JP5128987B2 - Pyrene compounds and polymer compounds containing the same - Google Patents

Description

  The present invention relates to a novel pyrene compound and a polymer compound containing the same, and in particular, the pyrene compound and the polymer compound can be used as, for example, an organic electronic material, a light emitting element material, and an optical material.

  (Meth) acrylic acid and derivatives thereof are important as raw material monomers for producing a polymer by homopolymerization or copolymerization, and in order to obtain a polymer having a desired performance, a further novel (meth) acrylate monomer Development is required.

On the other hand, pyrene compounds are widely used as blue light-emitting materials because they exhibit strong light emission in the blue region. It is known that when the luminescent molecule is present alone or at a high concentration, the luminescence efficiency is lowered by the interaction caused by the proximity of the luminescent molecule. Then, the synthesis | combination of the pyrene compound from which a structure differs is performed actively, and it is applied as a light emitting element material, a light emitting element (refer patent documents 1-5), and an organic photoconductive compound (refer patent document 6). In order to put these pyrene compounds into practical use, it is necessary to maintain luminescence continuously. It is known that the light emission of this pyrene group is determined by its orientation, and when the concentration is high, the light emission power and sustainability decrease. Therefore, it is used by being dispersed in a polymer such as polycarbonate. However, in this method, it is necessary to consider the compatibility with the polymer, and the practical use is limited.
JP 2001-118682 A JP 2003-272864 A JP 2004-75567 A JP 2007-77185 A JP 2007-224171 A Japanese Patent Laid-Open No. 5-301876

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a pyrene compound and a polymer compound useful as an organic electronic material, a light emitting device material, and an optical material.

The pyrene compound according to the present invention is:
Formula (I)

(Where
R _{1 to} R ₁₀ are:
Each may be the same or different, hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero Represents a substituent selected from the group consisting of an aryl group, halogen, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, phosphine oxide group and silyl group;
Adjacent substituents may form a ring; or at least one of R _{1 to} R ₁₀ is used for linking with an amide group;
R ₁₁ is an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group containing a polymerizable reactive functional group such as a vinyl group or a (meth) acryl group. Selected from the group consisting of a group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, phosphine oxide group, silyl group and pyrene group Represents a substituent. )
It is represented by.

  The polymer compound according to the present invention is obtained by copolymerization of the above-described pyrene compound with another monomer.

  The novel pyrene compound of the present invention and a polymer compound containing the same improve the compatibility with a copolymerizable monomer by imparting hydrophilicity derived from an amide group to a hydrophobic pyrene compound, and π due to a pyrene group It is a polymer whose structure is controlled by correlation between molecules such as stacking, and can be provided as an organic electronic material, light emitting device material, or optical material. Furthermore, since the pyrene group introduced into the polymer is chemically stable and is a highly safe polymer and polymer gel with suppressed elution, it can be provided as a medical device.

<Pyrene compound according to the present invention>
The pyrene compound represented by the general formula (I) used in the present invention will be described.

In the formula (I), R _{1 to} R ₁₀ may be the same as or different from each other, and are hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group. , Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, phosphine oxide group and silyl group. Moreover, R < ₁ > -R < ₁₀ > may form the ring with adjacent substituents. At least one of R _{1 to} R ₁₀ is used for linking with an amide group.

In the formula (I), R ₁₁ is an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group containing a polymerizable reactive functional group such as a vinyl group or a (meth) acryl group. Alkynyl group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, phosphine oxide group, silyl group and A substituent selected from the group consisting of a pyrene group is shown.

  Among these substituents, the alkyl group is, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. This may or may not have a substituent. There is no restriction | limiting in particular in the additional substituent in the case of being substituted, For example, an alkyl group, an aryl group, heteroaryl group etc. can be mentioned, This point is common also in the following description. Further, the number of carbon atoms of the alkyl group is not particularly limited, but is usually in the range of 1 to 20 and more preferably 1 to 8.

  The cycloalkyl group represents, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may or may not have a substituent. The carbon number of the alkyl group moiety is not particularly limited, but is usually in the range of 3 or more and 20 or less.

  The heterocyclic group refers to an aliphatic ring having atoms other than carbon, such as a pyran ring, a piperidine ring, and a cyclic amide, in the ring, which may or may not have a substituent. . Although carbon number of a heterocyclic group is not specifically limited, Usually, it is the range of 2-20.

  An alkenyl group shows the unsaturated aliphatic hydrocarbon group containing double bonds, such as a vinyl group, an allyl group, and a butadienyl group, and this may or may not have a substituent. Although carbon number of an alkenyl group is not specifically limited, Usually, it is the range of 2-20.

  The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group, which may have a substituent. You don't have to.

  An alkynyl group shows the unsaturated aliphatic hydrocarbon group containing triple bonds, such as an ethynyl group, for example, and may or may not have a substituent. Although carbon number of an alkynyl group is not specifically limited, Usually, it is the range of 2-20.

  The alkoxy group refers to, for example, a functional group having an aliphatic hydrocarbon group bonded through an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group may have a substituent. It may not have. Although carbon number of an alkoxy group is not specifically limited, Usually, it is the range of 1-20.

  The alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Usually, it is the range of 1-20.

  An aryl ether group refers to a functional group to which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Good. Although carbon number of an aryl ether group is not specifically limited, Usually, it is the range of 6-40.

  An aryl thioether group is one in which the oxygen atom of the ether bond of the aryl ether group is substituted with a sulfur atom. The aromatic hydrocarbon group in the aryl ether group may or may not have a substituent. The number of carbon atoms of the arylthioether group is not particularly limited, but is usually in the range of 6 to 40.

  The aryl group refers to an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, a phenanthryl group, a terphenyl group, and a birenyl group. The aryl group may or may not have a substituent. Although carbon number of an aryl group is not specifically limited, Usually, it is the range of 6-40.

  A heteroaryl group is a 5-membered aromatic group having one non-carbon atom in the ring, such as a furanyl group, a thiophenyl group, a benzofuranyl group, or a dibenzofuranyl group, one non-carbon atom such as a biridyl group or a quinolinyl group. Alternatively, a 6-membered aromatic group having a plurality of rings in the ring is shown, which may or may not have a substituent. Although carbon number of heteroaryl group is not specifically limited, Usually, it is the range of 2-30.

  The halogen atom represents fluorine, chlorine, bromine or iodine.

  The carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, and phosphine oxide group may or may not have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, and an aryl group. , Heteroaryl groups and the like, and these substituents may be further substituted.

  A silyl group refers to, for example, a functional group having a bond to a silicon atom, such as a trimethylsilyl group, which may or may not have a substituent. Although carbon number of a silyl group is not specifically limited, Usually, it is the range of 3-20. The number of silicon is usually 1 or more and 6 or less.

  A pyrene group shows the polycyclic aromatic group which four 6-membered rings (benzene ring) condensed, and this may or may not have a substituent. Further, the substituents may be the same or different, and adjacent substituents may form a ring.

When the condensed ring formed between adjacent substituents is described in the general formula (I), any adjacent two substituents selected from R _{1 to} R ₁₀ (for example, R ₁ and R ₂ ) are They are bonded to each other to form a conjugated or non-conjugated condensed ring. As a constituent element of the condensed ring, in addition to carbon, nitrogen, oxygen, sulfur, phosphorus, silicon atoms may be contained, and further, it may be condensed with another ring.

  Although it does not specifically limit as a pyrene compound represented by the above general formula (I), Specifically, the following examples (II), (III), and (IV) are mentioned.

  The novel pyrene compound of the present invention can be obtained by a conventional amide bond forming reaction. For example, a dehydration condensation reaction of a carboxyl group-containing monomer and aminopyrene, an activated ester such as a carboxylic acid halide, an acid anhydride, or a carboxylic acid azide. And a substitution reaction of aminopyrene.

  Examples of aminopyrene include 1-aminopyrene, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8-diaminopyrene, 1- (acetylamino) pyrene, and 1-aminopyrene is Tokyo Chemical Industry Co., Ltd. Is available from

  The carboxyl group-containing monomer that undergoes dehydration condensation with aminopyrene is one having at least one carboxyl group in the molecule. Examples thereof include methacrylic acid, succinic acid 1- (2-methacryloyloxyethyl), itaconic acid, and the like.

  As the dehydrating condensing agent used in the dehydrating condensation reaction between the carboxy group-containing monomer and aminopyrene, any coupling agent can be used. For example, a carbodiimide condensing agent such as DCC (N, N′-dicyclohexylcarbodiimide), TBTU, etc. Benzotriazole condensing agents such as (tetrafluoroboric acid 2- (1H-benzotriazol-1-yl) -1,1,3,3-tetramethyluronium), BOP reagent (benzotriazol-1-yloxy-tris) Dimethylaminophosphonium salt) can be used, and two or more thereof can be used in combination.

  Examples of the activated ester used for the substitution reaction with aminopyrene include (meth) acrylic anhydride, (meth) acrylic chloride, and the like.

<Polymer compound according to the present invention>
The novel pyrene compound of the present invention can synthesize the polymer compound of the present invention such as hard, soft and hydrous material by radical polymerization. The synthesis of the polymer compound is possible only with the novel pyrene compound of the present invention, but it is also possible to copolymerize with a monomer different from this pyrene compound. By copolymerizing with different monomers, the physical properties of the synthesized polymer can be controlled and used for various purposes. For example, an organic EL display, an operating state display of an audio device, an electronic display panel of an automobile, a digital watch, an electron-transporting organic thin film such as a personal computer, a light emitting element, an organic conductive compound, and the like can be given. Furthermore, since it can be stably introduced into a polymer, it can be used as a medical device taking advantage of the light emission characteristics of a pyrene group. Examples thereof include an ophthalmic lens, a DDS device, a wound dressing, and a cell culture device for supporting regenerative medicine.

  The monomer copolymerizable with the pyrene compound of the present invention has one or more polymerizable functional groups in the molecule. Examples of the polymerizable functional group include a methacrylate group, an acrylate group, a vinyl group, and an allyl group, and two or more kinds thereof can be used in combination.

  In the present invention, a crosslinking monomer can be used in addition to the above. The crosslinkable monomer may not be used, but the formation of a network structure and adjustment of the mechanical strength can be achieved by using the crosslinkable monomer. Further, when copolymerized with a hydrophilic monomer, a hydrogel is obtained. Examples of the crosslinkable monomer include ethylene glycol dimethacrylate, methylene bisacrylamide, 2-hydroxy-1,3-dimethacryloxypropane, trimethylolpropane triacrylate, and the like. The amount of the crosslinkable monomer used is preferably 0.1 to 4.0% by weight based on the total amount of monomers used. Particularly preferred is 0.1 to 1.0% by weight.

  In the production of the polymer compound containing the novel pyrene compound of the present invention, first, a polymerization initiator is added to the mixture of monomers, and further stirred and dissolved. As polymerization initiators, peroxides such as lauroyl peroxide, cumene hydroperoxide, and benzoyl peroxide, azobisvaleronitrile, azobisisobutyronitrile (AIBN), etc., which are general radical polymerization initiators, are used. it can. The addition amount of the polymerization initiator is preferably about 10 to 3500 ppm with respect to the total amount of monomers.

  Put the monomer mixture into a mold such as metal, glass, plastic, etc., seal it, raise the temperature stepwise or continuously in a constant temperature bath or the like in the range of 25 to 120 ° C., and complete the polymerization in 5 to 120 hours. . In the polymerization, ultraviolet rays, electron beams, gamma rays, or the like can be used. In addition, solution polymerization can be applied by adding water or an organic solvent to the monomer mixture.

  After completion of the above polymerization, it is cooled to room temperature, and the resulting polymer can be taken out of the mold and cut and polished as required to process it into a desired shape.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In addition, the number of the compound in each following Example points out the number of the compound described in said chemical formula.

(Evaluation method)
[Structural analysis of compounds]
¹ H-NMR and ¹³ C-NMR were measured in a deuterated chloroform solution using a superconducting FTNMR UNITY INOVA 400S (Varian).

[Measurement of infrared absorption spectrum]
The infrared absorption spectrum of the compound was measured using an infrared spectrophotometer (FT / IR-4100: Jusco).

[Measurement of light transmittance]
The light transmittance of the polymer compound was measured using an ultraviolet-visible spectrophotometer (UV-3150: Shimadzu Corporation).

[Measurement of absorption spectrum]
The absorption spectrum of the polymer was measured using an ultraviolet-visible spectrophotometer (UV-3150: Shimadzu Corporation).

[Evaluation of luminous properties]
The emission color was observed under light rays with wavelengths of 254 nm and 386 nm.

[Measurement of moisture content]
The water content of the polymer gel copolymerized with the hydrophilic monomer was measured according to “Measurement of water content of hydrogel lens (ISO 10339: 1997)”.

[Evaluation of dissolution]
After the polymer compound and polymer gel containing the pyrene compound were immersed in water for 24 hours, the elution property of pyrene was determined by irradiating the immersion liquid with ultraviolet rays. When elution was recognized, it evaluated as x, and when it was not recognized, it evaluated as (circle).

Example 1 (Synthesis Method of Compound [II])
A mixed solution of 1.17 g (10 mmol) of 1-aminopyrene, 1.03 g (12 mmol) of methacrylic acid, 1.86 g (12 mmol) of EDC and 40 mL of dichloromethane was stirred at room temperature for 24 hours under an argon atmosphere. The reaction solution was washed with 0.5N hydrochloric acid, saturated NaHCO ₃ aqueous solution and saturated NaCl aqueous solution, and then purified by silica gel column chromatography. The obtained solid was recrystallized and vacuum-dried to obtain 1.77 g (yield 62%) of pale green crystals. The results of ¹ H-NMR and ¹³ C-NMR analysis of the obtained powder are as follows, and it was confirmed that the pale green crystal obtained above was Compound [II].

¹ H-NMR (CDCl ₃ ) δ ppm; 2.12 (s, 3H), 5.50 (s, 1H), 5.95 (s, 1H), 7.67-8.17 (m, 10H)

¹³ C-NMR (CDCl ₃ ) δ ppm; 16.86, 118.00, 118.41, 120.28, 121.63, 122.36, 122.70, 122.74, 122.84, 123.19, 123.87, 123.90, 124.61, 125.03, 125.45, 126.91, 127.88, 128.48, 129.02, 138.47

Example 2 (Synthesis Method of Compound [III])
A mixed solution of 2.17 g (10 mmol) of 1-aminopyrene, 2.76 g (12 mmol) of methacryloyloxyethyl succinic acid, 1.86 g (12 mmol) of EDC and 40 mL of dichloromethane was stirred at room temperature for 24 hours under an argon atmosphere. The reaction solution was washed with 0.5N hydrochloric acid, saturated NaHCO ₃ aqueous solution and saturated NaCl aqueous solution, and then purified by silica gel column chromatography. The obtained solid was recrystallized and vacuum dried to obtain 2.57 g of gray crystals (yield 60%). The results of ¹ H-NMR and ¹³ C-NMR analysis of the obtained powder are as follows, and it was confirmed that the red crystal obtained above was Compound [III].

¹ H-NMR (CDCl ₃ ) δ ppm; 1.89 (s, 3H), 2.81 (s, 4H), 4.35 (s, 4H), 5.50 (s, 1H), 6.09 ( s, 1H), 7.78-8.36 (m, 9H)

¹³ C-NMR (CDCl ₃ ) δ ppm; 16.19, 27.50, 29.59, 60.25, 60.56, 118.35, 120.31, 121.60, 122.34, 122.71, 122.74, 122.77, 123.15, 123.88, 124.18, 124.59, 124.99, 125.48, 126.86, 127.96, 128.52, 129.02, 133. 71,165.12,168.64,170.98

Example 3 (Method for Synthesizing Compound [IV])
A mixed solution of 2.72 g (12.5 mmol) of 1-aminopyrene, 0.65 g (5 mmol) of itaconic acid, 1.94 g (12.5 mmol) of EDC and 40 mL of dichloromethane was stirred at room temperature for 24 hours under an argon atmosphere. The reaction solution was washed with 0.5N hydrochloric acid, saturated NaHCO ₃ aqueous solution and saturated NaCl aqueous solution, and then purified by silica gel column chromatography. The obtained solid was recrystallized and dried under vacuum to obtain 1.32 g (yield 50%) of red crystals. The results of ¹ H-NMR and ¹³ C-NMR analysis of the obtained powder are as follows, and it was confirmed that the red crystals obtained above were compound [IV].

¹ H-NMR (CDCl ₃ ) δ ppm; 2.25 (s, 2H), 6.64 (s, 2H), 7.80-8.25 (m, 20H)

¹³ C-NMR (CDCl ₃ ) δ ppm; 9.39, 108.05, 108.60, 109.19, 111.87, 111.90, 114.77, 118.08, 119.54, 121.46 121.66, 122.03, 122.19, 122.33, 123.01, 123.32, 123.41, 123.75, 123.91, 123.96, 123.99, 124.18, 124. 32, 125.01, 125.54, 125.86, 126.37, 126.79, 128.64, 128.92, 129.56, 129.85, 130.11, 138.82, 144.27, 161.93, 169.37

Examples 4 to 6 (Synthesis of polymer compounds including compounds [II, III, IV])
Compounds [II], [III] and [IV] (0.1 g), methyl methacrylate (9.9 g), and AIBN (2000 ppm) were mixed, and the mixture was stirred for about 1 hour while sufficiently purging with nitrogen. After stirring, the monomer mixture was placed in a mold and heated in the range of 50 to 100 ° C. over 25 hours to obtain a polymer. In the polymer compounds of Examples 4 to 6, a peak derived from a pyrene group was confirmed near 350 nm shown in FIGS. In addition, FIG. 1 is an infrared spectrum about the polymer obtained in Examples 4-6.

Examples 7 to 9 (Synthesis of polymer gel containing compounds [II, III, IV])
Compound [II], [III] and [IV] 0.1 g, 2-hydroxyethyl methacrylate 9.9 g, ethylene glycol dimethacrylate 0.01 g, and AIBN 2000 ppm were mixed and stirred for about 1 hour with sufficient nitrogen substitution. did. After stirring, the monomer mixture was placed in a mold and heated in the range of 50 to 100 ° C. over 25 hours to obtain a polymer. The obtained polymer was returned to room temperature, taken out from the container, and hydrated and swollen by being immersed in distilled water at about 60 ° C. for about 4 hours to obtain a hydrous gel.

(Comparative Example 1)
10 g of methyl methacrylate and 2000 ppm of AIBN were mixed and stirred for about 1 hour while sufficiently purging with nitrogen. After stirring, the monomer mixture was placed in a mold and heated in the range of 50 to 100 ° C. over 25 hours to obtain a polymer. As shown in FIG. 5, it was confirmed that no peak derived from a pyrene group appearing near 350 nm appeared.

(Comparative Example 2)
10 g of methyl methacrylate and 2000 ppm of AIBN were mixed, 1 g of aminopyrene was added, and the mixture was stirred for about 1 hour while sufficiently purging with nitrogen. After stirring, the monomer mixture was placed in a mold and heated in the range of 50 to 100 ° C. over 25 hours to obtain a polymer. As shown in Table 1, light emission derived from a pyrene group was observed, but elution into water was also observed.

(Comparative Example 3)
10 g of 2-hydroxyethyl methacrylate, 0.1 g of ethylene glycol dimethacrylate, and 2000 ppm of AIBN were mixed and stirred for about 1 hour while sufficiently purging with nitrogen. After stirring, the monomer mixture was placed in a mold and heated in the range of 50 to 100 ° C. over 25 hours to obtain a polymer. The obtained polymer was returned to room temperature, taken out from the container, and hydrated and swollen by being immersed in distilled water at about 60 ° C. for about 4 hours to obtain a hydrous gel.

(Comparative Example 4)
10 g of 2-hydroxyethyl methacrylate, 0.1 g of ethylene glycol dimethacrylate and 2000 ppm of AIBN were mixed, and 1 g of aminopyrene was added and stirred for about 1 hour while sufficiently purging with nitrogen. After stirring, the monomer mixture was placed in a mold and heated in the range of 50 to 100 ° C. over 25 hours to obtain a polymer. The obtained polymer was returned to room temperature, taken out from the container, and hydrated and swollen by being immersed in distilled water at about 60 ° C. for about 4 hours to obtain a hydrous gel. As shown in Table 1, light emission derived from a pyrene group was observed, but elution into water was also observed.

It is an infrared spectrum about the polymer obtained in Examples 4-6. It is a UV spectrum of Example 4. 6 is a UV spectrum of Example 5. It is a UV spectrum of Example 6. 2 is a UV spectrum of Comparative Example 1.

Claims (3)

Formula (III)
Or formula (IV)
The pyrene compound represented by these . A polymer compound obtained by copolymerization of the pyrene compound according to claim 1 with another monomer. Formula (III)
A pyrene compound represented by formula (IV)
A pyrene compound represented by formula (II)
A polymer compound obtained by copolymerization of a pyrene compound represented by formula (II) with another monomer.