, anionic polymerization of an acyl group-containing styrene derivative is difficult, and no examples of successful anionic polymerization of an acyl group-containing styrene derivative are known.

  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 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. Moreover, an object of this invention is to provide the manufacturing method of the compound used for the manufacturing method of the said high molecular compound, and the said compound. Another object of the present invention is to provide a polymer material containing at least one of the polymer compound and a modified product thereof.

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

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

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

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

[Wherein, 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 embodiment, the polymer compound may be a block copolymer having a block chain having a structure represented by the formula (1-2).

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

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

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

  In one embodiment, 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 above polymer compound, the method comprising a step of anionic polymerization of a monomer component containing a compound represented by the following formula (2-1).

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

  In one embodiment, the 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).

[Wherein 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, the method comprising a step of reacting a compound represented by the following formula (3) and a compound represented by the following formula (4).

[Wherein, X ¹ represents a halogen group. ]

[Wherein 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 polymer compound obtained by modifying an acyl group of the 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, 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 are provided. Moreover, according to this invention, the compound used for the manufacturing method of the said high molecular compound and the manufacturing method of the said compound are provided. Moreover, according to this invention, the polymeric material containing at least one of the said high molecular compound and its modified material is provided.

It is a chart showing ^{1 H-NMR} chart of Compound A used in Example. It is. It is a figure which shows the ¹³ C-NMR chart of the compound A used in the Example. It is a chart showing ^{1 H-NMR} chart of compound B used in Examples. It is a figure which shows the ¹³ C-NMR chart of the compound B used in the Example. It is a chart showing ^{1 H-NMR} chart of the compound C used in Examples. It is a figure which shows the ¹³ C-NMR chart of the compound C used in the Example. It is a chart showing ^{1 H-NMR} chart of compound D used in Examples. It is a figure which shows the ¹³ C-NMR chart of the compound D used in the Example. 1 is a diagram showing a ¹ H-NMR chart of a polymer compound obtained in Example 1. FIG. 6 is a diagram showing a ¹ H-NMR chart of a polymer compound obtained in Example 8. FIG. ¹ is a diagram showing a ¹ H-NMR chart of a polymer compound obtained in Example 15. FIG. 2 is a diagram showing a ¹ H-NMR chart of a polymer compound obtained in Example 16. FIG. ¹ is a diagram showing a ¹ H-NMR chart of a polymer compound obtained in Example 17. FIG. ¹ is a diagram showing a ¹ H-NMR chart of a homopolymer obtained in Example 17. FIG. It is a figure which shows the GPC measurement result of the high molecular compound and homopolymer obtained in Example 17. ¹ is a diagram showing a ¹ H-NMR chart of a polymer compound obtained in Example 18. FIG. 2 is a diagram showing an FT-IR chart of the polymer compound used in Example 19 and the polymer compound obtained in Example 19. FIG.

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

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. Carbon number of the said alkyl group may be 1-10, for example, may be 1-5, and may be 1-3. The carbon number of the aromatic group may be, for example, 6 to 37, 6 to 27, or 6 to 17.

Examples of the alkyl group represented by R ¹⁰ , R ¹¹ and R ¹² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, and a hexyl group. , A cyclohexyl group and the like. The aromatic group of R ¹⁰ , R ¹¹ and R ¹² may be, for example, a phenyl group.

R ¹ may be a group in which R ¹⁰ and R ¹¹ in the formula (a) are bonded to each other to form an alicyclic group, and R ¹⁰ , R ¹¹ and R ¹² are bonded to each other A ring group may be formed. 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 easy 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 a phenyl group or a methyldimethanocyclodecenyl group.

From the viewpoint of facilitating functional group conversion 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. A butyl group or a phenyl group is more preferable.

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

  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 Formula (1-2) may be 2 or more, for example, may be 100 or more, and may be 1000 or more. Moreover, n in Formula (1-2) may be 1.0 × 10 ⁶ or less, may be 1.0 × 10 ⁵ or less, and may be 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 , 5000 to 1.0 × 10 ⁶ , and 5.0 × 10 ^{4 to} 1.0 × 10 ^5. It may be.

  In the polymer compound, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / 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 a RALLS-GPC method (Right Angle Laser Light Scattering GPC). In addition, the measurement by RALLS-GPC method is performed by the method as described in an Example.

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

  The structural unit represented by formula (1-1) has the following advantages in terms of facilitating functional group conversion of the carbonyl group, mechanical properties and thermal properties, and excellent raw material availability. A structural unit represented by the formula (1-3) is preferable. 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 a 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 of the ends of the main chain.

  In one embodiment, the polymer compound may be a polymer compound composed only of 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 polymer compound include a homopolymer of a compound represented by the formula (2-1).

  In another embodiment, the polymer compound may have a structural unit other than the structural unit represented by Formula (1-1). Such a structural unit can be said to be 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”).

  As the other monomer, an anion polymerizable compound is preferably used. Examples of the anionic polymerizable compound include styrene, α-methylstyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, and 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. Of diene compounds; 2 Vinyl heteroarene compounds such as vinylpyridine and 4-vinylpyridine; (meth) acrylic acid esters such as tert-butyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate and methyl (meth) acrylate; N , Acrylamide compounds such as N-dialkyl (meth) acrylamide; acrylonitrile compounds such as (meth) acrylonitrile, and the like.

  The content of the structural unit represented by the 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 50 mass% or more, 70 mass% or more, and 90 mass% or more.

  In still another embodiment, 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 bonded 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 the 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 block chains are bonded. In the case of a 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 a plurality of block chains extend radially from the center. Furthermore, the polymer compound of this embodiment may be a block copolymer having four or more block chains (for example, (A-B) 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 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 other monomer described above.

  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 based on the total amount of the block chain A, and 30% by mass or more. It may be 50% by mass or more, 70% by mass or more, and 90% by 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 (block chain B, block chain C, etc.) having a different structure from the block chain A may have a structural unit derived from an anion polymerizable compound, for example. Examples of the anionic polymerizable compound include the compound represented by the formula (2-1) and the compounds exemplified as the other monomers described above.

The number average molecular weight Mn _A of the block chain A may be, for example, 500 to 1.0 × 10 ⁷ , 5000 to 1.0 × 10 ⁶ , and 5.0 × 10 ^{4 to} 1.0 × 10 6. 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, it may be 1.7 or less, 1.4 or less It may be. The lower limit of Mw _A / Mn _A is 1.

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

  The polymer compound according to the present 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 functional group conversion of the acyl group.

In this embodiment, for example, for the acyl group of the polymer compound, nucleophilic addition reaction, reduction reaction, oxidation reaction, photoreaction, coupling reaction, photocoupling reaction, radical reaction, Wittig reaction, acetalization reaction, A modified product can be obtained by performing an iminization reaction, esterification reaction, polymerization reaction (radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, etc.) and the like. More specifically, for example, a polymer such as a long-chain alkyl group or polystyrene can be added to a polymer compound by a nucleophilic addition reaction to obtain a graft polymer (comb polymer or the like). In addition, for example, a graft polymer (comb polymer or the like) can be obtained by polymerizing a polymerizable compound using an acyl group as a reaction site. 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 undergoes a photoreaction within a molecule or between molecules. Can be obtained. Such a polymer compound has a benzopinacol site.

  Examples of the polymer material containing the polymer compound according to the present embodiment and / or a modified product of the polymer compound include automobile elastomers, industrial elastomers, architectural elastomers, general-purpose elastomers, medical elastomers, and food elastomers. Suitable for applications such as various thermosetting or thermoplastic elastomers such as elastomers for resin modification, various adhesives, various sealing (coking) materials, films, resins, molding materials, paints, rubbers, coating materials, etc. Can do. Automotive elastomers include, for example, weather strips, hand brake 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. It can be used for Industrial elastomers can be used for applications such as gaskets, cap seals, tubes, silencer gears, tool grips, and the like. The elastomer for construction can be used for applications such as vibration control and seismic isolation rubber, for example. The general-purpose elastomer can be used for applications such as grips such as toothbrushes, pens, razors, 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, for example. The elastomer for resin modification can be used for applications such as improvement of impact resistance of polypropylene and improvement of heat resistance of polyethylene, for example.

(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 above-described polymer compound, and can be suitably used in a method for producing the polymer compound. The compound according to this embodiment may be rephrased as a ketone group-containing styrene derivative.

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 characteristics, mechanical characteristics, 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) and 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 be in accordance with the conditions of ordinary Grignard reaction, 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 (diglyme), diglyme (diglyme), triglyme (triglyme), benzene solvents such as toluene, xylene, benzene, etc. What is necessary is just to make it react at 20-100 degreeC 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, 1, 2- dibromoethane.

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

  One embodiment 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 includes anionic polymerization of the monomer component containing the compound represented by the formula (2-1) (hereinafter, “ The case of providing an anionic polymerization process ”) will be described in more detail.

  In the anionic polymerization step, the active species derived from the compound represented by formula (2-1) can exist stably 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 anion polymerization of the compound represented by the formula (2-1) is a living anion polymerization. Therefore, according to the production method, the polymer compound can be obtained with a designed molecular weight and a narrow molecular weight distribution.

  The monomer component may consist of only the compound represented by Formula (2-1), and may contain compounds other than the compound represented by Formula (2-1). When the monomer component consists only of the compound represented by the formula (2-1), a homopolymer of the compound represented by the 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 other monomers described above.

  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 components. , 50 mol% or more, 70 mol% or more, or 90 mol% or more.

  In the anionic polymerization step, for example, the monomer component may be anionically polymerized by a method in which a monomer component dispersed or dissolved in an organic solvent is reacted 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 the aromatic hydrocarbon 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. 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 in that a polymer compound having a narrower molecular weight distribution can be obtained. The present inventors presume the reason why a polymer compound having a narrower molecular weight distribution can be obtained by using an anionic polymerization initiator having these alkali metal elements as follows. In the following, for convenience, in the anionic polymerization initiator, a portion that becomes a nucleophilic species in the reaction with the monomer component is called an anion portion, and a portion that becomes a counter cation is called a cation portion.

  In anionic polymerization of a monomer having an acyl group, there is a possibility that a reaction between an anionic polymerization initiator and an acyl group or a reaction between a growth terminal anion and an acyl group occurs 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 is difficult to proceed. Since 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, the molecular weight is obtained by using an anionic polymerization initiator having these alkali metal elements. The present inventors presume 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. , A tert-butyl group, and the like. Since these anion parts are reasonably bulky and weak in nucleophilicity due to resonance stabilization, a polymer compound having a molecular weight as designed and a narrower molecular weight distribution can be obtained by using a polymerization initiator having these anion parts. 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, and diphenylmethyl. Sodium, diphenylmethyl potassium, diphenylmethyl cesium, triphenylmethyl lithium, triphenylmethyl sodium, triphenylmethyl potassium, triphenylmethyl cesium, methyl lithium, ethyl lithium, normal propyl lithium, isopropyl lithium, normal butyl lithium, isobutyl lithium, Examples include sec-butyllithium and tert-butyllithium.

  The amount of the anionic polymerization initiator can be appropriately adjusted according to the molecular weight 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.

  In the anionic polymerization step, a polymerization terminator may be used. 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 according to the conversion rate of the monomer component 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, and may be, for example, −100 ° C. to 100 ° C., and −50 ° C. to 50 ° C. It may be in ° C.

  In one embodiment, the polymerization step includes a step A in which a monomer component A containing a compound represented by the formula (2-1) is polymerized to obtain a block chain A, and a monomer component B is polymerized to block. Step B to obtain chain B may be included. According to a manufacturing method provided with such a polymerization process, the block copolymer which has the block chain A which has a structural unit represented by Formula (1-1) can be manufactured.

  In the above 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 the formula (2-1). As the said compound, the compound illustrated as said other monomer is mentioned.

  In the monomer component A, 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 A. It may be 50 mol% or more, may be 70 mol% or more, and may be 90 mol% or more.

  The monomer component B has only to 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 the compound represented by the formula (2-1) and the other monomers described above. Compounds.

  In the said manufacturing method, the order which performs the process A and the process B is not specifically limited.

  For example, in the 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. Step B to obtain a block chain B that binds to the block chain A may be included.

  In the polymerization step, 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 is reacted with the monomer component A. Step A for obtaining a block chain A that binds to the block chain B may be included.

  In addition, since the compound represented by Formula (2-1) has high electrophilicity, in the case where the monomer component is polymerized by anionic polymerization in Steps A and B, Step A is performed after Step B is performed. By performing, it tends to be easy to obtain a polymer compound having a molecular weight as designed and a narrower molecular weight distribution.

  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.

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

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

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

[Wherein Ph represents a phenyl group. ]

[Wherein, MD represents a methyldimethanocyclodecenyl group. ]

Example 1
Anionic polymerization of Compound A was performed by a break seal method using a Pyrex (registered trademark) reaction vessel.

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

  Subsequently, the break seal of the container in which the diphenylmethyl lithium solution was accommodated was broken, the diphenylmethyl lithium solution was transferred to the reaction container, and then cooled to -78 ° C. The reaction solution containing the diphenylmethyllithium solution was vigorously stirred, and the break seal of the container containing Compound A and THF, which had been cooled to −78 ° C., was split, added to the reaction solution, and allowed to react for 48 hours.

After completion of the polymerization, the reaction vessel was opened, and 2 ml of methanol as a polymerization terminator was added to stop the polymerization. When the reaction solution was poured into 100 ml of methanol, a white solid precipitated. The solid is filtered off under reduced pressure using Kiriyama funnel and Kiriyama filter paper, dissolved in 5 ml of benzene, and freeze-dried to give a polymer having a structural unit represented by the following formula (A-2) 30 mg of the compound (polymer compound 1) was obtained. A ¹ H-NMR chart of the resulting polymer compound 1 is shown in FIG. In addition, the conversion rate of the compound A calculated | required from ¹ H-NMR of the obtained high molecular compound 1 was 10%. Moreover, the polymer yield was 5 mass% with respect to the charged compound A.

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

  About the obtained high molecular compound 1, the calculated value of the number average molecular weight Mn was computed by the method of following (I). 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 were as 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 molecular weight of the polymer chain calculated on the basis of the ratio (molar) of the monomer component used (the amount of the monomer component used / the amount of the polymerization initiator used) is summed, and the calculated value of the number average molecular weight Mn did.

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

(Example 2)
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. Anion polymerization was carried out 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 compound A obtained from ¹ H-NMR of the obtained polymer compound 2 was 100%. Moreover, the polymer yield was 88 mass% with respect to the charged compound A.

  For the obtained polymer compound 2, the calculation 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). went. The results were as shown in Table 1.

Example 3
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) Anion polymerization was carried out to obtain 426 mg of a polymer compound (polymer compound 3) having a structural unit represented by formula (A-2). The conversion rate of compound A obtained from ¹ H-NMR of the obtained polymer compound 3 was 89%. Moreover, the polymer yield was 80 mass% with respect to the charged compound A.

  For the obtained polymer compound 3, the calculation 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). went. The results were as shown in Table 1.

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

  For the obtained polymer compound 4, the calculation 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) above. went. The results were as shown in Table 1.

The obtained polymer compound 4 was measured glass transition temperature Tg and 10% by weight reduction temperature _{T 10} in the manner described below (IV). Tg was 193 ° C. and T ₁₀ was 430 ° C. Incidentally, 10% by weight reduction temperature T _10, the mass of the polymer compound 4, means the temperature at which decreased 10% from the mass at the start of measurement.

(IV) was measured by using measuring DSC apparatus for a glass transition temperature Tg and 10% by weight reduction temperature _{T 10} a (Seiko Denshi "DSC6220"). In 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. Thereafter, the temperature was raised again 20 ° C. / min, to measure the glass transition temperature (Tg) and 10 wt% reduction temperature _{(T 10).}

(Example 5)
Example 1 was repeated except that 13.2 mg (0.0792 mmol) of potassium naphthalene (K-Naph) was used instead of diphenylmethyllithium, and the amount of 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 formula (A-2). The conversion rate of compound A obtained from ¹ H-NMR of the obtained polymer compound 5 was 100%. Moreover, the polymer yield was 89 mass% with respect to the charged compound A.

  For the obtained polymer compound 5, the calculation 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 carried out by the methods (I), (II) and (III). went. The results were as shown in Table 1.

(Example 6)
Example 1 was used except that 22.4 mg (0.0794 mmol) of triphenylmethyl potassium (Ph ₃ CK) was used instead of diphenylmethyl lithium, and the amount of Compound A used was 668.6 mg (2.51 mmol). Similarly, anionic polymerization was performed to obtain 595 mg of a polymer compound (polymer compound 6) having a structural unit represented by formula (A-2). The conversion rate of Compound A obtained from ¹ H-NMR of the obtained polymer compound 6 was 95%. Moreover, the polymer yield was 89 mass% with respect to the charged compound A.

  About the obtained polymer compound 6, the calculation 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 were as shown in Table 1.

(Example 7)
The same as Example 1 except that 20.9 mg (0.0697 mmol) of diphenylmethylcesium (Ph ₂ CHCs) was used instead of diphenylmethyllithium, and the amount of Compound A used was 623.3 mg (2.34 mmol). Anion polymerization was carried out to obtain 530 mg of a polymer compound (polymer compound 7) having a structural unit represented by formula (A-2). The conversion rate of compound A obtained from ¹ H-NMR of the obtained polymer compound 7 was 100%. Moreover, the polymer yield was 85 mass% with respect to the charged compound A.

  For the obtained polymer compound 7, the calculation 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) above. went. The results were as shown in Table 1.

(Example 8)
Anionic polymerization was carried out 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. A ¹ H-NMR chart of the resulting polymer compound 8 is shown in FIG. In addition, the conversion rate of the compound B calculated | required from ¹ H-NMR of the obtained high molecular compound 8 was 16%. Moreover, the polymer yield was 10 mass% with respect to the compound B prepared.

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

For the obtained polymer compound 8, calculation of the number average molecular weight Mn and 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) above. went. The results were as shown in Table 2. Further, in the method of the above (IV), were measured glass transition temperature (Tg) and 10 wt% reduction temperature _{(T 10).} Tg was 135 ° C. and T ₁₀ was 415 ° C.

Example 9
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. Then, anionic polymerization was carried out 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). Conversion of compound B obtained from ¹ H-NMR of the obtained polymer compound 9 was 100%. Moreover, the polymer yield was 85 mass% with respect to the charged compound B.

  For the obtained polymer compound 9, the calculation 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) above. went. The results were as shown in Table 2.

(Example 10)
Example 8 was used except that 9.8 mg (0.0517 mmol) of diphenylmethyl sodium 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 carried out in the same manner as above to obtain 441 mg of a polymer compound (polymer compound 10) having a structural unit represented by formula (B-2). The conversion rate of the compound B calculated | required from ¹ H-NMR of the obtained high molecular compound 10 was 83%. Moreover, the polymer yield was 78 mass% with respect to the charged compound B.

  For the obtained polymer compound 10, the calculation 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) above. went. The results were as shown in Table 2.

(Example 11)
Example 8 except that 8.8 mg (0.0428 mmol) of diphenylmethylpotassium was used in place of diphenylmethyllithium, the amount of compound B used was 431.1 mg (2.29 mmol), and the reaction time was 72 hours. Anion polymerization was carried out in the same manner as above to obtain 272 mg of a polymer compound (polymer compound 11) having a structural unit represented by formula (B-2). The conversion rate of Compound B obtained from ¹ H-NMR of the obtained polymer compound 11 was 100%. Moreover, the polymer yield was 63 mass% with respect to the compound B prepared.

  About the obtained high molecular compound 11, calculation 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 carried out by the methods (I), (II) and (III). went. The results were as shown in Table 2.

(Example 12)
Anionic polymerization was carried out in the same manner as in Example 8, except that 21.4 mg (0.0757 mmol) of triphenylmethyl potassium was used instead of diphenylmethyllithium, and the amount of compound B used was 679.7 mg (3.61 mmol). And 415 mg of a polymer compound (polymer compound 12) having the structural unit represented by formula (B-2) was obtained. The conversion rate of Compound B obtained from ¹ H-NMR of the obtained polymer compound 12 was 99%. Moreover, the polymer yield was 61 mass% with respect to the charged compound B.

  For the obtained polymer compound 12, calculation of the number average molecular weight Mn and 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) above. went. The results were as shown in Table 2.

(Example 13)
Anionic polymerization was carried out 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 used was 625.1 mg (3.32 mmol). As a result, 538 mg of a polymer compound (polymer compound 13) having a structural unit represented by the formula (B-2) was obtained. Conversion of compound B obtained from ¹ H-NMR of the obtained polymer compound 13 was 98%. Moreover, the polymer yield was 86 mass% with respect to the charged compound B.

  With respect to the obtained polymer compound 13, the calculation 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) above. went. The results were as shown in Table 2.

(Example 14)
Anionic polymerization was carried out 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 compound B used was 675.9 mg (3.59 mmol). Then, 412 mg of a polymer compound (polymer compound 14) having a structural unit represented by the formula (B-2) was obtained. The conversion rate of Compound B determined from ¹ H-NMR of the obtained polymer compound 14 was 98%. Moreover, the polymer yield was 61 mass% with respect to the charged compound B.

  For the obtained polymer compound 14, calculation of the number average molecular weight Mn and 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) above. went. The results were as 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 carried out in the same manner as in Example 1 except that the time was set to obtain 556.1 mg of a polymer compound (polymer compound 15) having a structural unit represented by the following formula (C-2). A ¹ H-NMR chart of the resulting polymer compound 15 is shown in FIG. In addition, the conversion rate of the compound C calculated | required from ¹ H-NMR of the obtained high molecular compound 15 was 100%. Moreover, the polymer yield was 100 mass% with respect to the compound C prepared.

For the obtained polymer compound 15, the calculation 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) above. went. The results were as shown in Table 2. Further, in the method of the above (IV), were measured glass transition temperature (Tg) and 10 wt% reduction temperature _{(T 10).} Tg was 120 ° C. and T ₁₀ was 408 ° C.

[Wherein Ph represents a phenyl group. ]

(Example 16)
Anion was obtained in the same manner as in Example 1, except that 462.7 mg (1.52 mmol) of compound D was used instead of compound A, and 8.7 mg (0.042 mmol) of diphenylmethyl potassium was used instead of diphenylmethyllithium. 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). A ¹ H-NMR chart of the obtained polymer compound 16 is shown in FIG. In addition, the conversion rate of the compound C calculated | required from ¹ H-NMR of the obtained high molecular compound 17 was 100%. Moreover, the polymer yield was 76 mass% with respect to the compound D prepared.

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

[Wherein, MD represents a methyldimethanocyclodecenyl group. ]

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

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

(Reference Example 3)
Anionic polymerization of styrene was carried out 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. And 13 g of polystyrene was obtained.

About the obtained polystyrene, the method of said (II), (III) and (IV) WHEREIN: Measurement of number average molecular weight Mn and molecular weight distribution Mw / Mn, and glass transition temperature (Tg) and 10 mass% reduction | decrease temperature ( Measurement of T ₁₀ ) was performed. Mn is 96000, Mw / Mn of 1.04, Tg is 104 ° _{C., T 10} was 396 ° C..

(Example 17)
Block copolymerization of Compound A and Compound B was performed by a break seal method using a Pyrex (registered trademark) reaction vessel.

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

  Next, the break seal containing the diphenylmethyl potassium solution was broken, and 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 the break seal containing compound A and THF cooled to −78 ° C. was split, added to the reaction solution, and allowed to react for 48 hours. Thereafter, a break seal containing Compound B and THF was broken, added to the reaction solution, and stirred as it was for 48 hours. After completion of the polymerization, the reaction solution was opened, and 2 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 off under reduced pressure using Kiriyama funnel and Kiriyama filter paper, dissolved in 5 ml of benzene, and freeze-dried, whereby the structural unit represented by formula (A-2) and formula (B- 881 mg of polymer compound 17 having the structural unit represented by 2) was obtained. A ¹ H-NMR chart of the resulting polymer compound 17 is shown in FIG. In addition, the polymer yield was 88 mass% with respect to the total amount of the compound A and the compound B which were prepared.

  For the obtained polymer compound 17, the calculation 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) above. went. The calculated value of the number average molecular weight Mn was 14100, whereas the measured value of the number average molecular weight Mn was 15000. Moreover, molecular weight distribution Mw / Mn was 1.07.

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

Further, calculation of the number average molecular weight Mn _A of the homopolymer and measurement of the number average molecular weight Mn _A and the molecular weight distribution Mw _A / Mn _A by the methods (I), (II) and (III) above. Went. The calculated value of the 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 a 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, an increase in the number average molecular weight Mn of the polymer compound 17 was confirmed. Further, when the GPC curve of the homopolymer and the GPC curve of the polymer compound 17 were compared, the movement of the peak position was confirmed (see FIG. 15). From these results, the polymer compound 17 was blocked. It was confirmed to be a copolymer. Moreover, when the molecular weight distribution Mw _A / Mn _{A of} the homopolymer was compared with the molecular weight distribution Mw / Mn of the polymer compound 17, there was almost no difference in the molecular weight distribution.

(Example 18)
[Synthesis of graft copolymer with living polystyrene]
First, anionic polymerization was carried out 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 molecular compound 1 ′) was obtained. About the obtained polymer compound 1 ′, calculation of the number average molecular weight Mn and measurement of the number average molecular weight Mn and the molecular weight distribution Mw / Mn by the methods (I), (II) and (III) above. 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. Moreover, molecular weight distribution Mw / Mn was 1.06.

  Next, graft polymerization of the obtained polymer compound 1 'and polystyrene was performed by a break seal method using a Pyrex (registered trademark) reaction vessel.

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

  Next, 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 added to the reaction solution and allowed to react for 10 minutes. Thereby, polystyrene was synthesized. The measured value of the number average molecular weight Mn was 4500.

  Thereafter, 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 completion of the polymerization, the reaction solution was opened, and 2 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 a Kiriyama funnel and Kiriyama filter paper, and then excessively used polystyrene was removed by fractional precipitation with a mixed solution of hexane and cyclohexane. As a result of separation and purification by fractional precipitation, 0.65 g of a polymer compound (modified product of polymer compound 1 ′, polymer compound 18) having a structural unit represented by the following formula (E) was obtained. A ¹ H-NMR chart of the resulting polymer compound 18 is shown in FIG. The ¹ H-NMR of the polymer compound 18 almost coincided with that of 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 charged polymer compound 1 ′ and styrene.

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

  For the obtained polymer compound 18, the calculation 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) above. went. The calculated value of the number average molecular weight Mn was 209000, whereas the measured value of the number average molecular weight Mn was 165000. The molecular weight distribution Mw / Mn was 1.02. There was almost no difference in the molecular weight distribution between 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]
The polymer compound having the structural unit represented by the formula (C-2) was subjected to a crosslinking reaction with the following contents.

  100 mg of the polymer compound 15 (containing 0.48 mmol of carbonyl group) was placed in the 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 carried out continuously for 11 hours using an ultrahigh pressure UV lamp (250 w, manufactured by USHIO INC., Trade name: USHIO optical module). After 11 hours of UV irradiation, it was confirmed that the solution lost its fluidity and gelled. Further, it was confirmed that the solution which was colorless and transparent before UV irradiation was changed to light yellow after UV irradiation.

  FT-IR measurement was performed on the solution before UV irradiation and the gel obtained after UV irradiation. In the measurement, a solution before UV irradiation and a gel obtained after UV irradiation were each applied on a KBr plate and evaporated to dryness. The 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 part of the carbonyl group of the polymer compound 15 is excited by UV irradiation, and a crosslinking reaction proceeds, and a crosslinked product of the polymer compound 15 is obtained. It was confirmed that

Claims (13)

The high molecular compound which has a structural unit represented by a following formula (1-1).

[Wherein R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ]   The high molecular compound of Claim 1 which is a block copolymer which has a block chain which has a structural unit represented by the said Formula (1-1). The high molecular compound of Claim 1 or 2 which has a structure represented by following formula (1-2).

[Wherein, R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position, and n represents 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 high molecular compound of Claim 1 which is a homopolymer of the compound represented by a following formula (2-1).

[Wherein R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ]   The polymer compound according to any one of claims 1 to 5, wherein a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 2.0 or less.   The polymer compound according to any one of claims 1 to 6, wherein the hydrocarbon group is an alkyl group having 4 to 40 carbon atoms. A method for producing the polymer compound according to any one of claims 1 to 7,
A manufacturing method provided with the process of anion-polymerizing the monomer component containing the compound represented by a following formula (2-1).

[Wherein R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ]   The manufacturing method according to claim 8, wherein an anionic polymerization initiator having at least one alkali metal element selected from the group consisting of lithium, sodium, potassium and cesium is used in the step. A compound represented by the following formula (2-1).

[Wherein R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. ] A method for producing the compound of claim 10, comprising:
A manufacturing method provided with the process with which the compound represented by following formula (3) and the compound represented by following formula (4) are made to react.

[Wherein, X ¹ represents a halogen group. ]

[Wherein R ¹ represents a hydrocarbon group having no hydrogen atom at the α-position. X ² represents a halogen group or an acyloxy group. ]   A modified product of the polymer compound obtained by modifying the acyl group of the polymer compound according to claim 1. A polymer material comprising the polymer compound according to claim 1 and / or the modified product according to claim 12.