JPH0834768A - New dimethacrylate - Google Patents

Abstract

PURPOSE:To obtain a new compound excellent in (co)polymerzability and cross- linking property, providing a resin having a high refractive index useful for a highly heat-resistant resin and a lens material by homopolymerization or copolymerization with another copolymerizable compound. CONSTITUTION:9,9-Bis(2-methacryloyloxyethylthio)fluorene of formula I. This compound is obtained by preparing fluorenone-bis-2-hydroxyethylmercaptol of formula II from 2-fluorenone and 2-mercaptoethanol and, for example, esterifying the compound with methacrylic acid of formula III in a dehydrating solvent such as toluene in the presence of an acid catalyst such as sulfuric acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a new and useful dimethacrylate.

[0002]

2. Description of the Related Art Hitherto, a dimethacrylate containing a fluorene skeleton represented by the formula 1 and a sulfur atom has not been known.

[0003]

The present invention has a high heat resistance,
Disclosed is a novel dimethacrylate that is a resin having a high refractive index and is highly polymerizable, copolymerizable, and crosslinkable.

[0004]

The present invention has the following formula:

Embedded image It is a novel dimethacrylate represented by.

Since the dimethacrylate represented by the above formula of the present invention has a fluorene skeleton, it can be made into a resin having high heat resistance as compared with general aliphatic methacrylate by polymerizing using this. In addition, there are two sulfur atoms in one molecule, which has a high refractive index. This compound has two polymerizable methacrylate groups in one molecule.
Alternatively, a high refractive index polymer material suitable for use as a heat resistant polymer or a lens material, which is useful for controlling physical and chemical properties by copolymerizing with another polymerizable compound, can be obtained.

Next, a production example of the novel dimethacrylate represented by the above formula 1 will be described, but the method is not limited to this method.

First, the following equation 2

Embedded image The diol represented by
-Synthesized from mercaptoethanol. This composition
M. S. Newman, W.C. B. Lutz, J .; Am.
Chem. Soc. , 78 , 2469 (1956). Next, the obtained diol represented by the formula 2 is reacted with any of the compounds of the formulas 3, 4 and 5 listed below to synthesize the novel dimethacrylate of the present invention.

[0008]

[Chemical 4]

[0009]

Embedded image

[0010]

[Chemical 6]

The reaction between the diol of the formula 2 and the methacrylic acid represented by the formula 3 is carried out by using sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid or a strongly acidic ion exchange resin in a dehydrating solvent such as toluene, hexane or cyclohexane. The dimethacrylate of the present invention can be obtained by dehydration esterification using a catalyst.

Further, a transesterification catalyst such as a titanium compound typified by titanium tetrabutoxide, a tin compound typified by dibutyltin oxide, or a general protic acid is used as the diol of the formula 2 and the alkyl methacrylate represented by the formula 4 is suitable. By selection, the dimethacrylate of the present invention is obtained.

As the alkyl group of the alkyl methacrylate represented by the above formula 4, those having 4 or less carbon atoms are preferable from the viewpoint of distillative removal, and the most preferable is the methyl group. If the carbon number is 4 or more, the boiling point of the alcohol to be eliminated becomes high, which is disadvantageous in the reaction process. Further, methyl methacrylate is preferable in consideration of the cost of alkyl methacrylate.

Further, the diol of the formula 2 and the methacrylic acid halide represented by the formula 5 (generally chloride) are removed in an inert general-purpose solvent such as chloroform or dichloromethane which dissolves the diol. The dimethacrylate of the present invention can be obtained by using a tertiary amine such as pyridine or triethylamine as an acid agent and reacting under a mild condition.

[0015]

INDUSTRIAL APPLICABILITY The dimethacrylate of the present invention has polymerizability, and is polymerized alone or copolymerized with another copolymerizable compound,
A resin having high heat resistance and high refractive index can be used.

[0016]

【Example】

9,9-bis (2-methacryloyloxyethylthio)
Synthesis of fluorene 12 g of fluorenone-bis-2-hydroxyethylmercaptor represented by formula 2 synthesized from 9-fluorenone and 2-mercaptoethanol by the method described above.
(0.0377 mol) was added to 400 m of dehydrated dichloromethane
16 g (0.202 mol) of dehydrated pyridine was added, and the mixture was stirred at room temperature under a nitrogen atmosphere.

Methacrylic acid chloride 8.87 g
A mixed solution of (0.0848 mol) and 20 ml of dichloromethane was added dropwise over 15 minutes while controlling the temperature of the reaction solution at 18 to 22 ° C. After completion of dropping, stirring was continued at room temperature for additional 2 hours, the reaction solution was taken in a separating funnel and washed with 5% aqueous sodium hydrogen carbonate. Further, it was washed with a 5% aqueous sodium hydroxide solution and water. Then, the dichloromethane layer was dried over anhydrous magnesium sulfate, and then dichloromethane was distilled off to obtain 19.53 g of a pale yellow oily crude product.

The resulting crude product was purified by silica gel column chromatography (distillate toluene) to obtain 12.17 g (0.10%) of the target 9,9-bis (2-methacryloyloxyethylthio) fluorene represented by the formula 1. 0268 mol,
Yield 71%) was obtained as an oily liquid. The data of the analysis and identification are shown below.

[Elemental analysis value] C ₂₅ H ₂₆ O ₄ S ₂ = 45
Calculated as 4.63; C: 66.04% H: 5.78% O: 1
4.10% S: 14.10% Found: C: 65.6% H: 5.8% O: 1
4.1% S: 14.0%

[ ¹ H-NMR spectrum] CDCl ₃
(Internal standard TMS) ¹ H-NMR spectrum is shown in FIG. 1. δ _H 1.87 (6H, s, -CH ₃ ) δ _H 2.54 (4H, t, S-CH ₂ ) δ _H 3.91 (4H, t, O-CH ₂ ) δ _H 5.52 ( 2H, t, HC =) δ H 6.03 (2H, s, HC =) δ H 7.36~7.43 (4H, m, fluorene ring) δ _H 7.69~7.72 (4H, m , Fluorene ring)

[ ¹³ C-NMR spectrum] CDCl ₃
(Internal standard TMS) ¹³ C-NMR spectrum is shown in FIG. 2. _{δ C 18.235 (-CH 3) δ} C 135.969 (= C-CH 3) δ C 30.131 (S-CH 2) δ C 125.805 (= CH 2) δ C 61.759 (S _{-C-S) δ C 166.842 (} C = O) δ C 62.970 (O-CH 2) δ C 120,356,124,796,128,320,129,135 138,891,146,461 (Fluorene ring)

[Infrared absorption spectrum] (KBr tablet method) The infrared absorption spectrum is shown in FIG. 1720 cm ^-1 (ester carbonyl) 1450 cm ^-1 (aromatic ring)

[Refractive index] n _D : 1.5948 (15 ° C.)

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR spectrum diagram of the compounds obtained in Examples.

FIG. 2 is a ¹³ C-NMR spectrum diagram of the compounds obtained in Examples.

FIG. 3 is an infrared absorption spectrum chart of the compounds obtained in Examples.

Claims (1)

[Claims] 1. The following formula: A new dimethacrylate represented by.