KR102276511B1 - Fluorene derivatives and lens using the same - Google Patents

Abstract

A fluorene derivative and a lens using the same are disclosed.

Description

Fluorene derivatives and lenses using the same

A fluorene derivative and a lens using the same are disclosed.

As a material of an optical element used in the optical system of various cameras, such as a smartphone camera and a video camera, optical glass or optical transparent resin is used.

Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials having various refractive indices (nD) and Abbe's number (υD). It is bad, and there is also the problem that productivity is low. In particular, in order to process an aspherical lens used for aberration correction, very high technology and high cost are required, which is a great obstacle in practical use.

On the other hand, an optical lens made of an optically transparent resin, particularly a thermoplastic transparent resin, can be mass-produced by injection molding, and has the advantage of easy manufacture of an aspherical lens, and is currently used as a lens for a camera.

Patent Document 1 discloses a resin composition containing a polycondensation or polyaddition polymer having a fluorene compound as a monomer unit and having at least one sulfur atom in a repeating unit, and an optical element formed by injection molding the resin composition.

1. Japanese Patent Laid-Open No. 2001-106761

One aspect of the present invention is to provide a fluorene derivative having high polarity and low molecular volume so that excellent optical properties are expressed.

Another aspect of the present invention is to provide a fluorene derivative having a low Tg for easy operation and molding.

Another aspect of the present invention is to provide a fluorene derivative having high transparency.

Another aspect of the present invention is to provide an environmentally friendly fluorene derivative.

Another aspect of the present invention is to provide a copolymer of the fluorene derivative.

Another aspect of the present invention is to provide a lens formed by molding the copolymer of the fluorene derivative.

According to one aspect of the present invention, there is provided a fluorene derivative represented by the following Chemical Formula 1:

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each the same or different from each other, and are represented by H or Formula 2 below _{, and at least two of R 1} , R ₂ , R ₃ and R ₄ are represented by Formula 2 below. selected from the compounds shown:

In the above formula, R ₅ is a C1-C5 alkyl group, and Ar is a C6-C22 aryl group.

According to another aspect of the present invention, a copolymer of the compound represented by Formula 1 is provided.

According to another aspect of the present invention, a lens formed by molding a copolymer of the compound represented by Formula 1 is provided.

The features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings.

Prior to this, the terms or words used in the present specification and claims should not be construed as conventional and dictionary meanings, and the inventor may properly define the concept of the term to describe his invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

1 is a view showing a schematic synthesis scheme for a copolymer of a fluorene derivative according to an embodiment of the present invention,
2 is an HPLC result of the compound obtained in Example 1,
^{3 is 1} H-NMR result of the compound obtained in Example 1,
4 is an HPLC result of the compound obtained in Example 2,
^{5 is a 1} H-NMR result of the compound obtained in Example 2.

The objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and examples taken in conjunction with the accompanying drawings. In the present specification, in adding reference numbers to the components of each drawing, it should be noted that only the same components are given the same number as possible even though they are indicated on different drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known technology may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. In this specification, terms such as first, second, etc. are used to distinguish one component from another component, and the component is not limited by the terms.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

fluorene derivative

The fluorene derivative according to an embodiment of the present invention is represented by the following Chemical Formula 1:

Formula 1

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each the same as or different from each other, and are represented by the following Chemical Formula 2, _{and at least two of R 1} , R ₂ , R ₃ and R ₄ are represented by the following Chemical Formula 2 compound is selected from:

Formula 2

- R ₅ -Ar -

In the above formula, R ₅ is a C1-C5 alkyl group, and Ar is a C6-C22 aryl group.

In the fluorene derivative, an aryl group having a low molecular volume is introduced into at least two or more benzene moieties of the fluorene structural unit, thereby increasing the polarity of the fluorene derivative itself to improve the refractive index.

In addition, since the alkyl group having a rotatable bond is disposed at the front end of the aryl group, Tg is lowered, and as a result, the viscosity is lowered, thereby improving moldability and workability.

The fluorene derivative is generally used to improve optical properties, but a halogen substituent such as Br or Cl, which has a disadvantage of causing a dioxin problem, is not introduced into the fluorene structural unit, so it is environmentally friendly. Furthermore, since sulfur or nitrogen atoms are not used, transparency can be ensured.

Here, according to an embodiment, Ar may be a phenyl group.

In another embodiment, Ar may be a naphthyl group.

According to another embodiment, Ar may be a biphenyl group.

According to another embodiment, Ar may be an anthryl group.

According to another embodiment, Ar may be a phenanthryl group.

The fluorene derivative represented by Formula 1 may be a compound represented by Formula 3 below:

Specifically, in the compound represented by Formula 3, a benzyl group is introduced into four benzene moieties of the fluorene structural unit, thereby increasing the polarity of the fluorene derivative itself, thereby improving the refractive index. In addition, since the benzyl group has a methyl group disposed at the front end, rotation of the substituent itself is possible, thereby lowering the viscosity of the derivative, thereby improving moldability and workability.

Formula 1 may be a compound represented by Formula 4 below:

Specifically, in the compound represented by Chemical Formula 4, a benzyl group is introduced into two benzene moieties of the fluorene structural unit, thereby increasing the polarity of the fluorene derivative itself to improve the refractive index. In addition, since the benzyl group has a methyl group disposed at the front end, rotation of the substituent itself is possible, thereby lowering the viscosity of the derivative, thereby improving moldability and workability.

Formula 1 may be a compound represented by Formula 5 below:

Specifically, in the compound represented by Formula 5, a methylnaphthyl group is introduced into four benzene moieties of the fluorene structural unit, thereby increasing the polarity of the fluorene derivative itself, thereby improving the refractive index. In addition, in the methylnaphthyl group, the methyl group is disposed at the front end, so that the substituent itself can be rotated, thereby lowering the viscosity of the derivative and improving moldability and workability can be expected.

Formula 1 may be a compound represented by Formula 6 below:

Specifically, in the compound represented by Formula 6, a methylnaphthyl group is introduced into two benzene moieties of the fluorene structural unit, thereby increasing the polarity of the fluorene derivative itself, thereby improving the refractive index. In addition, in the methylnaphthyl group, the methyl group is disposed at the front end, so that the substituent itself can be rotated, thereby lowering the viscosity of the derivative and improving moldability and workability can be expected.

fluorene Method for producing derivatives

Hereinafter, a method for producing a fluorene derivative according to an embodiment of the present invention will be described in detail. However, the specific reaction scheme to be described below is for illustrative purposes only, and those skilled in the art will be able to fully recognize that the method for preparing the fluorene derivative is not particularly limited thereto.

According to an embodiment, the compound represented by Formula 3 is subjected to a B-alkyl Suzuki coupling reaction using 2,7-dibromo-9-fluorene as a starting material, as shown in Scheme 1 below. , can be synthesized by proceeding with a fluorene structure build reaction.

(Scheme 1)

According to another embodiment, the compound represented by Formula 3 may be synthesized through the reaction shown in Scheme 2 below.

(Scheme 2)

Here, a basic catalyst may be used instead of an acid catalyst (Acid-cat.), and benzyl chloride may be used instead of benzyl alcohol reacting with fluorene bisphenol.

The compound represented by Formula 4 may be synthesized using 9-fluorene as a starting material, as shown in Scheme 3 below, according to an embodiment.

(Scheme 3)

Here, although the case of using o-benzylphenol is shown in the above reaction scheme, it is also possible to use m-benzylphenol depending on the introduction position of the substituent.

The compound represented by Formula 5 may be synthesized through a reaction as shown in Scheme 4 below, according to an embodiment.

(Scheme 4)

Here, 1-naphthylmethanol may be used instead of 1-(chloromethyl)naphthalene, which reacts with fluorene bisphenol.

The compound represented by Formula 6 may be synthesized using 9-fluorene as a starting material, as shown in Scheme 5 below, according to an embodiment.

(Scheme 5)

copolymer

The copolymer according to an embodiment of the present invention is a copolymer of the fluorene derivative represented by Formula 1 above. Hereinafter, the copolymer will be described with specific examples, but the following compounds are presented for the purpose of illustration for detailed description, and the copolymer of the present invention is not particularly limited thereto.

The copolymer is, for example, obtained by copolymerizing a fluorene derivative of Formula 3 in which a benzyl group is introduced into four benzene moieties among fluorene structural units, and may be represented by Formula 7 below.

In the above formula, R is a dicarboxylic acid component, and examples thereof include dicarboxylic acid, dicarboxylic acid derivative, dicarboxylic acid derivative capable of forming an ester bond, and ester-forming dicarboxylic acid derivative. A dicarboxylic acid component may be used individually by 1 type or in combination of 2 or more type. Representative dicarboxylic acids include, for example, alkanedicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid, and aliphatic dicarboxylic acids of alkenedicarboxylic acids such as maleic acid and fumaric acid. ; Alicyclics, such as tricycloalkanedicarboxylic acid, such as cycloalkanedicarboxylic acid, such as cyclohexanedicarboxylic acid, di or decarinedicarboxylic acid, norbornanedicarboxylic acid, and adamantane dicarboxylic acid dicarboxylic acid; Arenedicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and anthracenedicarboxylic acid, 2,2'-biphenyldicarboxyl Aromatic dicarboxylic acid of biphenyldicarboxylic acid, such as an acid, etc. are mentioned. In addition, acid anhydrides such as hexahydrophthalic anhydride and tetrahydrophthalic anhydride, lower (C1-C4) alkyl esters such as dimethyl ester and diethyl ester, and acid halides corresponding to dicarboxylic acid can be formed. Reactive derivatives thereof such as derivatives can be used. Of course, R may vary depending on the type of monomer applied during actual copolymerization.

The copolymer is, for example, obtained by copolymerizing a fluorene derivative of Formula 5 in which a methylnaphthyl group is introduced into four benzene moieties among fluorene structural units, and may be represented by Formula 8 below.

In the above formula, R is as described above.

A schematic synthesis scheme for the copolymers represented by Chemical Formulas 7 and 8 is summarized and shown in FIG. 1 .

A method for preparing the copolymer is not particularly limited, and a conventionally known conventional copolymerization method may be applied.

lens

The lens according to an embodiment of the present invention is obtained by molding a copolymer of the fluorene derivative represented by Chemical Formula 1 above.

The fluorene derivative and its copolymer are the same as described above, and a detailed description thereof will be omitted herein.

The lens obtained by molding the copolymer of the fluorene derivative exhibits high refractive properties and has excellent overall optical properties such as transparency.

The lens according to an embodiment of the present invention may be obtained by, for example, injection molding the copolymer of the fluorene derivative into a lens shape in an injection molding machine or an injection compression molding machine.

The lens may be used in the form of an aspherical lens if necessary. The aspherical lens is useful as a camera lens among optical lenses. On the surface of the lens, if necessary, a coating layer such as an antireflection layer or a hard coat layer may be formed.

The lens can also be used in various lenses such as pickup lenses, f-θ lenses, and spectacle lenses.

Specifically, it may be used as a lens of a single lens reflex camera, a digital still camera, a video camera, a camera-equipped mobile phone, a lens-mounted film, a telescope, binoculars, a microscope, a projector, and the like.

The present invention will be described in more detail through the following examples, but the scope of the present invention is not limited to the following examples.

Example 1

- Synthesis of disubstituted benzyl fluorene ethanol, Formula 4

After putting 400 ml of acetonitrile as a reaction solvent in a 3L reactor equipped with a reflux device, 9-fluorenon, 2-benzylphenol, 3-mercaptopropionic acid (3 -mercaptopropionic acid) is sequentially added and dissolved. Sulfuric acid, which is a reaction catalyst, is slowly added dropwise and maintained for 1 hour so that the reaction temperature is maintained at 80° C., and the end point of the reaction is confirmed by TLC. The reactor is cooled to maintain room temperature, and an aqueous potassium carbonate solution is added dropwise to neutralize the reaction solution to obtain a crystalline crude. The obtained product was recrystallized from hexane and methylene chloride to obtain a disubstituted benzyl fluorene intermediate with HPLC purity of 99.2% and yield of 91%. 100 g of the obtained disubstituted benzyl fluorene was placed in a 3-neck 2L reactor equipped with a reflux device, dissolved with dimethyl sulfoxide, a reaction solvent, and ethylene carbonate and 2-methylimidazole were sequentially added thereto, refluxed at 145° C., and TLC was performed. Identify the end point of the reaction. After completion of the reaction, the reactor is cooled to 50° C., and after crystallization by adding 500 ml of methanol dropwise, the reactor is cooled to room temperature. The obtained crude product was dissolved in ethyl acetate and precipitated in distilled water to obtain disubstituted benzyl fluorene ethanol of Formula 4 and dried under reduced pressure. HPLC purity 99.2%, yield 60%, ¹ H-NMR (CDCl ₃ ,δ): 3.89 (benzyl, CH ₂ )

HPLC and ¹ H-NMR results of the resulting compound are shown in FIGS. 2 and 3, respectively.

Example 2

- Synthesis of 4-substituted benzyl fluorene ethanol, formula 3

(Scheme 6)

With reference to Scheme 6, the reaction was carried out as follows.

[Intermediate 1]

2- (1,5- dimethyl -2,4- dioxa -3- borabicyclo [3.1.0] hexan-3- yl) -7- (4,4,5, 5- tetramethyl -1,3,2- dioxaborolan Synthesis of -2- yl )-9H- fluoren- 9- one )

After putting 2500 ml of 1,4-dioxane as a reaction solvent in a 12 L reactor equipped with a reflux device, 500 g 2,7-dibromo -9H-fluoren-9-one, 902 g bis (pinacolato) (diboron) ) (Bis(pinacolato)diboron), 50 g Pd(PPh ₃ ) ₄ , 613 g potassium carbonate were added to the reactor, stirred/dissolved, and refluxed at 100° C. for 30 hours or more, and the end point of the reaction was confirmed by TLC. The reactor is cooled to room temperature, an excess of methylene chloride is added to dissolve the crude, and activated carbon is added thereto, stirred, and then filtered. Excess distilled water is added to the filtered filtrate to remove residual by-products, and the methylene chloride layer is separated and concentrated. The obtained crude product was recrystallized with ethyl acetate/hexane 1:12 mixed solvent, and the crystals were filtered and dried to obtain an intermediate 1 with a synthetic yield of 68%.

[Intermediate 2]

2,7- dibenzyl -9H- fluoren -9- one synthesis

After putting 1100 ml of dimethoxyethane as a reaction solvent in a 12L reactor equipped with a reflux device, 270 g of intermediate 1, 2 equivalents or more of benzylbromide, 27 g Pd(PPh ₃ ) ₄ , 260 g of potassium carbonate were added to the reactor and stirred. /Dissolve and reflux at 80°C for at least 30 hours, and check the end point of the reaction by TLC. The reactor is cooled to room temperature, an excess of methylene chloride is added to dissolve the crude, and activated carbon is added thereto and stirred, followed by filtration. Excess distilled water is added to the filtered filtrate to remove residual by-products, and the methylene chloride layer is separated and concentrated. The obtained crude material was recrystallized with ethyl acetate/hexane 1:12 mixed solvent, and the crystals were filtered and dried to obtain an intermediate 2 with a synthetic yield of 73%.

[4-substituted benzyl fluorene]

In a 2L reactor equipped with a reflux device, 164 g of Intermediate 2 and 335 g of 2-benzylphenol were added and stirred. The reaction catalyst, P ₂ O ₅ and appropriate amounts of trifluoromethanesulfonic acid (Trifluoromethanesulfonic acid) are slowly added dropwise and maintained for 6 hours so that the reaction temperature is maintained at 50°C, and the end point of the reaction is confirmed by TLC. The reactor is cooled to maintain room temperature, and the crude is extracted with a methylene chloride layer using 1000 ml of methylene chloride and distilled water, and then extracted twice with an aqueous sodium hydrogen carbonate solution to separate and concentrate the methylene chloride layer. An aqueous potassium carbonate solution is added dropwise to neutralize the reaction solution to obtain a crystalline crude product. The obtained product was recrystallized with a 1:4 mixed solvent of ethyl acetate/hexane, and the crystals were filtered and dried to obtain a final compound, tetrasubstituted benzyl fluorene. HPLC purity 99.2%, yield 52%, ¹ H-NMR (CDCl ₃ ,δ): 3.86, 3.96 (benzyl, CH ₂ )

HPLC and ¹ H-NMR results of the resulting compound are shown in FIGS. 4 and 5, respectively.

[4-substituted benzyl fluorene ethanol]

The tetrasubstituted benzyl fluorene obtained above was ethanolized to synthesize a compound of Formula 3.

Example 3

- Synthesis of disubstituted benzyl fluorene-based homopolymer

A disubstituted benzyl fluorene monomer having a purity of 99% or more was dissolved in a sodium hydroxide aqueous solution and a mixed solution of methylene chloride to obtain a polymer by carbonation reaction using phosgene gas, and the GPC molecular weight and Tg are shown in Table 1. Disubstituted benzyl fluorene ethanol was also prepared by the same synthesis method.

Sample GPC molecular weight DSC TGA Mn, *1000 Mw, *1000 Mw/Mn Tg (℃) Td 5wt% (℃) disubstituted benzyl
fluorene 15.8 63.1 4.0 131 477 disubstituted benzyl fluorene ethanol 12.8 35.0 2.7 130 479

Example 4

- Synthesis of 4-substituted benzyl fluorene-based homopolymer

A tetrasubstituted benzyl fluorene monomer having a purity of 99% or more was dissolved in a sodium hydroxide aqueous solution and a mixed solution of methylene chloride to obtain a polymer by carbonation reaction using phosgene gas, and the GPC molecular weight and Tg are shown in Table 2. 4-substituted benzyl fluorene ethanol was also prepared by the same synthesis method.

Sample GPC molecular weight DSC TGA Mn, *1000 Mw, *1000 Mw/Mn Tg (℃) Td 5wt% (℃) tetrasubstituted benzyl
fluorene 16.0 81.0 5.1 142 460 4-substituted benzyl fluorene ethanol 18.2 92.3 5.1 140 470

Example 5

- Lens characteristics evaluation

Each of the polymer obtained in Examples 3 and 4 and the current high refractive index resin (reference) was put into a mold with a width and length of 2 cm and a thickness of 1 mm, melted by heating, and then the mold was removed to prepare a plate-shaped lens optical property evaluation specimen and Refractive index, ABBE number and transmittance were measured. The results are shown in Table 3 below.

Sample Reflective Index
587nm, 25℃ ABBE number permeability Disubstituted benzyl fluorene-based polymer 1.652 24 95% 4-substituted benzyl fluorene-based polymer 1.660 23 94% Reference 1.635 24 85%

As can be seen from Table 3, the polymer for lenses according to the present invention exhibited a high refractive index of 1.660 level, a high transmittance of 90% or more, and a low Tg suitable for injection property.

As described above, in the fluorene derivative according to an embodiment of the present invention, an aryl group having a low molecular volume is introduced into two or more benzene moieties in the fluorene structural unit, thereby increasing the polarity of the fluorene derivative itself to improve the refractive index. have.

Furthermore, since the alkyl group having a rotatable single bond is disposed at the front end of the aryl group, the Tg is lowered, and as a result, the viscosity is lowered, thereby improving workability and moldability.

The fluorene derivative according to an embodiment of the present invention is environmentally friendly because halogen substituents such as Br or Cl that cause dioxin problems are not introduced into the fluorene structural unit.

In addition, in the fluorene derivative according to an embodiment of the present invention, since sulfur or nitrogen atoms, which are usually introduced to improve optical properties, are not used in the fluorene structural unit, transparency can be secured.

Although the present invention has been described in detail through specific examples, this is intended to describe the present invention in detail, and the present invention is not limited thereto, and by those of ordinary skill in the art within the technical spirit of the present invention. It is clear that the modification or improvement is possible.

All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will be made clear by the appended claims.

Claims (12)

A fluorene derivative represented by the following formula (1):
(Formula 1)

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each the same as or different from each other, and are selected from compounds represented by the following formula (2):
(Formula 2)
- R ₅ -Ar
In the above formula, R ₅ is a C1-C5 alkyl group, and Ar is a C6-C22 aryl group.
The method according to claim 1,
wherein Ar is a phenyl group.
The method according to claim 1,
Wherein Ar is a naphthyl group fluorene derivative.
The method according to claim 1,
Wherein Ar is a fluorene derivative of a biphenyl group.
The method according to claim 1,
Wherein Ar is an anthryl group, a fluorene derivative.
The method according to claim 1,
Wherein Ar is a phenanthryl group fluorene derivative.
The method according to claim 1,
Formula 1 is a fluorene derivative which is a compound represented by Formula 3 below:
(Formula 3)

delete The method according to claim 1,
Formula 1 is a fluorene derivative which is a compound represented by Formula 5 below:
(Formula 5)

delete A copolymer of a compound represented by the following formula (1):
(Formula 1)

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each the same as or different from each other, and are selected from compounds represented by the following formula (2):
(Formula 2)
- R ₅ -Ar
In the above formula, R ₅ is a C1-C5 alkyl group, and Ar is a C6-C22 aryl group.
A lens formed by molding a copolymer of a compound represented by the following Chemical Formula 1:
(Formula 1)

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each the same as or different from each other, and are selected from compounds represented by the following formula (2):
(Formula 2)
- R ₅ -Ar
In the above formula, R ₅ is a C1-C5 alkyl group, and Ar is a C6-C22 aryl group.

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