KR100873986B1 - Aromatic acrylic compound and its preparation method, polymerizable resin composition comprising the same - Google Patents

Abstract

The present invention relates to a novel aromatic acrylic compound, a method for preparing the same, and a polymerizable resin composition including one or more thereof. More specifically, the present invention relates to a compound containing acryl and methacryl groups as shown in the following Chemical Formula 1 and containing phosphorous atoms and a polymerizable composition comprising the same.

[Formula 1]

[In Formula 1, R ₁₁ is a divalent organic group, X ₁₁ , X ₁₂ , X ₁₃ are each independently an oxygen atom, a sulfur atom, -C (= O) O-, or-(CH ₂ ) _m X ₁₄ (Wherein X ₁₄ is each independently an oxygen atom or a sulfur atom, m is an integer of 1 to 3), R ₁₂ is each independently a substituent containing a phosphorous atom, and R ₁₃ is each independently acrylic Or a methacryl group, and R ₁₄ is each independently a hydrogen atom or a methyl group.]

Since the aromatic acrylic compound of the present invention has a higher refractive index than other conventional acrylic compounds including phosphorous (phosphorous) as well as aromatic groups, it is possible to prepare coatings, films and plastic materials which can control the refractive index by mixing them alone or with other polymers. It is possible.

Description

Aromatic acrylic compounds, a method for preparing the same, and a polymerizable resin composition comprising the same {Aromatic acrylic compounds, their production methods, and polymerizable composition containing them}

The present invention relates to a polymerizable compound which can be applied to an optical coating and a material having high heat resistance, transparency and high refractive index, and a polymerizable resin using the same.

Acrylic compounds are easily applied to various light coatings and optical materials because polymerization occurs by easily reacting with radicals generated by light or heat. Examples of such applications include plastic lenses, reflector coatings, binder resins for LCD color filters, and the like. Synthesis of monomers and polymers or polymerizable resin compositions using the same have been mainly used.

Recently, in optical applications, optical materials used for holography, reflector plates, prism sheets, etc. of LCD backlight units are required to develop materials having high refractive index, and the refractive index of conventional acrylic resins is only about 1.48 to 1.5. There is a need for the development of polymeric materials with refractive indices. Although it is achievable by introducing a halogen substituent as a method of developing a polymer having a high tanning rate, environmental problems and deterioration of the device due to residual halogens become a problem and cause a deterioration of the device. It became.

Therefore, the present invention provides a new polymerizable monomer having a high refractive index, thereby providing a material suitable as an optical material that requires a high refractive index.

In order to solve the above problems, the present invention focused on the fact that the refractive index of a plastic material is proportional to the density of the plastic material, and developed a material having a high refractive index by substituting an aromatic group as a substituent and introducing elements such as sulfur and phosphorus. .

That is, the present invention relates to an unsaturated carboxylate compound containing a phosphorous atom and a polymerizable composition comprising the same, wherein the unsaturated carboxylate compound and the polymerizable composition comprising the same include phosphorus ( It refers to an unsaturated carboxylate compound containing a phosphorous atom and a polymerizable composition comprising the same, and by introducing a substituent having a chemical structure containing such a phosphorous atom, the unsaturated carboxylate compound and a polymerizable comprising the same An object of the present invention is to improve the refractive index of the composition over existing general acrylic resins.

The present invention relates to an unsaturated carboxylate compound containing a phosphorous atom and a polymerizable composition comprising the same.

In more detail, the present invention provides an unsaturated carboxylate compound containing a phosphorous atom having a structure of Formula 1 below.

[Formula 1]

In Formula 1, R ₁₁ is a divalent organic group,

X ₁₁ , X ₁₂ and X ₁₃ are each independently an oxygen atom, a sulfur atom, -C (= O) O-, or-(CH ₂ ) _m X _14- (wherein X ₁₄ is each independently an oxygen atom or a sulfur atom) , m is an integer of 1 to 3),

R ₁₂ are each independently a substituent containing a phosphorous atom, R ₁₃ is each independently an α, β-unsaturated carboxylate residue, and R ₁₄ is each independently a hydrogen atom or a methyl group.

Examples of the unsaturated carboxylate containing the phosphorus of the present invention include the same as the following formula (2) or formula (3). This may include compounds in which X ₁₁ is an oxygen atom in Formula 1, one of X ₁₂ and X ₁₃ is an oxygen atom, the other is —CH ₂ O—, and R ₁₄ is a hydrogen atom.

[Formula 2]

[Formula 3]

The preparation method of Chemical Formula 2 or Chemical Formula 3 may be obtained from starting materials such as Chemical Formula 4 below. That is, it can be prepared by reacting the epoxy having a halogen and diol as shown in Scheme 1, the preparation method thereof is Journal of Biomedical Materials and Research, 2002, vol. 62, p. 622, etc., so no further explanation is given.

[Formula 4]

Scheme 1

In the present invention, R ₁₃ which is an α, β-unsaturated carboxylate residue in Formula 2 or Formula 3 Is a (meth) acrylic acid residue, crotonic acid residue, thiglic acid residue, 3,3-dimethylacrylic acid residue, maleic acid residue, citraconic acid residue, 2,3-dimethylmaleic acid residue, itaconic acid residue and cinnamic acid residue. It may be selected from the group consisting of, but is not limited thereto.

As a more preferable example of the present invention, a compound in which R _{13, which} is an α, β-unsaturated carboxylate residue in Formula 2 or Formula 3, is an acrylic acid residue, as in Formula 5 or Formula 6 below. Such acrylic derivatives are particularly useful because they can be polymerized and cured by various methods such as light or heat, and thus can be applied to various fields such as film formation and coating.

[Formula 5]

[Formula 6]

In the present invention, R _{12 which} is a substituent containing a phosphorous atom in Formula 5 or Formula 6 is represented by the following Formula 7 or Formula 8:

[Formula 7]

(In Formula 7, R ₂₁ and R ₂₂ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aromatic hydrocarbon compound having 1 to 20 carbon atoms);

[Formula 8]

In Formula 8, R ₂₃ and R ₂₄ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aromatic hydrocarbon compound having 1 to 20 carbon atoms.

It may be selected from those represented by, but is not limited thereto.

As a more preferred example of the present invention, as shown in the following formula (9) or (10), R _{12 which} is a substituent containing a phosphorous atom in the formula (5) or (6) is a kind of formula (C ₆ H ₅ ) ₂ P A compound which is (= O) is mentioned. By containing a phosphorus substituent in which the aromatic is bonded, the compounds shown in the embodiments of the present invention can bring about an effect of further increasing the refractive index.

[Formula 9]

[Formula 10]

Reactions for synthesizing a phosphorous atom-containing unsaturated carboxylate compound such as Formula 9 or Formula 10 according to the present invention will be described in more detail with reference to the following specific examples, and the present invention will be described only in the following examples. Without being limited, any modification or change of the present invention can be easily made by those skilled in the art within the scope of the matter included in the specification and the appended claims.

By mixing an aromatic unsaturated carboxylate compound having a phosphorus component having the above structural formula of the present invention, a mixture thereof, or a polymerizable compound (monomer) which is a compound other than the present invention having a group capable of ultraviolet polymerization, It is possible to provide a photocurable composition having a refractive index.

In the present invention, a conventional polymerizable compound means a monomer copolymerizable with the compound of the present invention by an acrylic or methacrylic group or other photoinitiator except for the polymerizable compound of the present invention, and the polymerizable group has one or two or more groups. This may be easily adopted by those skilled in the art, and thus, further description thereof will be omitted.

The present invention relates to an aromatic unsaturated carboxylate compound containing a phosphorus atom as described above, a mixture thereof or a mixture with a compound other than the aromatic unsaturated carboxylate claimed in the present invention which can be cured by ordinary ultraviolet to these components. By mixing the photoinitiator and the solvent with a substrate such as spin coating and then UV curing, a coating layer, a film and a molded article having a high tanning rate can be produced.

In the present invention, a composition containing an aromatic unsaturated carboxylate compound containing a phosphorous element can be appropriately adjusted in composition ratio according to its needs, and the photoinitiator is used with respect to the compound or mixtures thereof or mixtures with other polymerizable monomers. It is preferable to add in an amount of 0.1 to 5% by weight, and the content of the compound and / or the polymerizable monomer is not particularly limited, but preferably 0.1 to 90% by weight, and more preferably 5 to 70% by weight, based on the total composition. Can be used as

Scheme 2 below shows the synthetic routes of Examples 1 and 2 of the present invention. Hereinafter, the present invention will be described in more detail through specific synthesis examples, and the present invention is not limited to the following examples.

Scheme 2

Example 1

[ Example  1-a]

Synthesis step of 9,9-bis (4- (3-diphenylphosphinoyl-2-hydroxy-propyloxy) phenyl) fluorene (1)

Put 26 mL (0.5 M in THF, 13 mmol) of lithium diphenylphosphide solution into 100 mL 2-neck round bottom flask and stir at 0 ° C ice-bath. Here, 2 g (4.3 mmol) of 9,9-bis (4-glycidyloxyphenyl) fluorene was dissolved in 20 mL of anhydrous THF and slowly dropped into the solution. Remove the ice-bath from the reactor, stir at room temperature for one day, lower the temperature to 0 ° C, add 1 mL of glacial acetic acid and 3.4 g of hydrogen peroxide (30 wt% in H ₂ O, 30 mmol). After an additional 4 hours of stirring, the reaction was extracted with dichloromethane / water and the organic layer was dried to give the product (1) (1.8 g, yield = 50%). ( ¹ H-NMR (δ, ppm, CDCl ₃ ): 7.71-7.82 (m, 10H), 7.20-7.55 (m, 18H), 6.78-6.93 (d, 4H), 6.65-6.70 (d, 4H), 3.90-4.22 (m, 4H), 3.65 -3.70 (m, 2H), 1.45-1.60 (m, 4H).

Example 1-b

Synthesis step of 9,9-bis (4- (3-diphenylphosphinoyl-2-acryloxy-propyloxy) phenyl) fluorene (2)

1 g (1.2 mmol) of 9,9-bis (4- (3-diphenylphosphinoyl-2-hydroxy-propyloxy) phenyl) fluorene synthesized in [Example 1-A] above in a 100 mL 2-neck round bottom flask Dissolve 0.74 mL (5.3 mmol) of triethylamine in 10 mL of dichloromethane and stir in a 0 ° C ice-bath. Here, a solution of 0.38 mL (4.7 mmol) of acryloyl chloride in 5 mL of dichloromethane is slowly dropped. Remove the ice-bath from the reactor and stir at room temperature for 12 hours. The solid salt in the reactor was filtered off and the remaining solution was dried and purified via column chromatography to give the product (2) (0.7 g, yield = 60%). Elemental Analysis: C, 75.14; H, 5.38. ¹ H-NMR (δ, ppm, CDCl ₃ ): 7.70-7.79 (m, 10H), 7.18-7.57 (m, 18H), 6.80-7.04 (d, 4H), 6.65-6.70 (d, 4H), 6.31 -6.37 (d, 2H), 5.97-6.08 (m, 2H), 5.76-5.80 (d, 2H), 5.25-5.33 (m, 2H), 4.05-4.33 (m, 4H), 1.45-1.60 (m, 4H).

Example 2

[ Example  2-ga]

Synthesis step of 9,9-bis (4- (3-acryloxy-2-hydroxy-propyloxy) phenyl) fluorene (3)

2 g (4.3 mmol) of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.9 mL (13.2 mmol) of acrylic acid, 0.005 g (0.043 mmol) of 4-methoxyphenol, dimethylaminopyridine 0.005 in a 100 mL 2-neck round bottom flask g (0.043 mmol) and 20 mL of THF were added and refluxed for 1 day. After cooling the reaction to room temperature, the reaction was extracted with dichloromethane / water and the organic layer was dried to give product (3) (2.2 g, yield = 85%). ¹ H-NMR (δ, ppm, CDCl ₃ ): 7.71-7.84 (d, 2H), 7.19-7.59 (m, 6H), 6.78-6.93 (d, 4H), 6.65-6.70 (d, 4H), 6.31 -6.37 (d, 2H), 5.97-6.08 (m, 2H), 5.76-5.80 (d, 2H), 5.25-5.33 (m, 2H), 3.97-4.43 (m, 6H).

Example 2-b

9,9-bis (4- (3- acryloxy -2- diphenylphosphinoyloxy Synthesis step of -propyloxy) phenyl) fluorene (4)

1 g (1.6 mmol) of 9,9-bis (4- (3-acryloxy-2-hydroxy-propyloxy) phenyl) fluorene synthesized in [Example 2-A] above in a 100 mL 2-neck round bottom flask 0.004 g (0.033 mmol) of dimethylaminopyridine, 0.9 mL (6.4 mmol) of triethylamine, and 10 mL of dichloromethane were added thereto, followed by stirring for one day. The reaction was extracted with dichloromethane / water and the organic layer was dried to give product (4) (1.0 g, yield = 65%). Elemental Analysis: C, 72.76; H, 5.20. ¹ H-NMR (δ, ppm, CDCl ₃ ): 7.71-7.86 (m, 10H), 7.26-7.67 (m, 18H), 6.78-6.93 (d, 4H), 6.65-6.70 (d, 4H), 6.31 -6.37 (d, 2H), 5.97-6.08 (m, 2H), 5.76-5.80 (d, 2H), 5.25-5.33 (m, 2H), 4.07-4.61 (m, 6H).

[Example 3] to [Example 14]

The compound of Examples 3 to 14 is the same as the synthesis method described in Example 1 or Example 2, the chemical formula of R _{11 which} is a divalent organic group in the formula (9) or formula (10) Prepared from each aromatic diol using the same compound as the structural formula. Table 1 shows the structure and elemental analysis of each compound.

Table 1. Structural Analysis Results According to Preparation Compound

Example 15

9,9-bis (4- (3-diphenylphosphinoyl-2-acryloxy-propyloxy) phenyl) fluorene (2), a compound synthesized in Example 1, Irgacure 369 as a photoinitiator, and PGMEA (propylene glycol monomethyl ether acteate) as a solvent The polymerizable composition mixed at a weight ratio of 1: 0.01: 50 was prepared. The polymerizable composition was spin coated to form a film through ultraviolet curing (wavelength 352 nm, 300 mJ / cm ² , 60 seconds).

The refractive index of the thus formed film could be measured through a prism coupler. Table 2 shows the measured refractive index values.

[ Example  16]

Except for using the compound synthesized in Example 2 9,9-bis (4- (3-acryloxy-2-diphenylphosphinoyloxy-propyloxy) phenyl) fluorene (4) instead of the compound (2) of Example 1 Was proceeded in the same manner as in Example 15. Table 2 shows the measured refractive index values.

[Example 17] to [Example 28]

The same procedure as in Example 15 was repeated except that the compound of Example 3 to Example 14 was used instead of the compound (2) of Example 1. Table 2 shows the measured refractive index values, respectively.

Example 29

Except that the compound (2) of Example 1 and Bisphenol A diacrylate which is a compound having the structure of formula (11) instead of the compound (2) of Example 1 in a weight ratio of 1: 1 Proceed as in 15. Table 2 shows the measured refractive index values.

[Formula 11]

Table 2. Refractive Index of Polymerizable Resin Compositions

As described above, according to the present invention, an optical resin having excellent optical properties, mechanical properties and thermal properties, good production, and high refractive index, that is, phosphorus atom-containing unsaturated carboxylate can be produced. Moreover, the hardened | cured material and optical component which were manufactured by superposing | polymerizing the polymerizable composition containing the phosphorus atom containing unsaturated carboxylate of this invention are excellent in an optical characteristic, a mechanical characteristic, and a thermal characteristic, and it is a short time polymerization and It can be obtained by molding / curing and has a high refractive index.

Claims (8)

An unsaturated carboxylate compound containing phosphorous represented by the following formula (1). [Formula 1]

In Formula 1, R ₁₁ is a divalent organic group selected from

Each X is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or halide group having 1 to 20 carbon atoms, X ₁₁ , X ₁₂ and X ₁₃ are each independently an oxygen atom, a sulfur atom, -C (= O) O-, or-(CH ₂ ) _m X _14- (wherein X ₁₄ is each independently an oxygen atom or a sulfur atom) , m is an integer of 1 to 3), R ₁₂ are each independently a substituent containing a phosphorous atom selected from the following structures:

R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ₁₃ are each independently an α, β-unsaturated carboxylate residue, and R ₁₄ is each independently a hydrogen atom or a methyl group. The method of claim 1, The α, β-unsaturated carboxylate residues include (meth) acrylic acid residues, crotonic acid residues, tiglic acid residues, 3,3-dimethylacrylic acid residues, maleic acid residues, citraconic acid residues, and 2,3-dimethylmaleic acid. An unsaturated carboxylate compound containing phosphorous independently selected from the group consisting of residues, itaconic acid residues and cinnamic acid residues. delete delete delete The method of claim 1, The R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently an unsaturated carboxylate compound, characterized in that the aromatic group represented by the following formula (12). [Formula 12]

(R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or halide group having 1 to 20 carbon atoms) delete A polymerizable composition comprising the unsaturated carboxylate compound of claim 1.