JP2000302718A - Reactive dendron and transition metal complex containing the dendron as ligand - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polybenzyldendron rich in various polymerization reactivities or addition reactivity, etc. such as hydroboration by including a vinyl inducing group in a nonfocal point terminal. SOLUTION: This polybenzyl ether dendron has a vinyl inducing group, e.g. vinylbenzyl group or acryloyl group n a nonfocal point terminal (the terminal on the spreading side of a fan when the dendron is schemtically regarded as a fan shape). The above polybenzyl ether dendron is obtained by carrying out an etherifying reaction in which plural kinds of benzyl halide dendrons containing at least one kind of vinylbenzyl halide dendron are successively reacted with hydroxybenzyl alcohols having plural phenolic hydroxyl groups without isolation. A transition metal complex containing the dendron as a ligand is capable of providing a copolymer, etc., with, e.g. a raw material monomer constituting an acrylic resin, etc., and the copolymer exhibits a good transparency and a good mechanical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive dendron having a vinyl-derived group at a terminal, a method for producing the same, a transition metal complex having the dendron as a ligand, a polymer thereof, and a use of the polymer. . Since the vinyl-derived group of the dendron has various reactivity such as radical polymerizability, when the dendron has a coordinating functional group, a transition metal complex containing the same as a ligand also has the same reactivity. . Therefore, for example, a copolymer of the complex with another polymerizable monomer or a homopolymer of the complex itself can be provided.

[0002] The polymer thus obtained has good transparency and mechanical strength, and can be used as a resin composition by utilizing the compatibility with various resins. Such a polymer or resin composition can be used as various functional sheets. For example, when the above-mentioned transition metal complex has a fluorescence generating ability, it provides a high-luminance fluorescent sheet, and thus is useful as a luminous body such as a display or a wavelength conversion layer for improving the output of a solar cell.

[0003]

2. Description of the Related Art An organic ligand constituting a transition metal complex comprises
It is well known that it affects the luminescence of transition metals. This is because not only the ligand field effect which has been known for a long time,
Recently, a contribution of a sensitizing effect based on the characteristic of the chemical structure of an organic ligand has been recognized (for example, LM Dupra).
y et al .; Am. Chem. Soc. , 119, 10
243 (1997)).

When the transition metal is a lanthanoid in particular, it exhibits an emission band having a very narrow wavelength width due to the transition of f-orbital electrons, and is generally less susceptible to the ligand field effect. A very large sensitizing effect based on the characteristics of the chemical structure was reported. That is, M. Kawa et al .; C
hem. Mater. 10, 286-296 (1
998), a lanthanoid trivalent cation having polybenzylether dendron as a ligand (hereinafter referred to as "L
n ³⁺ . ) Complex, wherein the dendron is T
Sensitizes b ³⁺ , Eu ^3+, etc. to greatly improve the fluorescence generating ability. In addition, dendron (Dendron) here is a dendrimer (Dendron) which has become popular in recent years.
rimer: a generic term for polymer structures having dendritic regular branches), which is an agreement with a term widely used in the meaning of a molecular building component having such a structural unit. R. Newcome by Newkome et al .; Dendri
ticMolecules, Concepts ・ Syn
these ・ Perspectives (VCH V
erlagsgesellschaft mbH; We
inheim, Germany; 1996, ISBN:
3-527-29325-6).

However, the transition metal complex having the above-mentioned fluorescent polybenzyl ether dendron as a ligand is
When a fluorescent resin composition is produced by incorporating it into an amorphous general-purpose resin (for example, an acrylic resin or a styrene resin), the compatibility between the resin and the transition metal complex is not always sufficient, Addition of the complex sometimes caused opacity due to phase separation or the like.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a polybenzyl ether dendron having a reactivity such as polymerization with a general-purpose resin, a method for producing the same, and a method for producing the same. To provide a transition metal complex having a dendron as a ligand, a polymer containing the complex as a monomer unit, a resin composition containing the same, and a sheet-like molded article obtained by molding the polymer. is there.

[0007]

Means for Solving the Problems As a result of diligent studies to achieve the above object, the present inventors have introduced various types of polybenzyl ether dendrons by introducing a vinyl derivative group at the non-focal point terminal of the dendron. It is possible to impart reactivity with the resin, and furthermore, it becomes possible to uniformly contain the transition metal complex having the dendron as a ligand in the resin, so that the resin can be applied to uses such as a display. Knowing that the present invention has been reached. That is, a first gist of the present invention resides in a polybenzyl ether dendron having a vinyl derivative group at a non-focal point terminal.

[0008] A second aspect of the present invention is to provide a method of sequentially treating a plurality of benzyl halide dendrons containing at least one vinylbenzyl halide dendron with hydroxybenzyl alcohols having a plurality of phenolic hydroxyl groups without isolation. The method for producing polybenzyl ether dendron, characterized by including an etherification reaction. A third gist of the present invention is a transition metal complex having the above-mentioned polybenzyl ether dendron as a ligand, a polymer containing the transition metal complex as a monomer unit constituting a polymer, and a transition metal complex. And a sheet-like molded product obtained by molding the polymer or the resin composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. [Polybenzyl ether dendron] The polybenzyl ether dendron of the present invention has a benzyl ether residue as a repeating unit. The specific chemical structure of the repeating unit is represented by the following formula (1):
5-branched structure such as 5-dioxybenzyl residue, 3,4-dioxybenzyl residue and 2,4-dioxybenzyl residue, or 3,4,5-trioxybenzyl residue,
Examples include a three-branched structure such as a 2,3,4-trioxybenzyl residue, a 2,4,5-trioxybenzyl residue, and a 2,3,5-trioxybenzyl residue. It is preferable from the viewpoint of light emission behavior when the 3,5-dioxybenzyl residue represented by 1) is a complex.

[0010]

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The polybenzyl ether dendron of the present invention has a vinyl group at a non-focal point terminal. Here, the focal point is, for example, as described in the above-mentioned book by Newkome et al., The starting point of the branch structure of the dendron (the fan point when the dendron is schematically considered to be a sector shape). (Equivalently) (see FIG. 1). Therefore, the non-focal point end means an end other than the focal point, in other words, an end on the spreading side of the fan when the dendron is schematically considered to be a fan shape. For example, in the case of FIG. 1 in which the dendron is composed only of a repeating unit having a two-branch structure, the number of non-focal point terminals is two in the first generation, four in the second generation, eight in the third generation, and four in the third generation. In the nth generation, the number is 2 n, such as 16 in the generation. Here, the generation of the dendron means the order of the branch as described in FIG.

The vinyl-derived group in the present invention means a carbon-carbon double bond residue to which a substituent represented by the following formula (2) may be bonded. However, in the formula (2), R ¹ to
R ³ each independently represents an alkyl group having 3 or less carbon atoms or a hydrogen atom. Specifically, an ethenyl group, a 1-methylethenyl group (isopropenyl group), a cis-1-propenyl group, a trans-1-propenyl group, and a 2-methyl-1
-Propenyl group, 1,2-dimethyl-1-propenyl group and the like. Of these, an ethenyl group and a 1-methylethenyl group are preferred in terms of reactivity, and among them, an ethenyl group is most preferred. Hereinafter, the vinyl group will be described as a representative.

[0013]

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The chemical properties of the vinyl group at the non-focal point terminal of the polybenzyl ether dendron of the present invention vary depending on the chemical structure in the dendron to which it is directly bonded due to an electronic effect or the like. The vinyl group can undergo various chemical reactions, such as radical polymerization, anionic polymerization,
Polymerization reaction such as cationic polymerization, or hydroboration, addition of hydrogen halide, addition of halogen molecule,
Since it undergoes an addition reaction such as addition of a water molecule or addition of a hydrogen molecule, it is used as a reaction point of the dendron of the present invention.

Therefore, it is necessary to select a vinyl group having a chemical property suitable for a desired type of reaction. For example, in the case of radical polymerization, vinyl benzyl group, vinyl phenyl group, vinyl naphthyl group, vinyl group conjugated with an aromatic ring such as isopropenyl benzyl group, or acryloyl group, methacryloyl group, crotonoyl group, fumaroyl group, maleinoyl A vinyl group conjugated with a carbonyl group such as a group is preferable, and in the case of anionic polymerization, a vinyl group conjugated with an aromatic ring such as a vinylbenzyl group, a vinylphenyl group, a vinylnaphthyl group, or an isopropenylbenzyl group is preferable. In the case of a general addition reaction such as hydroboration, other than the vinyl group suitable for the radical polymerization, a 2-propenyl group (allyl group), a butenyl group,
Alkenyl groups such as pentenyl, hexenyl and octenyl can also be used. Of these, from the viewpoint of versatility and ease of production, the purpose of the present invention is to provide a vinyl group conjugated to an aromatic ring such as a vinylbenzyl group or a vinylphenyl group, or a vinyl conjugated to a carbonyl group such as an acryloyl group or a methacryloyl group. Groups and the like are more preferred, and among them, a vinylbenzyl group is most preferred.

The number of vinyl groups at the non-focal point end of the polybenzyl ether dendron of the present invention is not limited, and is arbitrarily controlled according to desired reactivity (eg, degree of crosslinking during radical polymerization). When a specific structure is illustrated for a polybenzyl ether dendron having a 3,5-dioxybenzyl residue represented by the above formula (1) as a repeating unit, the first generation has one or two vinyl groups. Structure (general formula (3) below), 1 for the second generation
A structure having from 4 to 4 vinyl groups (the following general formula (4));
In the third generation, a structure having 1 to 8 vinyl groups (the following general formula (5)), and in the fourth generation, a structure having 1 to 16 vinyl groups (the following general formula (6)) are possible. is there. In the following general formulas (3) to (6), R ⁴ to
R ¹⁹ each independently represents a vinyl group or a hydrogen atom, and X represents a functional group at a focal point.

[0017]

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[0018]

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[0019]

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[0020]

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In the polybenzyl ether dendron of the present invention, an arbitrary functional group (corresponding to X in the above general formulas (3) to (6); hereinafter abbreviated as FP functional group) may be bonded to its focal point. Absent. Examples of useful FP functional groups include carboxyl groups, ester groups, amide groups, maleimide groups, acid anhydride groups, hydroxyl groups, amino groups, thiol groups, and halogenated alkyl groups such as benzyl halide groups as reactive functional groups. And the like, as the coordinating functional group, carboxyl group, β-diketone group, phenanthrenyl group, bipyridyl group and the like, respectively, among them, ester group,
Reactive functional groups such as hydroxyl groups and benzyl halide groups are particularly suitable in terms of their ability to be converted into various derivatives, and coordinating functional groups such as carboxyl groups are particularly suitable for luminescence properties due to coordination to lanthanoid cations Is important in that respect.

[Method for Producing Polybenzyl Ether Dendron] The dendron of the present invention having a polybenzyl ether structure can be obtained from C.I. J. Hawker et al .; Am. Che
m. Soc. , 112, 7638 (1990). <Synthesis of branched constituent unit at non-focal point end>

First, it is necessary to synthesize a non-focal point terminal branched structural unit having a vinyl group. For example, as described in the above-mentioned literature, an etherification reaction using potassium carbonate as a base (Williamson synthesis) in a solvent such as acetone, tetrahydrofuran, or N, N-dimethylformamide in the presence of 18-crown-6 ether ) Is carried out using benzyl halides having a vinyl group such as 4-vinylbenzyl chloride and 3,5-dihydroxybenzyl alcohol (hereinafter abbreviated as 35DHBA) as raw materials, whereby a 3,5-dioxybenzyl residue is obtained. A branched constituent unit is obtained. In this reaction example, 4-
When vinyl benzyl chloride is used in an amount of 2 equivalents or more with respect to 35DHBA, 3,5 which is the compound a in the following formula (7)
-Bis (4-vinylbenzyloxy) benzyl alcohol is obtained, but 4-vinylbenzyl chloride is converted to 35D
When less than 2 equivalents are used with respect to HBA and then benzyl bromide is reacted, the compound c in the following formula (8) is 3
-Benzyloxy-5- (4-vinylbenzyloxy)
It is possible to produce benzyl alcohol.

[0024]

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[0025]

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In the etherification reaction, when a low-reactivity benzyl halide such as benzyl chloride is used as a raw material, bromide ions such as tetraethylammonium bromide and tetraethylammonium iodide and quaternary ammonium iodide ions are used. In some cases, coexistence of a salt is preferable. When a structure other than a 3,5-dioxybenzyl residue is required as a branched structure of the dendron, hydroxybenzyl alcohol having a corresponding substitution position may be used as a raw material. For example, if branching by a 3,4-dioxybenzyl residue is required, use 3,4-dihydroxybenzyl alcohol instead of 35DHBA. In the etherification reaction, a suitable radical scavenger, for example, 2,6-
In some cases, addition of di-tert-butyl-4-methylphenol or the like is preferable.

The thus obtained branched benzyl alcohol having a vinyl group at a non-focal point end is then converted into a corresponding branched benzyl halide such as a corresponding branched benzyl bromide. For example, the compound a in the formula (7) is replaced by the compound b in the formula, 3,5-bis (4-vinylbenzyloxy) benzyl bromide,
Compound c in the above is converted to compound d in the formula, 3-benzyloxy-5- (4-vinylbenzyloxy) benzyl bromide. The bromination method is not particularly limited. For example, as described in the literature, a method of reacting carbon tetrabromide and triphenylphosphine in an ether solvent such as tetrahydrofuran, and a method of reacting phosphorus tribromide A method, a method of acting hydrogen bromide, etc. are possible,
The method of reacting carbon tetrabromide and triphenylphosphine is optimal in terms of conversion yield. The structures of the compounds a and b in the formula (7) are examples of a non-focal point terminal branched structural unit having two vinyl groups, and the structures of the compounds c and d in the formula (8) are one vinyl. It is an example of a non-focal point terminal branched constituent unit having a group.

<Method of increasing the number of dendron generations> The compounds which are non-focal point terminal branching constitutional units described in the above formulas (7) and (8) are nothing but the first generation polybenzyl ether dendrons of the present invention. Higher generations of the polybenzyl ether dendrons of the present invention can be prepared using lower generations of benzyl bromide dendrons (eg, compound b
And compound d) as a raw material in the above-mentioned etherification reaction.

In this case, by selecting the low-generation benzyl bromide dendron, which is the raw material on the non-focal point side, and controlling the use equivalent, the number and the bonding position of the non-focal point terminal vinyl groups of the high-generation dendron, which is the product, are determined. It can be controlled. That is, as shown in the following formula (9), for example, 2 equivalents or more of the first generation benzyl bromide dendron (compound b) having two vinyl groups (preferably 2.0
~ 2.5 equivalents) on 35DHBA to give compound e, a second generation benzyl alcohol dendron having four non-focal point terminal vinyl groups. When less than 2 equivalents (preferably about 1 equivalent) are applied, a dendron having no vinyl group in the reaction system ([G
-1] -Br; J. (Known from Hawker et al.) Can produce a second generation benzyl alcohol dendron having two non-focal point terminal vinyl groups, compound f. . In the etherification reaction in which a plurality of such benzyl halide dendrons are successively acted on without being isolated to hydroxybenzyl alcohols having a plurality of phenolic hydroxyl groups, if necessary, a plurality of benzyl halide dendrons may be used. The order of use may be changed. For example, synthetic strategies in which dendrons with fewer vinyl groups are reacted sequentially to minimize undesirable side reactions (eg, radical reactions) of the vinyl groups often give good results.

[0030]

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According to the same synthetic strategy, as shown in the following formula (10), 2 equivalents or more (preferably about 2.0 to 2.5 equivalents) of the first generation benzyl bromide dendron (compound d) having one vinyl group. On 35DHBA gives compound g, a second generation benzyl alcohol dendron with two non-focal point terminal vinyl groups, but less than 2 equivalents of compound d against 35DHBA (preferably about [G-1] -B which is a dendron having no vinyl group.
When r is acted upon, it is possible to produce a second generation benzyl alcohol dendron having a vinyl group at one non-focal point terminal which is compound h.

[0032]

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It should be noted that the compound f
And compound g are both second-generation benzyl alcohol dendrons having two non-focal point terminal vinyl groups, but are different isomers with different bonding positions of the vinyl groups. That is, compound b or compound d in the above formula,
Alternatively, according to the method for producing a dendron of the present invention, the method includes a etherification reaction in which plural kinds of benzyl halide dendrons such as [G-1] -Br are successively acted on hydroxybenzyl alcohols having plural phenolic hydroxyl groups such as 35DHBA. It became possible for the first time to precisely control the number and position of vinyl groups at the end of the non-focal point.
By the same synthesis strategy, 3
Second having two non-focal point terminal vinyl groups
A generation of polybenzyl ether dendrons (compound i) is also obtained.

[0034]

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The various second-generation benzyl alcohol dendrons thus synthesized can be converted to the corresponding second-generation benzyl bromide dendrons by the same bromination reaction as described above. Further, by using this as an etherification reaction raw material, a third group having a vinyl group at a non-focal point terminal whose number and position are controlled by the same synthesis strategy as described above.
A generation of polybenzyl ether dendrons is obtained. Thereafter, similarly, higher generation dendrons can be obtained. However, it is usually difficult to obtain the polybenzyl ether dendron of the present invention of the seventh generation or higher due to steric hindrance and the like.
The following generations are preferably produced.

<Method for Introducing Carboxyl Group into Focal Point> A polybenzyl ether dendron (hereinafter, carboxylate dendron) having a carboxyl group bonded to a focal point, which is suitably used as a ligand of the transition metal complex of the present invention described below. Is referred to as "M. K
As described in the literature by Awa et al., it is obtained by hydrolysis of a dendron in which a carboxylic acid ester group is bonded to a focal point as a precursor thereof (hereinafter, referred to as ester dendron). Such an ester dendron is synthesized by the above-mentioned etherification reaction in which any benzyl bromide dendron described above acts on hydroxybenzoic acid esters having a plurality of phenolic hydroxyl groups.

Examples of hydroxybenzoic esters having a plurality of phenolic hydroxyl groups that can be used for the synthesis of the ester dendron include, for example, methyl 3,4-dihydroxybenzoate, ethyl 3,4-dihydroxybenzoate,
3,4-dihydroxybenzoates such as n-butyl 3,4-dihydroxybenzoate and tert-butyl 3,4-dihydroxybenzoate, methyl 3,5-dihydroxybenzoate, and ethyl 3,5-dihydroxybenzoate 3,5-dihydroxybenzoic acid esters;
2,5-dihydroxybenzoates such as methyl dihydroxybenzoate and ethyl 2,5-dihydroxybenzoate, methyl 2,4-dihydroxybenzoate, 2,4-
2,4-dihydroxybenzoic acid esters such as ethyl dihydroxybenzoate, and 2,3 such as methyl 2,3-dihydroxybenzoate and ethyl 2,3-dihydroxybenzoate
3,4,5-trihydroxybenzoic acid esters such as dihydroxybenzoic acid esters, methyl 3,4,5-trihydroxybenzoate, ethyl 3,4,5-trihydroxybenzoate, 2,4,5 2,4,5-trihydroxybenzoic acid esters such as methyl trihydroxybenzoate and ethyl 2,4,5-trihydroxybenzoate;
Methyl 2,3,5-trihydroxybenzoate, 2,3
2,3,5-trihydroxybenzoic acid esters such as ethyl 5-trihydroxybenzoate, and 2,3 such as methyl 2,3,4-trihydroxybenzoate and ethyl 2,3,4-trihydroxybenzoate And 4-trihydroxybenzoic acid esters. Of these, 3,4-
3,4-dihydroxybenzoic acid esters such as methyl dihydroxybenzoate and ethyl 3,4-dihydroxybenzoate; methyl 3,5-dihydroxybenzoate;
3,5-dihydroxybenzoic acid esters such as ethyl dihydroxybenzoate; 2,5 such as methyl 2,5-dihydroxybenzoate and ethyl 2,5-dihydroxybenzoate;
2,4-dihydroxybenzoic acid esters such as dihydroxybenzoic acid esters, methyl 2,4-dihydroxybenzoate and ethyl 2,4-dihydroxybenzoate;
Methyl 3,4,5-trihydroxybenzoate, 3,4
3,4,5-Trihydroxybenzoic acid esters such as ethyl 5-trihydroxybenzoate are preferably used,
Among them, methyl 3,4-dihydroxybenzoate, 3,4
3,4-dihydroxybenzoic acid esters such as ethyl-dihydroxybenzoate, and 3,3 such as methyl 3,5-dihydroxybenzoate and ethyl 3,5-dihydroxybenzoate.
2,5-dihydroxybenzoates such as 5-dihydroxybenzoates, methyl 2,5-dihydroxybenzoate, and ethyl 2,5-dihydroxybenzoate;
Dihydroxybenzoates such as 2,4-dihydroxybenzoates such as methyl 2,4-dihydroxybenzoate and ethyl 2,4-dihydroxybenzoate are more preferable.

[Transition Metal Complex] The present invention provides a transition metal complex containing the above-mentioned polybenzyl ether dendron having a carboxyl group bonded to a focal point as a ligand. The transition metal contained in the transition metal complex of the present invention is usually contained as a cation, and the carboxyl group of the dendron coordinates to the carboxylate anion by ionic bond. The transition metal cations that can be generally used in the present invention have atomic numbers of 21 to 31, 39 to 39.
It is a cation of an element corresponding to any one of 50 and 57 to 82. The valence of the metal cation is not particularly limited, but usually 1 to 4 valences are preferable in order to bind a sterically bulky dendron to the vicinity of the metal cation and to avoid excessive spatial crowding. , More preferably 2 or 3
Valence, most preferably trivalent.

The transition metal complex of the present invention can be prepared as described below.
Give a polymer containing this as a monomer component,
Such a polymer, or a resin composition containing the polymer
In order to increase the refractive index of the
The higher the atomic number of ON, the more effective. Optical amplifiers and waves
Optical communication components such as long converters, laser-related members, or
For use as a phosphor, wavelength range from ultraviolet to infrared
Is important. The transition metal complex of the present invention,
Polymer containing as a nomer component or containing this
For the purpose of imparting such a fluorescence-generating ability to the resin composition.
Suitable transition metal cations are listed in the periodic table of the elements.
And Cr³⁺, Mn³⁺, Mn⁴⁺, Fe²⁺, Fe³⁺Etc. 3d
4th period transition metal cation that causes electron transition, C
u⁺, Ag⁺, Au⁺Group 1B cations such as Ga⁺, I
n⁺, Tl⁺3B cations such as Sn, Sn²⁺, Pb²⁺Etc.
4B cation, Ce³⁺, Pr³⁺, Nd³⁺, Nd⁴⁺, S
m²⁺, Sm³⁺, Eu ²⁺, Eu³⁺, Tb³⁺, Dy³⁺, Dy
⁴⁺, Ho³⁺, Er³⁺, Tm²⁺, Tm³⁺, Yb ²⁺, Yb³⁺
Lanthanoid cations and the like. Among these
But Pr³⁺, Nd³⁺, Sm²⁺, Sm³⁺, Eu²⁺, Eu
³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, Yb³⁺
Lanthanoid cations such as visible to near infrared region, long
Because it emits fluorescence with features such as lifetime and narrow wavelength width
Suitable for practical use, especially Sm³⁺, Eu³⁺, T
b³⁺, And Dy³⁺Is more preferred and Eu³⁺And Tb³⁺
Is most preferred.

Since the transition metal complex of the present invention has the same reactivity as the vinyl group of the polybenzyl ether dendron of the present invention, it has the above-described polymerizability and addition reactivity. In carrying out such a reaction, it is necessary to select the number and type of vinyl groups suitable for the desired reaction format, and this example is also the same as described above. The transition metal complex of the present invention may contain a plurality of kinds of polybenzyl ether dendrons as ligands.

The transition metal complex of the present invention can be produced, for example, by an anion exchange reaction. More specifically, a carboxylic acid salt of a transition metal cation such as formic acid, acetic acid, oxalic acid, or propionic acid is brought into contact with the polybenzyl ether dendron of the present invention having a carboxyl group at a focal point by heating to cause the exchange reaction. The method for removing the carboxylic acid generated from the salt of the raw material is simple and suitable.
The anion exchange reaction by such heating is carried out without stirring or in a suitable inert solvent such as chlorobenzene or toluene under stirring conditions. In order to suppress side reactions such as oxidative deterioration due to high temperatures, nitrogen or argon or the like is used. It is desirable to carry out under an inert atmosphere. In addition, the removal of the generated carboxylic acid,
It is often desirable to work under reduced pressure.

In the transition metal complex of the present invention, the ionic bond between the transition metal cation and the carboxylate anion of the dendron is confirmed by shifting the absorption band of the carboxylate group from the corresponding carboxylic acid in the infrared absorption spectrum. It is possible. In the present invention, the transition metal complex as described above, in practical use, as long as the purpose of the present invention is not significantly impaired, any additive, for example, an organic phosphorus compound such as trioctylphosphine oxide or tri-n-butylphosphine oxide. Is coordinated, it is also possible to suppress a decrease in fluorescence intensity due to hydration or the like.

[Polymer Containing Transition Metal Complex as Monomer Unit] The present invention provides a polymer containing the above transition metal complex as a monomer unit. Such polymers are:
It is synthesized by utilizing the reactivity of the vinyl group of polybenzyl ether dendron which is a ligand of the transition metal complex. Specifically, known polymerization modes of vinyl monomers such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization can be applied. Of these, radical polymerization is the most general and preferred.

The polymer containing the transition metal complex of the present invention as a monomer unit includes a homopolymer of the transition metal complex and a copolymer of the transition metal complex with any monomer copolymerizable with the transition metal complex. means. In the case of a copolymer, the content of the transition metal complex is not limited, but is usually 1 to 100 mol% as a mole percentage of all monomers constituting the copolymer, and in terms of the expression of functions such as fluorescence generating ability. Preferably 5 to 100 mol%,
More preferably 10 to 100 mol%, most preferably 2
0-100 mol%. Such a copolymerization ratio can be determined, for example, by nuclear magnetic resonance (NMR) measurement.

The degree of polymerization of the polymer is not limited, but the transition metal complex of the present invention having a plurality of vinyl groups is
Determining the degree of polymerization in such cases is generally difficult, as it usually produces a crosslinked structure. As the monomer copolymerizable with the transition metal complex, in radical polymerization, acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, a carbon conjugated with a carbonyl group such as maleic anhydride,
Carboxylic acids having a carbon double bond, methyl acrylate, ethyl acrylate, n-butyl acrylate, isopropyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate,
Acrylates such as adamantyl acrylate, phenyl acrylate, benzyl acrylate and 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, methacryl Methacrylates such as 2-ethylhexyl acrylate, isobornyl methacrylate, adamantyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, crotonic esters such as methyl crotonate and ethyl crotonate, crotonic acid Methyl, crotonic esters such as ethyl crotonate, dimethyl fumarate, diethyl fumarate, fumaric esters such as monoethyl fumarate, dimethyl maleate, diethyl maleate, Maleic acid esters such as maleic acid monoethyl, acrylamide, methacrylamide, N-
Methyl acrylamide, N-methyl methacrylamide,
N-isopropylacrylamide, N-isopropylmethacrylamide, N, N-dimethylacrylamide,
Acrylamide derivatives such as N, N-dimethylmethacrylamide, crotonylamide and fumaric diamide; acrylonitrile derivatives such as acrylonitrile, methacrylonitrile and crotonilonitrile; vinyl carboxylate esters such as vinyl acetate, vinyl propionate and vinyl butyrate , Styrene, α-methylstyrene, 4-chloro-α-
Styrene derivatives such as methylstyrene, 4-vinylbenzyl chloride, and 4-acetoxystyrene; and the like. Among them, carboxylic acid having a carbon-carbon double bond conjugated to a carbonyl group such as acrylic acid, methacrylic acid, and maleic anhydride. Acids, methyl acrylate, ethyl acrylate,
Acrylates such as n-butyl acrylate and 2-hydroxyethyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and 2-hydroxyethyl methacrylate; acrylamide; Methylacrylamide, N-
Acrylamide derivatives such as isopropylacrylamide and N, N-dimethylacrylamide; acrylonitrile derivatives such as acrylonitrile and methacrylonitrile;
Carboxylic acid vinyl esters such as vinyl acetate, and styrene derivatives such as styrene, 4-vinylbenzyl chloride and 4-acetoxystyrene are preferably used practically, and among them, carbon-conjugated with carbonyl groups such as acrylic acid and methacrylic acid. Carboxylic acids having a carbon double bond, acrylates such as methyl acrylate and ethyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, acrylonitrile derivatives such as acrylonitrile, styrene, 4-acetoxystyrene and the like Are more preferably used, and acrylates such as methyl acrylate and ethyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, and styrene are most preferably used. In the case of anionic polymerization, styrene derivatives such as styrene and α-methylstyrene are preferably used.

The production of the polymer by radical polymerization, which is a preferred polymerization mode, is usually carried out by using a thermally decomposable radical such as an azo compound such as azobisisobutyronitrile (AIBN) or a peroxide such as benzoyl peroxide. This is carried out by heating a solution of the transition metal complex of the present invention and the above-mentioned copolymerized monomers in the presence of an initiator. At this time, an appropriate solvent such as toluene or benzene may be used, or bulk polymerization of only polymerizable monomers may be used.

[Resin Composition] The present invention provides a resin composition containing the above polymer. The resin composition is a polymer containing the transition metal complex as a monomer unit,
A matrix resin that disperses this is an essential component. When the resin composition of the present invention is used for applications utilizing transparency or fluorescence, matrix resins used include polymethyl methacrylate, polyethyl acrylate, acrylic resins such as styrene / methyl methacrylate copolymer, and polystyrene. Transparent amorphous resins having thermoplasticity, such as styrene resins such as styrene and maleic anhydride copolymers, and aromatic polycarbonate resins such as bisphenol A polycarbonate are preferred. Among these, acrylic resins such as polymethyl methacrylate and polyethyl acrylate are particularly suitable for optical applications such as displays and optical fiber communications.

The content of the polymer in the resin composition of the present invention is usually 1 to 99% by weight.
90% by weight, more preferably 10-80% by weight, even more preferably 20-70% by weight, most preferably 30-70% by weight.
% By weight.

In the resin composition, for example, the matrix resin is dissolved in a suitable polymerizable liquid monomer (for example, an acrylic resin monomer such as methyl methacrylate or ethyl acrylate, or styrene), and the transition solution of the present invention is added to such a solution. It is preferably produced by dissolving a metal complex and then performing a polymerization reaction. When the polymer containing the transition metal complex as a monomer component has thermoplasticity or solvent solubility, an extruder, Brabender, a general-purpose melt-kneading method using a roll, or a common solvent of both components is used. It is manufactured by mixing the polymer and the matrix resin by a solution mixing method or the like used. The transition metal complex of the present invention is dissolved in the matrix resin solution (optionally any polymerizable monomer may be added if necessary), a polymerization reaction is performed in such a solution, and the solvent is removed from the resulting solution. The resin composition of the present invention can also be obtained.

As long as the effects of the present invention are not significantly impaired, glass fiber, glass flakes, glass beads, mica, talc, montmorillonite, smectite, synthetic mica, synthetic smectite and other inorganic fillers, polyester and polyamide, etc. Rubber components such as plastic resins and styrene-based thermoplastic elastomers, resin beads, hollow beads, heat stabilizers, antioxidants, ultraviolet absorbers, flame retardants, plasticizers and lubricants such as petrolatum and glycerin esters, metal powders, and semiconductor powders Any additives such as graphite, resin powder, pigments, dyes, fluorescent dyes and compatibilizers may be added.

[Sheet-shaped molded article] The present invention provides a sheet-shaped molded article containing the above-mentioned polymer or resin composition. The sheet-shaped molded body is not particularly limited in its thickness, but is generally 0.01 to 30 mm, preferably 0.05 to 30 mm.
It is a planar molded body having a thickness of about 20 to 20 mm, particularly preferably about 0.1 to 10 mm, and the shape of the surface is not particularly limited. Therefore, a film obtained by various molding methods described below,
It generally means a molded article having a flat surface or a curved surface such as a film, a sheet, or a plate, and may have irregularities as required, for example, like an optical disk substrate.

When the polymer of the present invention or the resin composition containing the same as the raw material thereof has thermoplasticity, the sheet-like molded article of the present invention may be formed by injection molding, press molding, injection compression molding, or die extrusion. It can be formed by a general-purpose melting method such as film formation or inflation film formation, and when the raw material has solvent solubility, it can be formed by a solution casting method such as a solution casting method. The most common molding method suitable is an acrylic resin monomer such as methyl methacrylate or ethyl acrylate or a polymerizable monomer such as styrene as a solvent, where the transition metal complex of the present invention and an acrylic resin or styrene This is a casting polymerization method in which a solution obtained by dissolving a resin is poured into a desired sheet mold and then subjected to bulk polymerization. In the case of such a cast polymerization method, a suitable radical initiator (for example, thermal decomposition of an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide) is required to perform radical polymerization in a mold. It is preferable to add an initiator or a photoinitiator.

[Uses of Sheet-shaped Molded Articles] The sheet-shaped molded articles of the present invention have a wide range of uses utilizing the ability to generate fluorescence when they have the ability to generate fluorescence. For example, when the sheet-shaped molded body of the present invention is used for a backlight light guide plate for a display of a notebook personal computer or a mobile phone, it is possible to achieve an improvement in luminance by adding an ultraviolet light component to a white light backlight light source, Further, if ultraviolet light is used as the light source, light emission with good color purity can be achieved only by the fluorescence of the sheet-shaped molded article of the present invention. The thickness of the light guide plate is not limited, but is usually 0.1 to 1
0 mm, preferably about 0.5 mm to 7 mm, and more preferably about 0.5 to 5 mm.

When the light source of the projection equipment such as a liquid crystal projector contains ultraviolet light, the illuminance in the visible region can be improved by providing the sheet-shaped molded body of the present invention as a wavelength conversion plate in the optical path. Since the sheet-shaped molded body of the present invention converts ultraviolet light in sunlight from visible to near-infrared region,
As an ultraviolet light cut film, for example, it is used as a window covering film for houses, vehicles, aircraft, etc., a film for beverage containers such as PET bottles, a coating for eyeglass lenses, and the like. Further, the film can be used as an agricultural film having a function of converting ultraviolet light harmful to plant growth into various useful wavelength regions.

[0055]

EXAMPLES Specific examples of the present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.
Raw material reagents and solvents were used without purification, unless otherwise specified.

[Measurement Apparatus and Conditions, etc.] (1) NMR: JNM-EX270 type FT manufactured by JEOL Ltd.
-NMR ⁽¹ H: 270.05MHz) solvent: CDCl
₃ . (2) FT-IR: FT / IR-80 manufactured by JASCO Corporation
Measured by KBr disk method or liquid film method (create a cast film of methylene chloride solution of sample on salt crystals) using 00 type FT-IR. (3) MALDI mass spectrum: KOM manufactured by Shimadzu Corporation
PACT MALDI III type laser ionization TOF-
MS was used. Cations were detected using 3-indoleacrylic acid as the matrix material. (4) Fluorescence intensity: Measured with a F-4500 type fluorometer manufactured by Hitachi, Ltd. using a quartz cell having an optical path length of 10 mm.

[Preparation of anhydrous lanthanoid acetate] Terbium (III) acetate or europium (III) acetate hydrate was prepared by heating at 170 ° C. in a nitrogen stream. [Reference Example: Preparation of dendron carboxylate having no vinyl group] According to the procedure described by Kawa et al., A dendron carboxylate having first and fourth generation 3,5-dioxybenzoic acid residues as focal point units ([G-1] -CO
₂ H, and [G-4] -CO ₂ H abbreviated, were prepared following the same).

[Synthesis of Dendron Having Vinyl Terminal and 3,4-dioxybenzoic Acid Residue as Focal Point Unit] <Example 1: First-generation ester dendron having one vinyl group and dendron carboxylate> Synthesis of

(1) Etherification reaction 4-vinylbenzyl chloride (manufactured by Aldrich,
1.0 equivalent), ethyl 3,4-dihydroxybenzoate (1.0 equivalent), anhydrous potassium carbonate (2.5 equivalent),
8-Crown-6 ether (0.2 eq) and tetraethylammonium bromide (1.0 eq) were added to dry acetone and a catalytic amount of 2,6-di-tert-butyl- was added.
4-Methylphenol was added and the mixture was heated and stirred at 60 ° C.
The reaction was monitored by commercially available silica gel thin layer chromatography (TLC), and after confirming disappearance of 4-vinylbenzyl chloride, benzyl bromide (1.0 equivalent) was added, and the reaction was further continued. After confirming disappearance of benzyl bromide by TLC, the mixture was concentrated. The residue was partitioned between methylene chloride and water, and the organic phase was concentrated to give a crude product. This was purified by silica gel column chromatography (n-hexane / ethyl acetate system), and a first-generation ester dendron (hereinafter, referred to as a "first-generation") in which a vinylbenzyl group and a benzyl group were ether-bonded to a 3,4-dioxybenzoic acid residue one by one. , V-34G1-CO ₂ Et). In this structure, an absorption band derived from a carbonyl group of an ester group was observed around 1710 cm ^-1 in an FT-IR spectrum, and a methyl group (triplet / 3H) and a methylene group of an ethoxy group in a ¹ H-NMR spectrum. (Quartet / 2H), benzylic proton (4H),
This was confirmed by the observation of signals of three types of vinyl group protons (doublet / 1H, double doublet / 1H, and double doublet / 1H) and aromatic protons (1H, 9H, and 2H).

(2) Hydrolysis of ester group V-34G1-CO ₂ Et obtained above was dissolved in tetrahydrofuran (THF) / methanol system, and a 40% by weight aqueous solution containing 3 equivalents of potassium hydroxide was added. The obtained homogeneous solution was heated under reflux to hydrolyze the ester group. After confirming the completion of the reaction by TLC, the mixture was added dropwise to an aqueous solution containing an excess of hydrochloric acid in excess of potassium hydroxide with stirring under ice-cooling. The obtained precipitate was extracted with methylene chloride, washed with water, dried and concentrated, and purified by silica gel column chromatography (developing solvent: methylene chloride / diethyl ether system). First generation acid dendrons thus obtained structure (hereinafter, V-34G1-CO ₂ H and approximately) is the absorption band of the carbonyl group which is attributable to a carboxyl group by FT-IR spectrum was observed, and ¹ H
It was confirmed from the fact that no signal attributed to the ethoxy group was observed in -NMR.

Example 2: First having one vinyl group
Synthesis of next generation benzyl alcohol dendron and benzyl bromide dendron> (1) Etherification reaction In the etherification reaction of Example 1, instead of ethyl 3,4-dihydroxybenzoate, 3,5-dihydroxybenzyl alcohol (manufactured by Aldrich) was used. , 1.0 equivalent). The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate system).
First-generation benzyl alcohol dendrons (hereinafter abbreviated as V-G1-OH) were obtained by ether-bonding one by one. In the ¹ H-NMR spectrum, this structure shows a benzylic proton (2H and 4H), three kinds of vinyl group protons (doublet / 1H, double doublet / 1H, and double doublet / 1H), an aromatic proton (1H, 9
H, and 2H) were confirmed.

(2) Bromination reaction V-G1-OH obtained as described above was converted to C.I. J. Hawk
The compound was converted to the corresponding benzyl bromide dendron according to the bromination reaction described in the literature by Er et al. That is, V-G1
-OH was dissolved in a minimum amount of dry tetrahydrofuran, carbon tetrabromide (1.25 eq) was added with ice cooling and stirring, and then triphenylphosphine (1.25 eq) was added. After confirming the disappearance of the raw materials by TLC, the reaction solution was poured into a large amount of ice water and extracted with methylene chloride. The organic phase thus obtained is dried (anhydrous sodium sulfate), filtered, concentrated,
Purified by silica gel column chromatography (n-hexane / ethyl acetate system), the first generation wherein the desired 3,5-dioxybenzyl bromide residue is ether-bonded to a 4-vinylbenzyl group and a benzyl group one by one. (Hereinafter abbreviated as VG1-Br) was obtained. This structure corresponds to 3400c observed in the raw material V-G1-OH in the FT-IR spectrum.
A broad absorption band derived from the OH group near m ^-1 is not observed, and in the ¹ H-NMR spectrum, the benzylic proton at the focal point (2H) is shifted to a higher magnetic field than the raw material V-G1-OH. , Other benzylic protons (4H), three types of vinyl group protons (doublet / 1H, double doublet / 1H, double doublet / 1H), and aromatic protons (1H, 9H, and 2H) I confirmed from what was done.

Example 3 Second having One Vinyl Group
Synthesis of Next Generation Ester Dendrons and Carboxylic Acid Dendrons> (1) Etherification Reaction Two benzyl groups prepared by the method described in the document by Hawker et al.
Generation of benzyl bromide dendron ([G-
1] -Br), 1.0 equivalent, 3,4-
Ethyl dihydroxybenzoate (1.0 equiv), anhydrous potassium carbonate (2.5 equiv), 18-crown-6 ether (0.2 equiv) were added to dry acetone, and a catalytic amount of 2,6-di-tert was added. -Butyl-4-methylphenol was added and the mixture was heated and stirred at 60 ° C. [G-1]-by TLC
After confirming the disappearance of Br, V-G1-Br which is the first generation benzyl bromide dendron synthesized in Example 2 was used.
(1.0 equivalent) was added, and the reaction was further continued. The reaction was monitored by TLC, and after confirming the disappearance of V-G1-Br, the mixture was concentrated. The residue was partitioned between methylene chloride and water, and the organic phase was concentrated to give a crude product. This was purified by silica gel column chromatography (methylene chloride / diethyl ether system) to produce a second generation having one 4-vinylbenzyl group and three benzyl groups with a 3,4-dioxybenzoic acid residue as a focal point unit. (Hereinafter, abbreviated as V-34G2-CO ₂ Et) was obtained. This structure corresponds to 17 in the FT-IR spectrum.
An absorption band derived from the carbonyl group of the ester group was observed around 10 cm ^-1 , and the methyl group of the ethoxy group (triplet / 3H) in the ¹ H-NMR spectrum
And a methylene group (quartet / 2H), a benzylic proton (12H), and three types of vinyl group protons (doublet /
1H, double doublet / 1H, double doublet / 1H), and aromatic protons (1H and 27H) were confirmed from their respective signals.

(2) Hydrolysis of ester group The V-34G2-CO ₂ Et obtained above was treated and purified in the same manner as in the ester group hydrolysis method described in Example 1 to obtain the corresponding second-generation product. Dendron carboxylate (hereinafter referred to as V-3)
4G2-CO ₂ H). This structure is FT-I
It was confirmed from the fact that an absorption band of a carbonyl group attributed to a carboxyl group was observed in the R spectrum and that no signal attributed to an ethoxy group was observed in ¹ H-NMR.

Example 4: First having two vinyl groups
Synthesis of Next Generation Ester Dendron and Carboxylate Dendron> (1) Etherification Reaction 4-vinylbenzyl chloride (manufactured by Aldrich,
2.05 equivalents), ethyl 3,4-dihydroxybenzoate (1.0 equivalent), anhydrous potassium carbonate (2.5 equivalents), 1
8-Crown-6 ether (0.2 eq) and tetraethylammonium bromide (1.0 eq) were added to dry acetone and a catalytic amount of 2,6-di-tert-butyl- was added.
4-Methylphenol was added and the mixture was heated and stirred at 60 ° C.
The reaction was monitored by TLC, and after confirming disappearance of 4-vinylbenzyl chloride, the mixture was concentrated. The residue was partitioned between methylene chloride and water, and the organic phase was concentrated to give a crude product. This was subjected to silica gel column chromatography (n-
A first-generation ester dendron in which two 4-vinylbenzyl groups are ether-linked to 3,4-dioxybenzoic acid residues (hereinafter referred to as V2-3)
4G1-CO ₂ Et). This structure is FT-
1710 cm ^-1 near the absorption band derived from the carbonyl group of the ester group was observed in the IR spectrum, and, ¹ H-NMR methyl group of ethoxy groups in the spectrum (triplet / 3H) and methylene group (quartet / 2H), Benzyl proton (4H), three types of vinyl group protons (doublet / 2H, double doublet / 2
H, double doublet / 2H), and aromatic protons (1H, 8H, and 2H).

(2) Hydrolysis of ester group V2-34G1-CO ₂ Et obtained above was treated and purified in the same manner as in the ester group hydrolysis method described in Example 1.
First generation acid dendron having corresponding two vinyl groups (hereinafter, abbreviated as V2-34G2-CO ₂ H) was obtained. This structure was confirmed by the fact that an absorption band of a carbonyl group attributed to a carboxyl group was observed in the FT-IR spectrum, and that no signal attributed to an ethoxy group was observed in ¹ H-NMR.

Example 5: First having two vinyl groups
Synthesis of next generation benzyl alcohol dendron and benzyl bromide dendron> (1) Etherification reaction In the etherification reaction of Example 4, instead of ethyl 3,4-dihydroxybenzoate, 3,5-dihydroxybenzyl alcohol (manufactured by Aldrich) , 1.0 equivalent). The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate system), and as a main product, a first generation in which two 4-vinylbenzyl groups were ether-linked to a 3,5-dioxybenzyl alcohol residue. (Hereinafter, abbreviated as V2-G1-OH) was obtained. This structure is ¹ H
The benzylic proton (2
H, and 4H), three types of vinyl group protons (doublet / 2H, double doublet / 2H, and double doublet / 2H), aromatic protons (1H, 8H, and 2H)
Was confirmed from the fact that each signal was observed.

(2) Bromination reaction In the bromination reaction of Example 2, the same operation was carried out using V2-G1-OH obtained above instead of V-G1-OH to obtain the desired 3,5 A first group in which two 4-vinylbenzyl groups are ether-linked to a dioxybenzyl bromide residue;
Generation benzyl bromide dendron (hereinafter referred to as V2-G1
-Br). This structure, in FT-IR spectra, it broad absorption band derived from the OH group near 3400 cm ^-1 which is observed in the raw material V2-G1-OH is not observed, and, in the ¹ H-NMR spectrum, the focal Point benzylic proton (2
H) is shifted to a higher magnetic field than the raw material V2-G1-OH,
Other benzylic protons (4H), three types of vinyl group protons (doublet / 2H, double doublet / 2
H, double doublet / 2H), and aromatic protons (1H, 8H, and 2H).

<Example 6: Second having two vinyl groups>
Synthesis of Next Generation Ester Dendron and Carboxylate Dendron: Part 1> (1) Etherification Reaction V-G1-Br (2.05 equivalents), which is the first generation benzyl bromide dendron synthesized in Example 2, 3,4 −
Ethyl dihydroxybenzoate (1.0 equiv), anhydrous potassium carbonate (2.5 equiv), 18-crown-6 ether (0.2 equiv) were added to dry acetone, and a catalytic amount of 2,6-di-tert was added. -Butyl-4-methylphenol was added and the mixture was heated and stirred at 60 ° C. The reaction was monitored by TLC, and after confirming the disappearance of V-G1-Br, the mixture was concentrated. The residue was partitioned between methylene chloride and water, and the organic phase was concentrated to obtain a crude product. This was purified by silica gel column chromatography (methylene chloride / diethyl ether system) to obtain a first-generation dendron having a 3,4-dioxybenzoic acid residue as a focal point unit and a 4-vinylbenzyl group and one benzyl group. A second-generation ester dendron (hereinafter referred to as [VB] 2-34G2-
CO ₂ Et). According to this structure, an absorption band derived from a carbonyl group of an ester group was observed around 1710 cm ^-1 in the FT-IR spectrum, and ¹ H
In the NMR spectrum, the ethoxy group methyl group (triplet / 3H) and methylene group (quartet / 2
H), benzylic proton (12H), three kinds of vinyl group protons (doublet / 2H, double doublet / 2
H, double doublet / 2H), and aromatic protons (1H and 26H).

(2) Hydrolysis of Ester Group [VB] 2-34G2-CO ₂ Et obtained above was treated and purified in the same manner as in the ester group hydrolysis method described in Example 1, and the corresponding second generation acid dendron _{(hereinafter, [VB] 2-34G2-CO 2} H and approximately) was obtained. This structure was confirmed by the fact that an absorption band of a carbonyl group attributed to a carboxyl group was observed in the FT-IR spectrum, and that no signal attributed to an ethoxy group was observed in ¹ H-NMR.

<Example 7: Second having two vinyl groups>
Synthesis of Next Generation Ester Dendron and Carboxylic Acid Dendron: Part 2> (1) Etherification Reaction In Example 3, Example 5 was used instead of VG1-Br.
V, the first generation benzyl bromide dendron obtained in
The same experimental operation was performed using 2-G1-Br, and
A second-generation ester dendron in which a dioxybenzoic acid residue is a focal point unit, and a first-generation dendron having two 4-vinylbenzyl groups and a first-generation dendron having two benzyl groups are respectively bonded to each other; hereinafter, to obtain a V2B2-34G2-CO ₂ Et approximately). This structure corresponds to 171 in the FT-IR spectrum.
An absorption band derived from the carbonyl group of the ester group was observed at about 0 cm ^-1 , and in the ¹ H-NMR spectrum, the methyl group of the ethoxy group (triplet / 3H), the methylene group (quartet / 2H), and the benzylic proton (12H) Three types of vinyl group protons (doublet / 2
H, double doublet / 2H, and double doublet /
2H) and aromatic protons (1H and 26H).

(2) Hydrolysis of ester group V2B2-34G2-CO ₂ Et obtained above was treated and purified in the same manner as in the ester group hydrolysis method described in Example 1, and the corresponding second generation hydrolyzate was obtained. Dendron carboxylate (hereinafter, referred to as
V2B2-34G2-CO ₂ H). This structure shows that the absorption band of the carbonyl group attributed to the carboxyl group was observed in the FT-IR spectrum, and that ¹ H
It was confirmed from the fact that no signal attributed to the ethoxy group was observed in -NMR.

Example 8 Second Having Three Vinyl Groups
Synthesis of Generation Ester Dendron and Dendron Carboxylate> (1) Etherification Reaction V-G1-Br (1.0 equivalent), which is the first generation benzyl bromide dendron synthesized in Example 2, 3,4-dihydroxybenzoate Ethyl acid (1.0 eq.), Anhydrous potassium carbonate (2.5 eq.), 18-crown-6 ether (0.2 eq.) Are added to dry acetone and a catalytic amount of 2,6-di-tert-butyl is added. -4-Methylphenol was added, and the mixture was heated and stirred at 60 ° C. After monitoring the reaction by TLC and confirming the disappearance of V-G1-Br, V2 which is the first-generation benzylbromide dendron obtained in Example 5 was used.
The reaction was further continued by adding 1.0 equivalent of -G1-Br.
After confirming disappearance of V2-G1-Br by TLC, the mixture was concentrated. The residue was partitioned between methylene chloride and water, and the organic phase was concentrated to give a crude product. This was purified by silica gel column chromatography (methylene chloride / diethyl ether system), and a first-generation dendron having two 4-vinylbenzyl groups with a 3,4-dioxybenzoic acid residue as a focal point unit and 4-vinyl the first generation dendron having one benzyl group and a benzyl group, a second generation of esters dendron bonded one each (hereinafter, V2VB-34G2-CO ₂ Et approximately) was obtained. This structure corresponds to 171 in the FT-IR spectrum.
An absorption band derived from the carbonyl group of the ester group was observed at about 0 cm ^-1 , and in the ¹ H-NMR spectrum, the methyl group of the ethoxy group (triplet / 3H), the methylene group (quartet / 2H), and the benzylic proton (12H) It was confirmed from the observation of signals of three kinds of vinyl group protons (doublet / 3H, respectively) and aromatic protons (1H and 25H).

(2) Hydrolysis of ester group V2VB-34G2-CO ₂ Et obtained above was treated and purified in the same manner as in the ester group hydrolysis method described in Example 1 to obtain the corresponding second generation. Dendron carboxylate (hereinafter, referred to as
V2VB-34G2-CO ₂ H). This structure shows that the absorption band of the carbonyl group attributed to the carboxyl group was observed in the FT-IR spectrum, and that ¹ H
It was confirmed from the fact that no signal attributed to the ethoxy group was observed in -NMR.

Example 9: Second having four vinyl groups
Synthesis of Next Generation Ester Dendron and Carboxylic Acid Dendron> (1) Etherification Reaction First generation benzyl bromide dendron synthesized in Example 5, V2-G1-Br (2.05 equivalents), 3,4
-Ethyl dihydroxybenzoate (1.0 eq.), Anhydrous potassium carbonate (2.5 eq.), 18-crown-6 ether (0.2 eq.) Are added to dry acetone and a catalytic amount of 2,6-di- Tert-butyl-4-methylphenol was added, and the mixture was heated and stirred at 60 ° C. After monitoring the reaction by TLC and confirming the disappearance of V2-G1-Br, the mixture was concentrated,
The residue was partitioned between methylene chloride and water, and the organic phase was concentrated to give a crude product. This was purified by silica gel column chromatography (methylene chloride / diethyl ether system) to obtain a second compound having four 4-vinylbenzyl groups with a 3,4-dioxybenzoic acid residue as a focal point unit.
Generation of ester dendron (hereinafter referred to as V4-34G2-C
O ₂ Et). According to this structure, an absorption band derived from a carbonyl group of an ester group was observed around 1710 cm ^-1 in the FT-IR spectrum, and ¹ H-
In the NMR spectrum, a methyl group (triplet / 3H) and a methylene group (quartet / 2H) of an ethoxy group,
It was confirmed from the observation of signals of benzylic proton (12H), three kinds of vinyl group protons (doublet / 4H, double doublet / 4H, and double doublet / 4H) and aromatic protons (1H and 24H). .

(2) Hydrolysis of ester group V4-34G2-CO ₂ Et obtained above was treated and purified in the same manner as in the ester group hydrolysis method described in Example 1.
The corresponding second generation dendron carboxylate (hereinafter referred to as V4
-34G2-CO ₂ H and approximately) was obtained. This structure is FT
That the absorption band of the carbonyl group attributed to the carboxyl group was observed in the -IR spectrum, and that the ¹ H-NMR
Was confirmed because no signal attributable to the ethoxy group was observed.

Example 10 Synthesis of Second-Generation Benzyl Alcohol Dendron and Benzyl Bromide Dendron Having One Vinyl Group (1) Etherification Reaction In Example 3, instead of ethyl 3,4-dihydroxybenzoate, The same experimental operation was carried out using 3,5-dihydroxybenzyl alcohol, having a 3,5-dioxybenzyl alcohol residue as a focal point unit and having one 4-vinylbenzyl group and three benzyl groups. A second generation benzyl alcohol dendron (hereinafter abbreviated as VG2-OH) was obtained. This structure is ¹ H-
In the NMR spectrum, the benzylic proton (14
H) three types of vinyl group protons (doublet / 1H, double doublet / 1H, and double doublet / 1
H) and signals of aromatic protons (1H and 27H) were observed, and a signal corresponding to the target structure was observed in the MALDI mass spectrum.

(2) Bromination reaction In the bromination reaction of Example 2, the same operation was carried out using V-G2-OH obtained above in place of V-G1-OH, and the corresponding second generation Benzyl bromide dendron (hereinafter abbreviated as VG2-Br) was obtained. This structure is
In the T-IR spectrum, the raw material V-G2-O
No broad absorption band derived from the OH group near 3400 cm ^-1 observed in H is observed, and ¹ H-NMR
In the spectrum, the benzylic proton (2H) at the focal point is shifted to a higher magnetic field than the raw material VG2-OH, and the other benzylic protons (12H), 3H
This was confirmed by the observation of the signals of the various types of vinyl group protons (doublet / 1H, double doublet / 1H, and double doublet / 1H) and aromatic protons (1H and 27H).

Example 11 Synthesis of Third-Generation Ester Dendron and Carboxylic Acid Dendron Having One Vinyl Group> (1) Etherification Reaction J. 1.0 equivalent of a second-generation benzyl bromide dendron prepared by a method described in the literature by Hawker et al. In which four benzyl groups are ether-linked (described in the literature as [G-2] -Br, and the same hereinafter);
Ethyl 3,4-dihydroxybenzoate (1.0 equivalent),
Anhydrous potassium carbonate (2.5 equivalents), 18-crown-6
Ether (0.2 equivalent) was added to dry acetone, and a catalytic amount of 2,6-di-tert-butyl-4-methylphenol was further added, followed by heating and stirring at 60 ° C. [G-
2] After confirming the disappearance of -Br, V-G2 which is the second generation benzyl bromide dendron synthesized in Example 10
-Br (1.0 equivalent) was added to continue the reaction. T
After monitoring the reaction by LC and confirming the disappearance of V-G2-Br, the mixture was concentrated. The residue was partitioned between methylene chloride and water, and the organic phase was concentrated to give a crude product. This was purified by silica gel column chromatography (methylene chloride / diethyl ether system) to produce a second generation having one 4-vinylbenzyl group and three benzyl groups with a 3,4-dioxybenzoic acid residue as a focal point unit. and dendrons, a second generation dendron having four benzyl, third generation ester dendron bonded one each (hereinafter, V-34G3-CO ₂ Et approximately) was obtained. This structure corresponds to 171 in the FT-IR spectrum.
An absorption band derived from the carbonyl group of the ester group was observed at about 0 cm ^-1 , and in the ¹ H-NMR spectrum, the methyl group of the ethoxy group (triplet / 3H), the methylene group (quartet / 2H), and the benzylic proton (28H) Signals of three types of vinyl group protons (doublet / 1H, respectively) and aromatic protons (60H) were observed, and a signal corresponding to the target structure was observed in the MALDI mass spectrum. Confirmed from.

(2) Hydrolysis of ester group The V-34G3-CO ₂ Et obtained above was treated and purified in the same manner as in the ester group hydrolysis method described in Example 1 to obtain the corresponding third generation. Dendron carboxylate (hereinafter referred to as V-3)
4G3-CO ₂ H and approximately) was obtained. This structure is FT-I
The absorption spectrum of the carbonyl group attributed to the carboxyl group was observed in the R spectrum, and the signal attributed to the ethoxy group was not observed in ¹ H-NMR. It was confirmed from the fact that a corresponding signal was observed.

Example 12 Synthesis of Third-Generation Benzyl Alcohol Dendron and Benzyl Bromide Dendron Having One Vinyl Group (1) Etherification Reaction In Example 11, instead of ethyl 3,4-dihydroxybenzoate, The same experimental operation was carried out using 3,5-dihydroxybenzyl alcohol, having 3,5-dioxybenzyl alcohol residue as a focal point unit, having one 4-vinylbenzyl group and seven benzyl groups. A third generation benzyl alcohol dendron (hereinafter abbreviated as V-G3-OH) was obtained. This structure is ¹ H-
In the NMR spectrum, the benzyl position proton (30
H) Signals of three types of vinyl group protons (each doublet / 1H) and aromatic protons (60H) were observed, and the signals corresponding to the target structure were observed in the MALDI mass spectrum. .

(2) Bromination reaction In the bromination reaction of Example 2, the same operation was carried out using V-G3-OH obtained above instead of V-G1-OH, and the corresponding third generation Benzyl bromide dendron (hereinafter abbreviated as V-G3-Br) was obtained. This structure is
In the T-IR spectrum, the raw material V-G3-O
No broad absorption band derived from the OH group near 3400 cm ^-1 observed in H is observed, and ¹ H-NMR
In the spectrum, the benzylic proton (2H) at the focal point is shifted to a higher magnetic field than the raw material VG2-OH, and the other benzylic protons (28H), 3H
Kinds of vinyl group protons (doublet / 1
H) and aromatic protons (60H) were confirmed from their respective signals.

<Example 13: Synthesis of fourth-generation ester dendron and carboxylic acid dendron having one vinyl group> (1) Etherification reaction J. 1.0 equivalent of a third-generation benzyl bromide dendron prepared by a method described in the literature by Hawker et al. In which four benzyl groups are ether-linked (described in the literature as [G-3] -Br, the same applies hereinafter),
Ethyl 3,4-dihydroxybenzoate (1.0 equivalent),
Anhydrous potassium carbonate (2.5 equivalents), 18-crown-6
Ether (0.2 equivalent) was added to dry acetone, and a catalytic amount of 2,6-di-tert-butyl-4-methylphenol was further added, followed by heating and stirring at 60 ° C. [G-
2] After confirming the substantial disappearance of -Br, V-G3-Br (1.0 equivalent), a third-generation benzylbromide dendron synthesized in Example 12, was added, and the reaction was further continued. The reaction was monitored by TLC, and the concentrated residue was partitioned between methylene chloride and water, and the organic phase was concentrated to give a crude product. This was purified by silica gel column chromatography (methylene chloride / diethyl ether system),
A 3,4-dioxybenzoic acid residue is used as a focal point unit, and one 4-vinylbenzyl group and seven benzyl groups are used.
Generation dendron (hereinafter referred to as V-34G4) in which a third generation dendron having eight benzyl groups and a third generation dendron having eight benzyl groups are respectively bonded.
—CO ₂ Et). This structure can be observed an absorption band originating from the carbonyl group of the ester group near 1710 cm ^-1 in the FT-IR spectra, and, ¹
In the H-NMR spectrum, the methyl group of ethoxy group (triplet / 3H) and the methylene group (quartet / 2
H), benzylic proton (60H), three types of vinyl group protons (1H each), aromatic protons (124H)
H) were observed, and MALD
It was confirmed from the fact that a signal corresponding to the target structure was observed in the I mass spectrum.

(2) Hydrolysis of ester group V-34G4-CO ₂ Et obtained above was treated and purified in the same manner as in the ester group hydrolysis method described in Example 1 to obtain the corresponding fourth generation. Dendron carboxylate (hereinafter referred to as V-3)
4G4-CO ₂ H). This structure is FT-I
The absorption spectrum of the carbonyl group attributable to the carboxyl group was observed in the R spectrum, and the signal attributable to the ethoxy group was not observed in ¹ H-NMR. It was confirmed from the fact that a signal was observed. [Synthesis of dendron having vinyl group terminal and having 3,5-dioxybenzoic acid residue as focal point unit]

<Example 14: Synthesis of first-generation ester dendron having one vinyl group and dendron carboxylate> (1) Etherification reaction In the etherification reaction procedure of Example 1, 3,4-dihydroxybenzoic acid was used. The same experimental operation was performed using ethyl 3,5-dihydroxybenzoate instead of ethyl,
First generation ester dendron (hereinafter, V-35G1-CO ₂ Et approximately) a vinylbenzyl group and a benzyl group and an ether bond one each in 5-dioxy benzoic acid residues was obtained. This structure, 1710 cm ^-1 absorption band derived from the carbonyl group of the ester group can be observed near the FT-IR spectrum, and, ¹ H-NMR methyl group of ethoxy groups in the spectrum (triplet /
3H) and methylene groups (quartet / 2H), benzylic protons (4H), three vinyl group protons (doublet / 1H, double doublet / 1H, and double doublet / 1H), aromatic protons (1H, 9H, and 2
H) was confirmed by the observation of each signal.

(2) Hydrolysis of ester group The V-35G1-CO ₂ Et obtained above was treated and purified in the same manner as in the hydrolysis method of the ester group in Example 1 to obtain the corresponding first-generation carboxylic acid. Dendron (hereinafter V-35G1
-CO ₂ H), an absorption band of a carbonyl group attributed to a carboxyl group was observed in the FT-IR spectrum, and no signal attributed to an ethoxy group was observed in ¹ H-NMR. I confirmed from that.

<Example 15: Synthesis of second-generation ester dendron having one vinyl group and dendron carboxylate> (1) Etherification reaction The procedure of the etherification reaction of Example 3 was repeated to prepare The same experimental operation was carried out using ethyl 3,5-dihydroxybenzoate instead of ethyl acetate,
Dioxybenzoic acid residue as focal point unit,
Second-generation ester dendrons having one 4-vinylbenzyl group and three benzyl groups (hereinafter referred to as V-35G2
—CO ₂ Et). This structure can be observed an absorption band originating from the carbonyl group of the ester group near 1710 cm ^-1 in the FT-IR spectra, and, ¹
In the H-NMR spectrum, the methyl group of ethoxy group (triplet / 3H) and the methylene group (quartet / 2
H), benzylic proton (12H), three types of vinyl group protons (doublet / 1H, double doublet / 1
H, double doublet / 1H), and aromatic protons (1H and 27H).

(2) Hydrolysis of ester group The V-35G2-CO ₂ Et obtained above was treated in the same manner as the ester group hydrolysis method described in Example 1 to obtain the corresponding second-generation carboxylic acid. Dendron (hereinafter V-35G2
—CO ₂ H). This structure was confirmed by the fact that an absorption band of a carbonyl group attributed to a carboxyl group was observed in the FT-IR spectrum, and that no signal attributed to an ethoxy group was observed in ¹ H-NMR.

<Example 16: Synthesis of third-generation ester dendron having one vinyl group and dendron carboxylate> (1) Etherification reaction In the etherification reaction procedure of Example 11, 3,4-dihydroxybenzoic acid was used. The same experimental operation was performed using ethyl 3,5-dihydroxybenzoate instead of ethyl,
A 3,5-dioxybenzoic acid residue is used as a focal point unit, and one 4-vinylbenzyl group and three benzyl groups are used.
Generation dendron (hereinafter, referred to as V-35G3) in which a second generation dendron having two benzyl groups and a second generation dendron having four benzyl groups are respectively bonded.
—CO ₂ Et). This structure can be observed an absorption band originating from the carbonyl group of the ester group near 1710 cm ^-1 in the FT-IR spectra, and, ¹
In the H-NMR spectrum, the methyl group of ethoxy group (triplet / 3H) and the methylene group (quartet / 2
H), benzylic protons (28H), three types of vinyl group protons (each doublet / 1H), and aromatic protons (60H), and a signal corresponding to the target structure in the MALDI mass spectrum. Was confirmed from the fact that was observed.

(2) Hydrolysis of ester group The V-35G3-CO ₂ Et obtained above was treated in the same manner as in the ester group hydrolysis method described in Example 1, and the corresponding third-generation carboxylic acid was obtained. Dendron (hereinafter V-35G3
—CO ₂ H). This structure was characterized by the fact that an absorption band of a carbonyl group attributed to a carboxyl group was observed in the FT-IR spectrum, and that no signal attributed to an ethoxy group was observed in ¹ H-NMR,
Furthermore, it was confirmed from the fact that a signal corresponding to the target structure was observed in the MALDI mass spectrum.

<Example 17: Synthesis of fourth-generation ester dendron having one vinyl group and dendron carboxylate> (1) Etherification reaction In the etherification reaction procedure of Example 13, 3,4-dihydroxybenzoic acid was used. The same experimental operation was performed using ethyl 3,5-dihydroxybenzoate instead of ethyl,
A 3,5-dioxybenzoic acid residue is used as a focal point unit, and one 4-vinylbenzyl group and 7
Generation dendron (hereinafter, referred to as V-35G4) in which a third generation dendron having eight benzyl groups and a third generation dendron having eight benzyl groups are respectively bonded.
—CO ₂ Et). This structure can be observed an absorption band originating from the carbonyl group of the ester group near 1710 cm ^-1 in the FT-IR spectra, and, ¹
In the H-NMR spectrum, the methyl group of ethoxy group (triplet / 3H) and the methylene group (quartet / 2
H), benzylic proton (60H), three types of vinyl group protons (1H each), aromatic protons (124H)
H) were observed, and MALD
It was confirmed from the fact that a signal corresponding to the target structure was observed in the I mass spectrum.

(2) Hydrolysis of ester group The V-35G4-CO ₂ Et obtained above was treated in the same manner as in the ester group hydrolysis method described in Example 1 to obtain the corresponding fourth-generation carboxylic acid. Dendron (hereinafter V-35G4
—CO ₂ H). This structure was characterized by the fact that an absorption band of a carbonyl group attributed to a carboxyl group was observed in the FT-IR spectrum, and that no signal attributed to an ethoxy group was observed in ¹ H-NMR,
Furthermore, it was confirmed from the fact that a signal corresponding to the target structure was observed in the MALDI mass spectrum. [Synthesis of dendron having vinyl group terminal and having 2,4-dioxybenzoic acid residue as focal point unit]

<Example 18: Synthesis of first-generation ester dendron having one vinyl group and dendron carboxylate> (1) Etherification reaction In the etherification reaction procedure of Example 1, 3,4-dihydroxybenzoic acid was used. The same experimental operation was performed by using methyl 2,4-dihydroxybenzoate (supplied by Aldrich) instead of ethyl, and a vinylbenzyl group and a benzyl group were added to the 2,4-dioxybenzoic acid residue, respectively. One by first generation esters dendron was ether bond (hereinafter, V-24G1-CO ₂ Et approximately) was obtained.
This structure corresponds to 1710c in the FT-IR spectrum.
The absorption band derived from the carbonyl group of the ester group was observed near m ⁻¹ , and in the ¹ H-NMR spectrum, the methyl group of the ethoxy group (triplet / 3H), the methylene group (quartet / 2H), and the benzylic proton (4
H) three types of vinyl group protons (doublet / 1H, double doublet / 1H, and double doublet / 1
H) and aromatic protons (1H, 9H, and 2H) were confirmed from their respective signals.

(2) Hydrolysis of ester group The above-obtained V-24G1-CO ₂ Et was treated and purified in the same manner as in the ester group hydrolysis method of Example 1 to obtain the corresponding first-generation carboxylic acid. Dendron (hereinafter referred to as V-24G1
-CO ₂ H), an absorption band of a carbonyl group attributed to a carboxyl group was observed in the FT-IR spectrum, and no signal attributed to an ethoxy group was observed in ¹ H-NMR. I confirmed from that.

[Synthesis of Tb ³⁺ Complex] <Example 19: First Generation Complex: Part 1> First generation carboxylic acid dendron V-34G1-CO ₂ H having one vinyl group obtained in Example 1 (3.0 equivalents), anhydrous terbium (III) acetate (1.0 equivalent), and a catalytic amount of 2,6-
Di-tert-butyl-4-methylphenol was mixed and heated at 80 ° C. while stirring under reduced pressure in chlorobenzene, and acetic acid generated was distilled off together with the solvent. The resulting residue was in the form of a transparent glass, and in the FT-IR spectrum, the absorption band of the carbonyl group attributed to the carboxyl group given by the raw material V-34G1-CO ₂ H was not observed. Since a unique ¹ H-NMR spectrum broadening was observed, a first-generation dendron complex having a target vinyl group (hereinafter referred to as [V
-34G1] 3-Tb).

<Example 20: First generation complex: part 2> In Example 19, instead of V-34G1-CO ₂ H,
The same experimental operation was performed using the first-generation dendron carboxylate V-35G1-CO ₂ H having one vinyl group obtained in Example 14. The obtained residue was in the form of a transparent glass, and was found to have a raw material V-35 in FT-IR spectrum.
The absence of the absorption band of the carbonyl group attributed to the carboxyl group given by G1-CO ₂ H and the broadening of the ¹ H-NMR spectrum peculiar to the lanthanoid complex were observed. Generation dendron complex having a group (hereinafter referred to as [V-35G1] 3-T
b).

<Example 21: Second generation complex: part 1> In Example 19, instead of V-34G1-CO ₂ H,
The same experimental operation was performed using the second-generation dendron carboxylate V-34G2-CO ₂ H having one vinyl group obtained in Example 3. The resulting residue was in the form of a transparent glass, and was found to have a raw material V-34G in the FT-IR spectrum.
Since the absorption band of the carbonyl group attributed to the carboxyl group given by 2-CO ₂ H was not observed and the broadening of the ¹ H-NMR spectrum peculiar to the lanthanoid complex was observed, the desired vinyl was obtained. Second with a group
Generation dendron complex (hereinafter referred to as [V-34G2] 3-Tb
Abbreviated) was generated.

<Example 22: Second generation complex: part 2> In Example 19, instead of V-34G1-CO ₂ H,
The same experimental operation was performed using the second-generation dendron carboxylate V-35G2-CO ₂ H having one vinyl group obtained in Example 15. The obtained residue was in the form of a transparent glass, and was found to have a raw material V-35 in FT-IR spectrum.
From the fact that no absorption band of the carbonyl group attributed to the carboxyl group given by G2-CO ₂ H was observed and that the ¹ H-NMR spectrum peculiar to the lanthanoid complex was broadened, the desired vinyl was obtained. Generation dendron complex having a group (hereinafter referred to as [V-35G2] 3-T
b).

<Example 23: Third generation complex: part 1> In Example 19, instead of V-34G1-CO ₂ H,
The same experimental operation was performed using the third-generation dendron carboxylate V-34G3-CO ₂ H having one vinyl group obtained in Example 11. The resulting residue was in the form of a transparent glass, and was found to be the starting material V-34 in the FT-IR spectrum.
Since no absorption band of the carbonyl group attributed to the carboxyl group given by G3-CO ₂ H was observed, and broadening of the ¹ H-NMR spectrum peculiar to the lanthanoid complex was observed, the desired vinyl was obtained. Generation dendron complex having a group (hereinafter referred to as [V-34G3] 3-T
b).

<Example 24: Third generation complex: part 2> In Example 19, instead of V-34G1-CO ₂ H,
The same experimental operation was performed using the third-generation dendron carboxylate V-35G3-CO ₂ H having one vinyl group obtained in Example 16. The obtained residue was in the form of a transparent glass, and was found to have a raw material V-35 in FT-IR spectrum.
Since the absorption band of the carbonyl group attributable to the carboxyl group given by G3-CO ₂ H was not observed and the broadening of the ¹ H-NMR spectrum peculiar to the lanthanoid complex was observed, the desired vinyl was obtained. Generation dendron complex having a group (hereinafter referred to as [V-35G3] 3-T
b).

Example 25 Fourth Generation Complex: Part 1 Instead of V-34G1-CO ₂ H in Example 19,
The same experimental operation was carried out using the fourth-generation dendron carboxylate V-34G4-CO ₂ H having one vinyl group obtained in Example 13. The resulting residue was in the form of a transparent glass, and was found to be the starting material V-34 in the FT-IR spectrum.
From the fact that no absorption band of the carbonyl group attributed to the carboxyl group given by G4-CO ₂ H was observed and that the ¹ H-NMR spectrum peculiar to the lanthanoid complex was broadened, the desired vinyl was obtained. Generation dendron complex having a group (hereinafter referred to as [V-34G4] 3-T
b).

<Example 26: 4th generation complex: part 2> In Example 19, instead of V-34G1-CO ₂ H,
The same experimental operation was carried out using the fourth-generation dendron carboxylate V-35G4-CO ₂ H having one vinyl group obtained in Example 17. The obtained residue was in the form of a transparent glass, and was found to have a raw material V-35 in FT-IR spectrum.
Since the absorption band of the carbonyl group attributed to the carboxyl group given by G4-CO ₂ H was not observed, and the broadening of the ¹ H-NMR spectrum peculiar to the lanthanoid complex was observed, the desired vinyl was obtained. Generation dendron complex having a group (hereinafter referred to as [V-35G4] 3-T
b).

<Example 27: Mixed-generation complex: Part 1> First-generation dendron carboxylate V-34G1-CO ₂ H (2.0 equivalents) having one vinyl group and obtained in Example 1, Example Third-generation dendron carboxylate V-34G3-CO ₂ H having one vinyl group obtained in 11
(1.0 equivalent), terbium (III) acetate anhydride (1.0 equivalent), and a catalytic amount of 2,6-di-tert-butyl-4.
-Methylphenol was mixed and heated at 80 ° C. while stirring under reduced pressure in chlorobenzene, and acetic acid formed was distilled off together with the solvent. The resulting residue is in the form of a transparent glass,
The FT-IR spectrum did not show the absorption band of the carbonyl group attributed to the carboxyl group provided by the raw material carboxylate dendron, and the broadening of the ¹ H-NMR spectrum specific to the lanthanoid complex was observed. A mixed generation dendron complex having a target vinyl group (hereinafter referred to as [V-34G1 / 34G3] 3-T
b).

[0104] <Example 28: Mixed Generation Complex: Part 2> In Example _{27, V-34G3-CO 2} H in place of, the third-generation acid dendron having one vinyl group obtained in Example 16 The same experimental operation was performed using V-35G3-CO ₂ H. The obtained residue is in the form of a transparent glass, and in the FT-IR spectrum, the absorption band of the carbonyl group attributable to the carboxyl group provided by the raw material carboxylic acid dendron is not observed, and ¹ H specific to the lanthanoid complex is observed. Since the broadening of the NMR spectrum was observed, the mixed-generation dendron complex having a target vinyl group (hereinafter referred to as [V-34G1 / 35]
G3] (abbreviated as 3-Tb).

Example 29 Complex Containing Dendron Carboxylate Having No Vinyl Group: Part 1> 1 Complex Obtained in Example 1
First-generation carboxylic acid dendron V-34G1-CO2H (1.0 equivalent) having _two vinyl groups, first-generation carboxylic acid dendron [G-1]-having no vinyl group prepared in Reference Example CO ₂ H (2.0 equiv), terbium (III) acetate anhydride (1.0 equiv) and a catalytic amount of 2,6-di-tert-butyl-4-methylphenol were mixed,
The mixture was heated at 80 ° C. while stirring under reduced pressure in chlorobenzene, and the generated acetic acid was distilled off together with the solvent. The resulting residue is transparent vitreous, the absorption band of the carbonyl group attributed to carboxyl groups carboxylic acid dendrons gave the starting material in FT-IR spectrum is not observed, and specific to the lanthanide complexes ¹ H Since the broadening of the NMR spectrum was observed, a dendron complex (hereinafter referred to as [V-34G1 / G1] 3- (Abbreviated as Tb) was confirmed.

<Example 30: Complex containing carboxylic acid dendron without vinyl group: part 2> Fourth generation carboxylic acid dendron having one vinyl group obtained in Example 13 V-34G4-CO ₂ H (1.0 equivalent), the fourth-generation dendron carboxylate [G-4] -CO ₂ H (2.0 equivalents) having no vinyl group prepared in Reference Example, terbium (III) acetate anhydride (1. 0 equivalent), and a catalytic amount of 2,6-
Di-tert-butyl-4-methylphenol was mixed and heated at 80 ° C. while stirring under reduced pressure in chlorobenzene, and acetic acid generated was distilled off together with the solvent. The resulting residue is transparent vitreous, the absorption band of the carbonyl group attributed to carboxyl groups carboxylic acid dendrons gave the starting material in FT-IR spectrum is not observed, and specific to the lanthanide complexes ¹ H -The broadening of the NMR spectrum was observed, so that a fourth-generation dendron complex (hereinafter referred to as [V-34G4 / G4 ] Abbreviated as 3-Tb)
Was generated.

[Synthesis of Eu ³⁺ complex] <Example 31: First-generation complex> The same experimental operation as in Example 20 was carried out except that europium (III) acetate anhydride was used instead of terbium (III) acetate anhydride. Was. The obtained residue was in the form of a transparent glass, and in the FT-IR spectrum, the absorption band of the carbonyl group attributed to the carboxyl group given by the raw material V-35G1-CO ₂ H was not observed. Since broadening of a unique ¹ H-NMR spectrum was observed, a first-generation dendron complex having a target vinyl group (hereinafter referred to as [V
-35G1] 3-Eu).

<Example 32: Second generation complex> Example 22
, The same experimental operation was performed using europium acetate (III) in place of terbium acetate (III). The resulting residue is in the form of a transparent glass, and FT-IR
In the spectrum, the absorption band of the carbonyl group attributed to the carboxyl group given by the raw material V-35G2-CO ₂ H is not observed, and the characteristic of the lanthanoid complex is not observed.
Broadening of the ¹ H-NMR spectrum was observed, and it was confirmed that a second-generation dendron complex having a target vinyl group (hereinafter, abbreviated as [V-35G2] 3-Eu) was generated.

<Example 33: Third generation complex> Example 24
, The same experimental operation was performed using europium acetate (III) in place of terbium acetate (III). The resulting residue is in the form of a transparent glass, and FT-IR
In the spectrum, the absorption band of the carbonyl group attributed to the carboxyl group given by the raw material V-35G3-CO ₂ H was not observed, and the characteristic characteristic of the lanthanoid complex was not observed.
Broadening of the ¹ H-NMR spectrum was observed, and it was confirmed that a third-generation dendron complex having a target vinyl group (hereinafter, abbreviated as [V-35G3] 3-Eu) was produced.

Example 34 Fourth Generation Complex Example 26
, The same experimental operation was performed using europium acetate (III) in place of terbium acetate (III). The resulting residue is in the form of a transparent glass, and FT-IR
In the spectrum, the absorption band of the carbonyl group attributed to the carboxyl group given by the raw material V-35G4-CO ₂ H is not observed, and the characteristic characteristic of the lanthanoid complex is not observed.
Broadening of the ¹ H-NMR spectrum was observed, and it was confirmed that the desired fourth-generation dendron complex having a vinyl group (hereinafter, abbreviated as [V-35G4] 3-Eu) was generated. [Copolymer of dendron complex and methyl methacrylate or styrene]

[0111]: first generation Tb ³⁺ complex obtained in <Example 35 first ones containing generation Tb ³⁺ complex> Example 19 [V
-34G1] 3-Tb (80 parts by weight), methyl methacrylate (20 parts by weight), and a mixed solution of azobisisobutyronitrile (hereinafter abbreviated as AIBN, approximately 1 part by weight) are mixed with 0.1 wt.
It was inserted between two glass plates sandwiching a 5 mm thick spacer. This was heated at 80 ° C. in a nitrogen atmosphere to perform radical polymerization, thereby obtaining a visually transparent film of a methyl methacrylate copolymer.

[0112]: second generation Tb ³⁺ complex [V obtained in <Example 36 second ones containing generation Tb ³⁺ complex> Example 21
-34G2] 3-Tb (50 parts by weight), styrene (50 parts by weight)
Parts by weight) and a mixed solution of AIBN (1 part by weight) were subjected to the same experimental operation as in Example 35 to obtain a visually transparent styrene copolymer film.

[0113] <Example 37: Third Generation Tb ³⁺ those containing complex> 3G Tb ³⁺ complex obtained in Example 23 [V
-34G3] A mixed solution of 3-Tb (10 parts by weight), methyl methacrylate (88.4 parts by weight), tri-n-butylphosphine oxide (1.6 parts by weight), and AIBN (1 part by weight) was carried out. Example 35 The same experimental operation was performed to obtain a visually transparent film of a methyl methacrylate copolymer.

[0114] <Example 38: fourth generation Tb ³⁺ those containing complex> 4G obtained in Example 25 Tb ³⁺ complex [V
-34G4] The same experimental operation as in Example 35 was performed on a mixed solution of 3-Tb (35 parts by weight), methyl methacrylate (65 parts by weight), and AIBN (1 part by weight), and a visually transparent methyl methacrylate copolymer was obtained. A combined film was obtained.

[0115] <Example 39: Mixed Generation Tb ³⁺ those containing complex> first-generation dendron and Tb ³⁺ complexes to third-generation dendrons a mixed ligand obtained in Example 27 [V
-34G1 / 34G3] The same experimental operation as in Example 35 was performed on a mixed solution of 3-Tb (200 parts by weight), styrene (80 parts by weight), and AIBN (1 part by weight), and a visually transparent styrene copolymer was obtained. A combined film was obtained.

<Example 40: Complex containing Td ³⁺ complex containing dendron carboxylate having no vinyl group>
Fourth-generation dendron complex [V-34G4 / G4] 3- in which the carboxylic acid dendron having a vinyl group and the carboxylic acid dendron having no vinyl group obtained in Example 30 were mixed.
For a mixed solution of Tb (35 parts by weight), methyl methacrylate (65 parts by weight), and AIBN (1 part by weight),
The same experimental operation as in Example 35 was performed to obtain a visually transparent film of a methyl methacrylate copolymer.

Example 41: First-generation Eu ³⁺ complex containing first-generation Eu ³⁺ complex [V]
[-35G1] A mixed solution of 3-Eu (90 parts by weight), methyl methacrylate (10 parts by weight), and AIBN (1 part by weight) was inserted between two glass plates sandwiching a 0.5 mm thick spacer. This was heated at 80 ° C. in a nitrogen atmosphere to perform radical polymerization, thereby obtaining a visually transparent film of a methyl methacrylate copolymer.

Example 42: Third-generation Eu ³⁺ complex containing third-generation Eu ³⁺ complex [V]
-35G3] 3-Eu (30 parts by weight), styrene (70
Parts by weight) and AIBN (1 part by weight) were subjected to the same experimental operation as in Example 35 to obtain a visually transparent styrene copolymer film.

[Polymer of Complex Having Vinyl Group] <Example 43: Polymer of first-generation Tb ³⁺ complex> Example 1
First-generation Tb ³⁺ complex [V-34G1] 3-T obtained in Example 9
b (100 parts by weight) and AIBN (1 part by weight) were dissolved in methylene chloride. This solution was cast on a glass plate, dried under a stream of dry nitrogen, and further heated in a vacuum oven at 100 ° C. The film thus obtained is transparent and tough, and does not dissolve in methylene chloride.
^It was considered that the vinyl group of the ³⁺ complex was radically polymerized to increase the molecular weight and crosslink.

Example 44 Polymer of Complex Tb ³⁺ Complex Containing Dendron Carboxylate Having No Vinyl Group Obtained in Example 29 instead of [V-34G1] 3-Tb in Example 43 First generation dendron complex [V-34G1 / G1] 3-T in which carboxylic acid dendron having a vinyl group and carboxylic acid dendron having no vinyl group are mixed.
The same experimental operation was performed using b. The obtained film was transparent and tougher than the film derived from the first-generation complex having no vinyl group in Comparative Example 1, so that the vinyl group of the used Tb ³⁺ complex was subjected to radical polymerization. It was considered that the increase in the molecular weight proceeded.

Example 45 Polymer of Third Generation Eu ³⁺ Complex In Example 43, the third generation Eu ³⁺ complex obtained in Example 33 in place of [V-34G1] 3-Tb [ V-
The same experimental operation was performed using [35G3] 3-Eu.
Since the obtained film was transparent and tough, and did not dissolve in methylene chloride, it was considered that the vinyl group of the used Eu ³⁺ complex was radically polymerized and the molecular weight was increased and the crosslinking was advanced.

Example 46 Acrylic Resin Composition First-generation Tb ³⁺ complex [V-34G1] obtained in Example 19
3-Tb (30 parts by weight), ethyl acrylate (30 parts by weight), polymethyl methacrylate (supplied from Aldrich, having an average molecular weight of 120,000, an intrinsic viscosity of 0.20, and a glass transition point of 114 ° C .; 40 parts by weight) ) And AIBN (1 part by weight)
It was inserted between two glass plates sandwiching a spacer having a thickness of mm. This was heated at 80 ° C. in a nitrogen atmosphere to perform radical polymerization, and a visually transparent film of a polymethyl methacrylate resin composition was obtained.

<Example 47: Styrene resin composition> In Example 46, [V-34G1] 3-Tb was replaced by 40 parts by weight, styrene (30 parts by weight) instead of ethyl acrylate, and polymethyl methacrylate instead of polymethyl methacrylate. Polystyrene (supplied by Aldrich, having a weight average molecular weight of 230,000 and a number average molecular weight of 140,000;
(30 parts by weight) to obtain a visually transparent film of a polystyrene resin composition.

Comparative Example Comparative Example 1: Film of First-Generation Tb ³⁺ Complex Having No Vinyl Group The first-generation dendron carboxylate [G-1] -CO ₂ H prepared in Reference Example was used. M. Kaw
A Tb ³⁺ complex having no vinyl group (in the literature, abbreviated as [G-1] ₃ -Tb, hereinafter the same) was prepared according to the method described in the literature by A. et al. Then, in Example 44, instead of [V-34G1 / G1] 3-Tb, [G-
1] An experimental operation similar to that of Example 44 was performed using _3- Tb to obtain a film. This film was very brittle and could not be folded.

Comparative Example 2: Fourth Generation Tb ³⁺ Complex Having No Vinyl Group Using the fourth generation dendron carboxylate [G-4] -CO ₂ H prepared in Reference Example, the above M.V. Ka
In accordance with the method described in Wa et al., a Tb ³⁺ complex having no vinyl group ([G-4] ₃ -Tb
(Hereinafter abbreviated as the same).

Comparative Example 3: Acrylic resin composition containing fourth-generation Tb ³⁺ complex having no vinyl group Example 38
In the above, instead of [V-34G4] 3-Tb, the Tb ³⁺ complex having no vinyl group obtained in Comparative Example 2 [G-4] ₃ −
The same experimental operation was performed using Tb. Visual transparency of the obtained film was poor as compared with Example 38.

[Evaluation of Fluorescent Brightness] The fourth example obtained in Example 25
Generation Tb³⁺Complex [V-34G4] 3-Tb, Example 3
4th generation Tb obtained at 0³⁺Complex [V-34G4 / G4]
3-Tb and fourth-generation Tb obtained in Comparative Example 2³⁺Complex
[G-4]_Three-Tb was compared. 3 × 10 for each complex ^-6M
Of methylene chloride solution with a wavelength of 290 nm
545 nm fluorescence intensity when excited by irradiation with ultraviolet light
The ratio is shown in Table 1. In addition, the dendron complex of Example
Of copolymers with butyl methacrylate or styrene
Film and the resin composition film are all 290
When excited by ultraviolet light having a wavelength of nm, Tb³⁺Contains complex
In this case, the main fluorescence band around 545 nm is converted to Eu.³⁺Complex
, The main fluorescent band around 614 nm
Was given.

[0128]

Table 1 Experiment number Ratio of Tb ³⁺ complex 545 nm fluorescence intensity Example 25 [V-34G4] 3-Tb 2.5 Example 30 [V-34G4 / G4] 3-Tb 2.4 Comparative Example 2 [G -4] 3-Tb 1.0

Example 48 Synthesis of Copper (II) Complex of First Generation Copper (II) acetate hydrate was heated at 100 ° C. in vacuo to obtain the corresponding anhydrous salt. In Example 31, copper (II) acetate anhydride was used instead of europium (III) acetate anhydride, and a dendron carboxylate V-35G1-
The same experimental operation was performed using 2.0 equivalents of CO ₂ H.
The obtained residue was in the form of a transparent glass, and in the FT-IR spectrum, the absorption band of the carbonyl group attributed to the carboxyl group given by the raw material V-35G1-CO ₂ H was not observed, and the elemental analysis value Is 0.2% of the theoretical value
From the results, it was confirmed that a first-generation dendron complex having the desired vinyl group (abbreviated as [V-35G1] 2-Cu) was generated.

<Example 49: Second generation palladium (I
I) Synthesis of Complex> In Example 32, palladium (II) acetate anhydrous supplied from Aldrich was used instead of europium (III) acetate anhydride, and a dendron carboxylate V-35G2-CO ₂ H serving as a ligand was used. The same experimental operation was performed using 2.0 equivalents. The obtained residue was in the form of a transparent glass, and in the FT-IR spectrum, the absorption band of the carbonyl group attributed to the carboxyl group given by the raw material V-35G2-CO ₂ H was not observed. Was within 0.2% of the theoretical value, it was confirmed that a second generation dendron complex having the desired vinyl group (abbreviated as [V-35G2] 2-Pd) was formed.

Example 50 Synthesis of Third Generation Lead (II) Complex Lead hydrate of lead (II) acetate was heated at 130 ° C. in a nitrogen stream to obtain a corresponding anhydrous salt. In Example 33, instead of anhydrous europium acetate (III), anhydrous lead (II) acetate was used.
And a carboxylic acid dendron V-35G as a ligand
3-CO ₂ H was subjected to the same experimental procedure using 2.0 equiv. The resulting residue is in the form of a transparent glass, and FT-IR
In the spectrum, the absorption band of the carbonyl group attributed to the carboxyl group given by V-35G3-CO ₂ H of the raw material was not observed, and the elemental analysis value was 0.1% of the theoretical value.
Since the agreement was found within 2%, a third-generation dendron complex having a target vinyl group (hereinafter referred to as [V-35G3]
(Abbreviated as 3-Pb) was confirmed.

[0132]

Since the reactive polybenzyl ether dendron of the present invention has a vinyl derivative group at its terminal, it has useful reactivity such as various polymerization reactivity or addition reactivity such as hydroboration. When such a dendron has a coordinating functional group such as a carboxyl group, a transition metal complex containing the same as a ligand also has useful reactivity. Therefore, the transition metal complex gives, for example, a copolymer with a raw material monomer constituting an acrylic resin or a styrene resin, or a polymer of the complex itself, and a polymer obtained in this way has good transparency and mechanical properties. Has strength. These polymers can be used as a resin composition using, for example, an acrylic resin or a styrene resin as a matrix resin. Such a polymer or resin composition,
Various functional sheet-like molded articles, for example, when the above-mentioned transition metal complex has a fluorescent ability, a high-intensity fluorescent sheet is provided. It is useful as a layer or the like.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing dendron generations and focal points.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C07F 5/00 C07F 5/00 D C08G 65/34 C08G 65/34 C08J 5/18 C08J 5/18 C08L 71 / 00 C08L 71/00 C09K 11/00 C09K 11/00 A 11/06 11/06 F term (reference) 4F071 AA01 AA22 AA22X AA28X AA31X AA33 AA76 AH12 BA02 BB01 BC01 4H006 AA01 AA02 AB46 AC43 BJ50 BP30 BS30 GP03 GP03 GP12 AA01 AA03 AB92 VA00 VA20 VA70 VB10 4J002 BC031 BC071 BG041 BG061 BH011 CG001 CH062 EA046 EH076 GQ00 4J005 AA24 BA00

Claims (9)

[Claims] 1. A polybenzyl ether dendron having a vinyl-derived group at a non-focal point end. 2. The polybenzyl ether dendron according to claim 1, wherein the vinyl-derived group is derived from a vinylbenzyl group. 3. The polybenzyl ether dendron according to claim 1, wherein a carboxyl group is bonded to the focal point. 4. An etherification reaction in which a plurality of benzyl halide dendrons including at least one vinyl benzyl halide dendron are successively acted on hydroxybenzyl alcohols having a plurality of phenolic hydroxyl groups without isolation. Characterized in that:
3. The method for producing a polybenzyl ether dendron according to any one of 3. 5. A transition metal complex having the polybenzyl ether dendron according to claim 3 as a ligand. 6. The transition metal complex according to claim 5, wherein the transition metal contains at least one selected from a terbium cation and a europium cation. 7. A polymer comprising the transition metal complex according to claim 5 as a monomer unit constituting the polymer. 8. A resin composition containing the transition metal complex according to claim 5 or 6. 9. The polymer according to claim 7, or claim 8.
A sheet-like molded product obtained by molding the resin composition according to the above.