JPH07110938B2 - Light-heat energy storage / conversion material and its composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a light-heat energy storage / conversion material. More specifically, the invention is easy to handle, capable of storing and converting energy.
The present invention also relates to a light-heat energy storage / conversion material having good practicability.

(Conventional Technology and Its Problems) Conventionally, norbornadiene compounds are known to have a function of storing and converting light-heat energy,
For example, as shown in the following equation, Norbornadiene (NBD) and its derivative compounds are converted to the corresponding quadricyclane (QC) and its derivative compounds by irradiation with ultraviolet rays or visible light. The quadricyclenes (QCs) are easily reconverted to norbonadienes (NBDs) by heating or contact with a catalyst.
During this reconversion, about 22 Kcal of heat energy is released per mole of molecule. This energy is the energy of the irradiated light accumulated as strain energy in quadricycles (QCs).

Therefore, the photoreaction of norbonagen (NBD) / quadricyclane (QC) has been attracting attention as an excellent system of light-heat energy storage / conversion reaction.

However, this reaction system known so far is
Since both are reaction systems of low molecular weight compounds consisting of norbonagen (NBD) or its derivatives, in this state of low molecular weight compounds, light-heat energy storage / conversion is a peculiar feature, and the notable function is practically applied. It was almost impossible to develop into. Energy storage
It can be said that it was almost impossible to create functional materials for conversion.

In view of such circumstances, the inventor of the present invention has proceeded with a study for developing a light-heat energy storage / conversion system composed of the above-mentioned photoreaction system as a functional material, and has already reported that polymer It has been found that a non-low molecular weight reaction system can be realized by introducing a norbornadiene-derived group into the side chain.

However, there are still insufficient points in the search for those that are more reactive and that can be easily synthesized and handled as polymeric materials. In the past, quadricycline (QC) -derived groups The use of a solution of the catalyst was essential for the conversion to norbornadiene (NBD) -derived groups.

Such a point has been a major obstacle to the practical development of the photoreactive system as a functional material.

The present invention was made by further studying the present inventors as described above and further developing a polymer material system for storage / conversion of light-heat energy. New light that enables the development of
It is intended to provide a thermal energy storage / conversion material and its composition.

(Means for Solving the Problems) As a solution to the above problems, the present invention comprises a polymer compound having an epoxy group in a side chain and an esterification reaction of norbornadienecarboxylic acid or a derivative thereof. A light-heat energy storage / conversion material is provided.

The present invention also provides a composition comprising the above-mentioned material, which is characterized as a reaction system in a completely solid state, and a catalyst substance for converting a quadricyclenyl-derived group into a norbonagenenyl-derived group. The composition may have various shapes such as a film, a sheet and a bulk.

The photo-thermal energy storage / conversion material obtained by the esterification reaction of the present invention is characterized as a polymer compound having a norbornadienyl derivative group in its side chain. (R is an ester linkage structure to the polymer main chain, R ₁
To R ₇ are each a hydrogen atom, alkyl, cycloalkyl,
Alkenyl, cycloalkenyl, aryl, arylalkyl, alkylaryl, halogen, hydrocarbon, alkoxy, ether, ester, amine, amide, cyano, nitro, or any other organic group) The thing can be illustrated.

Various compounds can be used as the polymer compound having an epoxy group in the side chain used in synthesizing these compounds. For example (S ₁ and S ₂ represent a polymer main chain unit, n may be 0. A is any aliphatic, alicyclic or aromatic hydrocarbon group, and l is 0 or 1 or more. Shows the number of.

R ₀ represents an aliphatic, alicyclic or aromatic hydrocarbon group, a functional group bond composed of atoms such as oxygen, sulfur and nitrogen, or a bond between them and a hydrocarbon group. On the other hand, as the norbornadienecarboxylic acid derivative, a carboxylic acid of norbonadiene, an acid halide thereof, an ester thereof, a metal salt thereof, an ammonium salt thereof, which has a substituent of R _{1 to} R _{7 in accordance} with the above formula. And other compounds can be used.

Further, as a catalyst to be added to the composition of the light-heat energy storage / conversion material of the present invention, for example, cobalt-
Tetraphenylporphyrin complex (Co-TPP), cobalt-tetraphenylporphyrin tetracarboxylic acid complex, AgClO ₄ , cobalt-phthalocyanine complex, N, N-disalicylidene-4-carboxyl-1,2-phenylenediiminate-cobalt complex, etc. Any one can be used, including various known ones.

Examples of the present invention will be shown below, and the present invention will be described in more detail.

Example 1 (Synthesis of 3-phenyl-2,5-norbornadiene-2-carboxylic acid) Synthesis was carried out according to the reaction formula (A).

That is, first, 20.9 g of phenylpropyl acid chloride was placed in a 100 ml round-bottomed flask, 16 ml (0.24 mol) of cyclopentadiene obtained by cracking dicyclopentadiene was added, and 0.4 g of picric acid was added and stirred. Fever was recognized (about
58 ° C). After 1 hour, 8 ml of cyclopentadiene (0.12
Mol) was added and heated and refluxed for 1 hour. After air-cooling, the unreacted cyclopentadiene was removed by distillation under reduced pressure, and the residue was dissolved in about 100 ml of dry toluene, placed in a separating funnel and vigorously shaken with a 5w% aqueous sodium hydrogen carbonate solution to collect an aqueous layer. A 20w% aqueous solution of sulfuric acid was added to the aqueous layer for acid precipitation. The crystals were collected by filtration and washed with slightly acidic to neutral water. After sufficiently drying in a desiccator, it was recrystallized using n-hexane.

Yield: 11.2 g (Yield: 41.5%) Melting point: 134.0-135.0 ° C (literature value 135-136 ° C) Example 2 (Synthesis of Copolymer of Glycidyl Methacrylate (GMA) and Methyl Methacrylate (MMA)) GMA 34.117 g (0.24 mol), MMA 6.
007 g (0.06 mol) was added, and 90 ml of dioxane as a solvent and 0.75 mmol of AIBN as an initiator were added, followed by nitrogen substitution for 1 hour, 60
Polymerization was carried out at 5 ° C for 5 hours and at 80 ° C for 2 hours. It was poured into about 31 n-hexane and recovered. The obtained polymer is about 200
It was dissolved in ml and reprecipitated twice with about 31 n-hexane. After sufficiently drying, the reduced viscosity was measured at 30 ° C. in DMF at C = 0.5 g / dl. The epoxy equivalent was determined by the pyridine hydrochloride method. First, about 1 g of a sample was accurately weighed and placed in a 100 ml round-bottomed flask, 20 ml of a pyridine solution of hydrochloric acid (concentrated hydrochloric acid 16 ml + purified pyridine 984 ml) was added, and the mixture was refluxed for 30 minutes. 20 ml of a pyridine hydrochloride solution was titrated with 0.1N sodium hydroxide aqueous solution using phenolphthalein as an indicator. The refluxed solution was similarly titrated. Utilizing the reactivity between the epoxy group in the polymer and hydrochloric acid, the number of grams of the polymer (epoxy equivalent) per epoxy group was determined from the degree of decrease of hydrochloric acid in the solution.
The composition ratio of GMA-MMA was obtained from this epoxy equivalent.

With 36.7 g (yield 91.5%), a copolymer having GMA: MMA = 7.1: 2.9 and an epoxy equivalent of 182.66 was obtained.

Example 3 (Synthesis of GMA Radical Polymer) A three-necked flask GMA (49.745 g, 0.35 mol) was charged, a solvent and 1.75 mmol of AIBN as an initiator were added, and nitrogen substitution was carried out for 1 hour. Radical polymerization was carried out for 5 hours at 80 ° C. for 2 hours. THF was added and the mixture was put into n-hexane of about 31 to collect a polymer. It was dissolved in THF and reprecipitated twice with about 31 n-hexane. DM at 30 ℃ after drying under reduced pressure
The reduced viscosity was measured at C = 0.5 / dl in F. The epoxy equivalent was measured in the same manner as above by the pyridine hydrochloride method. The epoxy content was determined from the epoxy equivalent.

35.2 g (70.1% yield) of a polymer having an epoxy equivalent of 154.63 was obtained.

Example 4 (Reaction of GMA-MMA copolymer with 3-phenyl-2,5-norbonadiene-2-carboxylic acid (PNBA)) An esterification reaction was carried out according to the reaction formula (B). That is, first, in a 50 ml three-necked flask, 1.827 g of the copolymer synthesized in Example 2 (10 mmol as an epoxy group), 2.123 g of PNBA synthesized in Example 1 (10 mmol), and TB as a catalyst.
AB0.097g (0.3mmol, 3mol%), dehydrated as solvent D
20 ml of MF and a small amount of MQ were added, and the change with time of the addition reaction rate at 60 ° C, 70 ° C, 80 ° C, 90 ° C was measured. For the measurement of the addition reaction rate, exactly 1 ml of the solution was taken every hour, and the carboxylic acid in the solution was titrated with an alcoholic 0.1N potassium hydroxide solution using phenolphthalein as an indicator. The difference between the amount of carboxylic acid in the charged PNBA and the amount of unreacted carboxylic acid in the solution was determined from the titration value, and the addition reaction rate of the carboxylic acid and the epoxy group was calculated back from this value. The results are shown in FIG.

The display in the figure shows the following.

▲: Addition reaction temperature 60 ℃ ●: Addition reaction temperature 70 ℃ △: Addition reaction temperature 80 ℃ ○: Addition reaction temperature 90 ℃ Example 5 (GMA-MMA copolymer and 3-phenylcarbamoyl-2,5
-Reaction with norbornadiene-2-carboxylic acid (PCND)) An esterification reaction was performed according to the reaction formula (C). That is, first, in a 50 ml three-necked flask, 1.827 g of the copolymer synthesized in Example 2 (10 mmol as an epoxy group), PCND2.
553 g (10 mmol), TBAB 0.097 g (0.3 mmol, 3 mm%) as a catalyst, dehydrated DMF 20 ml as a solvent, and a small amount of MQ were added, and the change with time of the addition reaction rate at 80 ° C, 90 ° C and 100 ° C was measured. The addition reaction rate was measured by titration of unreacted carboxylic acid with an alkaline aqueous solution as in the above. The results are shown in FIG.

The display in the figure shows the following.

△: Addition reaction temperature 80 ° C ○: Addition reaction temperature 90 ° C □: Addition reaction temperature 100 ° C Example 6 (Reaction between GMA-MMA copolymer and acid chloride) GMA ₇₄ -MMA ₂₆ copolymer (0.189 g; 1.0 mmol) and catalyst TBAB
(0.032 g; 0.1 mmol) was dissolved in 2 ml of anisole, and 3-phenylcarbamoyl-2, was added according to the reaction formula (D).
5-Norbornadiene-2-carboxylic acid chloride (0.327 g;
1.0 mmol) was added and the reaction was carried out at 80 and 100 ° C.,
The results are shown in FIG. The reaction rate was measured by H-NMR spectrum.

Example 7 GMA ₇₄ -MMA ₂₆ copolymer (0.283 g; 1.5 mmol) and catalyst TBAB
(0.024 g; 0.075 mmol) was dissolved in 3 ml of anisole, and thereto was added 3- (4-R-phenyl) carbamoyl-2,5-norbonadiene-2- (4-nitrophenyl) carboxylate (according to reaction formula (E). 0.565 g; 1.5 mmol) (wherein R is H or COOH) is added to 80 and 100, respectively.
The results are shown in FIG. The reaction rate was measured by H-NMR spectrum.

Example 8 GMA ₇₄ -MMA ₂₆ copolymer (0.189 g; 1.0 mmol) and catalyst TBAB
(0.032 g; 0.1 mmol) was dissolved in 2 ml of anisole, 3-phenyl-2,5-norbonadiene-2-carboxylic acid chloride (0.233 g; 1.0 mmol) was added thereto, and the mixture was heated at 80 ° C and 100 ° C.
The reaction was carried out for up to 6 hours. The results are shown in FIG. The reaction rate was measured from the 1 H-NMR spectrum.

Example 9 GMA ₇₄ -MMA ₂₆ copolymer (0.189 g; 1.0 mmol) and catalyst TBAB
(0.032 g; 0.1 mmol) was dissolved in 2 ml of anisole, 3-phenyl-2,5-norbonadiene-2- (4-nitrophenyl) carboxylate (0.413 g; 1.0 mmol) was added thereto, and the reaction was carried out at 100 ° C. It was The results are shown in FIG.
The reaction rate was measured from the 1 H-NMR spectrum.

Example 10 (Photovalent isomerization reaction) A small amount of each of the polymers obtained by introducing PNBA, PCND, PCND derivatives (methoxy type) and (acetyl type) into the copolymer synthesized in Example 2 was dissolved in THF, It was applied to a quartz cell and photoreacted by an external irradiation method using a 250 W high pressure mercury lamp.

As a result, NBD residues in the polymer chain efficiently correspond to QC.
It was revealed that the photovalence isomerization reaction proceeds to the derivative.

FIG. 3 shows the conversion into the QC derivative in the case of the PNBA-introduced polymer compound as a change in the ultraviolet absorption spectrum. Irradiation time (minutes) 0,0.25,0.5,1,2,3, from above in the figure
5 and 10 are shown respectively.

Example 11 0.01 g of a polymer having an NBD residue in the side chain shown in Example 4
Was dissolved in 3 ml of THF to prepare a polymer solution. In polymer solution, 10, 15, 20, 30 and 40 mol for NBD residue
% Co-TPP was added to each to prepare a mixed solution of polymer and catalyst. This mixed solution was applied to a quartz cell and dried. The polymer film obtained on the quartz cell was irradiated with light from a distance of 30 cm using a 250-W ultra-high pressure mercury lamp, and the photoreaction rate was determined from the reduction rate of the UV spectrum before and after the light irradiation. As a result, the NBD residue in the polymer film containing no Co-TPP was quantitatively converted into QC in about 7 minutes of light irradiation, but in the polymer film containing 5 or 10 mol-% Co-TPP, the NBD residue by light irradiation was changed. -Isomerization reaction to QC,
Since the QC produced at the same time is converted into NBD again by contact with Co-TPP, the reaction rate from NBD to QC is about 70-7.
Equilibrium was reached around 5% and 40-45%. That is, this means that heat is generated at the same time as light irradiation. Further, each polymer film was irradiated with light for 10 minutes, and the re-conversion rate of QC residue in the produced polymer to NBD group was measured. Co-TP in polymer film
The higher the P content, the faster the conversion rate from QC to NBD. Furthermore, this means that the polymer film containing Co-TPP gradually radiates heat after light irradiation.
It suggests that it has been converted to NBD.

Example 12 Polymer alone synthesized in Example 5, and this polymer and Co
Each film made of -TPP was prepared on a quartz cell, and its photoreaction and the reverse isomerization reaction of the QC residue in the produced polymer film were measured. From this result, the reaction rate of NBD reached 100% after 6 minutes of light irradiation with the polymer alone.
Polymer films containing TPP have NBD conversions of approximately 30-40
Equilibrium was reached at mol%. When the polymer film containing Co-TPP after irradiation with light was allowed to stand at room temperature, the generated QC residue of the polymer side chain was gradually reconverted to NBD. This suggests that the functional film consisting of polymer and Co-TPP converts light energy into heat energy.

[Brief description of drawings]

FIG. 1 and FIG. 2 are correlation diagrams of the reaction time and the conversion rate showing the change with time of the esterification addition reaction rate of the present invention. FIG. 3 is a correlation diagram between the wavelength and the absorption of the photoisomerization reaction. FIG. 4, FIG. 5, FIG. 6 and FIG. 7 are correlation diagrams of the reaction time and the conversion rate showing the changes with time of the reaction rates of Examples 6, 7, 8 and 9 of the present invention.

Claims (2)

[Claims] 1. A photo-thermal energy storage / conversion material comprising a polymer compound having an epoxy group in a side chain and an esterification reaction of norbornadienecarboxylic acid or a derivative thereof. 2. A photo-thermal energy storage / conversion material composition comprising the material according to claim (1) and a catalyst substance for converting a quadricyclen-derived group into a norbornadienyl derived group.