JP3083162B2 - Norbornadiene photoenergy storage / conversion polymer having rigid main chain structure and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer compound useful as a light energy storage / conversion polymer and a method for producing the same.

[0002]

2. Description of the Related Art Norbornadiene (hereinafter referred to as "NBD") light energy storage / conversion polymer is synthesized by the reaction of poly (chloromethylstyrene) with a carboxylic acid derivative of norbornadiene or by polymerization of a styrene derivative of norbornadiene and a vinyl ether derivative. Was.

[0003]

The polymer having NBD in the side chain synthesized from conventional poly (chloromethylstyrene) is known as quazorisicran (hereinafter referred to as "Q
In the case of reverse isomerization of-)-NBD, there was a problem that NBD generated due to heat generation is gradually decomposed by a side reaction such as a reverse Diels-Under reaction and deteriorates when used repeatedly.

[0004] That is, an object of the present invention is to provide a light energy storage / conversion polymer in which the thermal stability of NBD in the side chain is improved.

[0005]

The polymer compound of the present invention has the following formula (I):

[0006]

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Wherein X ¹ and X ² are a hydrogen atom, a bromine atom or the following formula (IIa):

[0008]

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(Wherein R ¹ , R ² and R ³ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an arylcarbamoyl group). Wherein the molar ratio of the bromine atom represented by X ¹ and / or X ² and the group represented by the formula (IIa) to the structural unit (I) is X ¹ and X ² . In total, 0 to 90 mol% of a bromine atom, a group represented by the formula (IIa)
A compound having a molecular weight of 10,000 to 1,000,000 (hereinafter referred to as “polymer P-4” or “P
-4 ").

In the above formula (I), the molar ratio is
0 to 10 mol% of a bromine atom, a group represented by the formula (IIa) 100
It is preferably about 50 mol%. In the above formula (I), examples of the halogen atom represented by R ¹ , R ² or R ³ include a fluorine atom, a chlorine atom and an iodine atom.
The alkyl group is a linear or branched alkyl group having ₁ to ₁₂ carbon atoms, preferably ₁ to ₄ carbon atoms, and examples thereof include a methyl, ethyl, propyl, and butyl group. . Examples of the aryl group include a phenyl group, a naphthyl group, a p-chlorophenyl group, a p-acetylphenyl group, and a p-methylphenyl group. Examples of the arylcarbamoyl group include a phenylcarbamoyl group and a p-acetylphenyl. A carbamoyl group, a p-methylphenylcarbamoyl group, a p-chlorophenylcarbamoyl group and the like.

The polymer compound of the present invention has, for example, the following formula:
(II):

[0012]

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(Wherein M represents a metal atom or an ammonium salt, and R ¹ , R ² and R ³ are as defined above), and the following formula (III):

[0014]

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(Wherein, Y ¹ and Y ² represent a hydrogen atom or a bromine atom), and the structural unit of the bromine atom represented by Y ¹ and / or Y ² (III molar ratio) is, together Y ¹ and Y ^2, 10 to 200
It can be produced by reacting a polymer compound which is mol%. In the formula (II), the metal atom represented by M is preferably an alkali metal atom such as potassium or sodium, and the ammonium salt is preferably triethylammonium or trimethylammonium.

The polymer compound comprising the structural unit represented by the above formula (III) (hereinafter sometimes referred to as "polymer P-2" or "P-2") may have a bromination ratio of 10 to 200 mol%,
That is, in the formula (III), the molar ratio of the bromine atom represented by Y ¹ and / or Y ² to the structural unit (III) is
A polymer in which Y ¹ and Y ² together account for 10 to 200 mol%.

This reaction is carried out in a solvent such as chlorobenzene, methylene chloride, nitrobenzene, tetrahydrofuran, etc.
Tetrabutylammonium bromide (hereinafter "TBAB")
The reaction is preferably carried out at 30 to 100 ° C. for 5 to 24 hours in the presence of a phase transfer catalyst such as tetrapentyl ammonium bromide or tetrahexylammonium bromide.
For example, as shown in the following reaction formula, the polymer P-2 is obtained by oxidative polymerization of 2,6-dimethylphenol,
10,000 to 1,000,000 poly (2,6-dimethyl-p-phenylene ether) (hereinafter sometimes referred to as "Polymer P-1")
Or "P-1") and then reacting with bromine.

[0018]

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[0019]

EXAMPLES The present invention will be described in more detail with reference to the following Examples and Test Examples, which do not limit the scope of the present invention. Example (1) Poly (2,6-dimethyl-p-phenylene ether)
Synthesis of

[0020]

[Formula 10]

Nitrobenzene (200 ml), pyridine (70 m
l), copper (I) chloride (1 g) was charged and oxygen (300 ml / min)
While agitating vigorously. 15 g (0.12 mol) of 2,6-dimethylphenol was added, and when the mixture became sticky, the reaction was continued for 12 minutes and diluted with chloroform (100 ml).
The solution was dropped into methanol (1.1 l) containing concentrated hydrochloric acid (3 ml), and filtration and reprecipitation were repeated three times. After washing with methanol, drying was performed at 110 ° C. for 3 hours.

Yield 13.1 g (97.0%) Reduced viscosity 1.62 (measured in chloroform at 30 ° C., C = 0.5 g /
dl) Molecular weight The polymer P-1 has an absorption range of NBD.
From the above, it was confirmed that it did not have strong absorption in the ultraviolet region of 450 nm. (2) Radical bromination

[0023]

[Formula 11]

4.8 g (0.04 mol) of poly (2,6-dimethyl-p-phenylene ether) was dissolved in 1,1,2,2-tetrachloroethane (200 ml). 0.5 ml (0.01 mol) of bromine to 50 ml
It was dissolved in 1,1,2,2-tetrachloroethane and refluxed for 1.5 hours while dropping the solution into the boiling solution. Further, it was dissolved in 1 l of methanol, reprecipitated, and dried. After dissolving in chloroform and reprecipitating in methanol, the same process was carried out with mol% of bromine at (50, 75, 100). Table 1 shows the results.

[0025]

【table 1】

A) This reaction produced a small amount of gel.
After removing the gel, the yield of soluble polymer was measured. b) Measured in chloroform at 30 ° C, C = 0.5 g / dl. As a result of the synthesis, it was found that the bromination ratio of the obtained polymer was slightly lower than the charge ratio. 50% charge ratio
Above, a small amount of gel was formed, and at the same time, decomposition occurred.
I decided to use -2b. (3) Synthesis of polymer having side chain NBD

[0027]

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Polymer P-2b having a bromination ratio of 0.44 mol%
47 g (1.5 mmol) and 0.44 g (1.5 mmol) of potassium carboxylate of three kinds of NBD derivatives were added to 20 ml of chlorobenzene at 80 ° C. using 0.15 mmol of TBAB as a phase transfer catalyst.
Reacted for hours. Table 2 shows the results.

[0029]

[Table 2]

Test Example 1 Photo-Atomization Isomerization Reaction (1) Solution The obtained polymer having a side chain NBD was dissolved in dichloromethane to prepare a 7.5 × 10 ⁻⁵ (mol / l) solution. This was put into a quartz cell for UV spectrum, and irradiated with light from an ultra-high pressure mercury lamp (illuminance: 2.1 mWcm ^-2 ) having a light source of 500 W. The conversion and reaction rate constants were determined by following the change in the UV spectrum, and compared with each other.

P-4a in solution and the following model compound
For comparison with the photoreactivity of (M-1) and P-5a having a polystyrene skeleton, the results obtained by substituting into the primary reaction formula are shown in FIG. It has already been reported that the polymer (P-5a) having a polystyrene type skeleton progresses faster than the low molecular weight model compound (M-1), but the P-4a polymer of the present invention is It's getting late. This seems to be affecting the photoreactivity because the main chain has a rigid structure.

[0032]

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[0033]

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(2) Film Similarly, the photo-atomization isomerization reaction of a polymer having various side chains NBD in the form of a film was carried out using an ultra-high pressure mercury lamp (illuminance: 2.2 mWcm ^-2 ) with a light source of 250 W and a xenon lamp of 500 W. Was. That is, the NBD polymer of the present invention and the polymer having a polystyrene type skeleton reported so far.
The photoreactivity of (P-5a) in a film state was examined. The result is shown in FIG. The polymer (P-4a) of the present invention was expected to have reduced photoreactivity due to the rigid main chain as compared with the polymer (P-5a) having a polystyrene type skeleton. Reactivity was about the same. It has been found that the NBD polymer (P-4b) having a phenyl group (P-4c) or a p-acetylphenylcarbamoyl group as a substituent has extremely high reactivity. From these facts, it became clear that the effect of the main chain structure was very small in the film, and the effect of the NBD substituent was larger than that.

Test Example 2 Reverse isomerization reaction (1) Reverse isomerization with a catalyst
³ ml of a solution of 10 ^-3 (mol / l) of cobalt-tetraphenylporphyrin / methylene chloride was added, and the reverse isomerization was performed from QC to NBD at a reaction temperature of 25 ° C, followed by tracking by UV spectrum. FIG. 3 shows the result obtained by substituting the increase rate of the absorption at 324 nm of NBD into the linear equation. When a photoreaction occurs, the polymer undergoes partial cross-linking and swells, so it is not possible to compare it unequivocally compared to the homogeneous solvent of the model compound. It became. (2) Reverse isomerization by heat
The reverse isomerization reaction was carried out by heating at 40 ° C. and 160 ° C., and by repeating this, the thermal stability at the time of reverse isomerization was examined.

FIG. 4 shows the change of UV spectrum when NBD is isomerized to QC by irradiating polystyrene type P-5a with a xenon lamp from a distance of 50 cm for 20 minutes and then heating at 160 ° C. for 5 minutes. Show. Even after heating after irradiation, the absorption at 324 nm based on NBD did not increase, and no reverse isomerization reaction occurred. Similarly, the results of the IR spectrum are shown in FIG. When heated at 160 ° C. for 30 minutes after light irradiation, the QC polymer showed a completely different absorption than the original NBD polymer. QC
It is considered that the polymer was decomposed by heat generated when the isomerized polymer was reverse isomerized.

FIG. 6 shows the result of repeating irradiation of the polymer film of P-4a with light and heating at 160 ° C. for 30 minutes seven times. As a result, unlike P-5a, the reverse isomerization reaction due to heat proceeds smoothly, and the polymer gradually deteriorates during repetition, but can withstand repeated use even under severe conditions, It has been found that the composition has high stability against the heat generated during the heat treatment.

Similarly, phenylcarboxylic acid type NBD
A film of P-4c having the following isomerization reaction (light irradiation for 5 minutes) and reverse isomerization reaction (160 ° C.) at 160 ° C.
FIG. 7 shows the result of repeating (heating at 10 ° C. for 10 minutes). Since phenylcarboxylic acid type NBD has high thermal stability, it can be used repeatedly even with polystyrene type polymer. However, it became clear that the amplitude was significantly smaller than that of P-4c and thermal stability was poor.

[0039]

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From the above, it can be seen that a poly-
The NBD polymer of the present invention having (2,6-dimethyl-p-phenylene oxide) shows remarkably higher thermal stability than a polystyrene type polymer, and is repeatedly used in such severe heat-induced QC-NBD reverse isomerization reaction. Since it can be used, it is expected that an NBD light energy storage / conversion polymer that can be used stably for a long period of time by employing a QC-NBD reverse isomerization reaction with a catalyst that can be performed under mild conditions.

[0041]

According to the present invention, it is possible to provide an NBD polymer having extremely excellent thermal stability as compared with a conventional polystyrene type NBD polymer.

[Brief description of the drawings]

FIG. 1 is a diagram showing the results of substituting into a first-order reaction equation of a photoatomization isomerization reaction in a solution.

FIG. 2 is a view showing the result of substituting into a first-order reaction equation of a photoatomization isomerization reaction in a film form.

FIG. 3 is a diagram showing the result of substituting into a linear equation of a reverse isomerization reaction using a catalyst.

FIG. 4 is a diagram showing a change in UV spectrum of a P-5a film.

FIG. 5 is a diagram showing a change in IR spectrum of a P-5a film.

FIG. 6 is a diagram showing changes in QC groups in a polymer when light irradiation and heating are repeated.

FIG. 7 is a diagram showing a change in a QC group in a polymer when light irradiation and heating are repeated.

Claims (2)

(57) [Claims] (1) The following formula (I): Wherein X ¹ and X ² are a hydrogen atom, a bromine atom or the following formula (IIa): (Wherein R ¹ , R ² and R ³ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an arylcarbamoyl group). Wherein the molar ratio of the bromine atom represented by X ¹ and / or X ² and the group represented by the formula (IIa) to the structural unit (I) is X ¹ and X ² . Together, the bromine atom 0
A high molecular compound having a molecular weight of 10,000 to 1,000,000, containing 90 mol% and 10 to 200 mol% of the group represented by the formula (IIa); (2) The following formula (II): (Wherein M represents a metal atom or an ammonium salt, and R ¹ ,
R ² and R ³ are as defined above. ) And a compound of the following formula (III): (Wherein, Y ¹ and Y ² represent a hydrogen atom or a bromine atom.) Wherein Y ¹ and / or Y 2
Molar ratio of the structural units of a bromine atom represented by ² (III) is, together Y ¹ and Y ^2, claim 1, comprising reacting a polymeric compound is 10 to 200 mol%
A method for producing the polymer compound according to the above.