JP2009280566A - 2,2-bis(4-hydroxycyclohexyl)propanedi(meth)allyl ether compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To industrially produce and provide 2,2-bis(4-hydroxycyclohexyl)propanedi(meth)allyl ether with slight impurity content, as an aliphatic low-molecular compound useful as a raw material for compositions for optical materials, having two allyl groups and efficiently allyl-etherified with a few unreacted hydroxy groups. <P>SOLUTION: A method for producing 2,2-bis(4-hydroxycyclohexyl)propanedi(meth)allyl ether by conducting a desalting reaction using an allyl halide and an alkali metal hydroxide with a hydrogenated bisphenol A as a precursor is provided. In this method, by using an ether-based solvent inert to an alkali such as diethylene glycol dimethyl ether, the objective compound is obtained in a high yield as well as with effective purity in an industrial production process. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a novel compound having two carbon-carbon double bonds having reactivity with SiH groups, which is an aliphatic low-molecular compound useful as a composition material for optical materials, and a method for producing the same.
Specifically, highly purified diallyl ether of hydrogenated bisphenol A and hydrogenated bisphenol A dimethallyl ether having a hydrogenated bisphenol A skeleton as a chemical structure providing heat resistance and optical transparency, and these are obtained with high purity. It is related with the manufacturing method which can do.

Conventionally, when an allyl ether compound is produced, a hydroxyl group-containing compound and an allyl halide (usually allyl chloride) are produced by a desalting reaction at a maximum of about 80 ° C. in the presence of excess alkali metal hydroxide.
The reaction proceeds easily if the starting hydroxyl group-containing compound is liquid even at a temperature lower than the reaction temperature or if it is compatible with allyl halide. In the case of a starting material containing a phenolic hydroxyl group such as bisphenol A, even if it is a solid below the reaction temperature, it is phenolated and dissolved in an alkaline aqueous solution. The reaction proceeds.
However, hydrogenated bisphenol A has a melting point of about 145 ° C., and is not compatible with allyl chloride. When an alkaline aqueous solution is used, it is not alcoholated and does not dissolve. Therefore, the reaction hardly proceeds.

  Patent Document 1 below discloses a method for synthesizing divinyl ether of hydrogenated bisphenol A, and a method of reacting acetylene gas with dimethyl sulfoxide as a solvent in the presence of an alkali catalyst in the synthesis example. However, this method has a very low yield and is further purified using a silica gel column, which is not practical as an industrial production method.

JP 2003-286216 A

  An object of the present invention is to solve the above conventional problems and achieve the following object. That is, the present invention is an aliphatic low-molecular compound useful as a raw material for optical materials, and is a compound having two unreacted hydroxyl groups as a compound having two carbon-carbon double bonds reactive with SiH groups. An object of the present invention is to industrially produce and provide 2,2-bis (4-hydroxycyclohexyl) propanedi (meth) allyl ether, which is allyletherified and is low in impurities.

As a result of intensive studies, the present inventors have found that in a method of desalting reaction using hydrogenated bisphenol A as a precursor using an allyl halide and an alkali metal hydroxide, an alkali such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, or tetrahydrofuran is used. On the other hand, by using a non-reactive ether solvent, it was found that not only the target compound can be obtained in a high yield but also an effective purity can be obtained by an industrial production method, and the present invention has been completed.
That is, the present invention is represented by the following chemical formulas (1) and (2), the chlorine content is 100 ppm or less, and the allyl etherification rate at both ends or the methallyl etherification rate at both ends is 95% or more. 2,2-bis (4-hydroxycyclohexyl) propane di (meth) allyl ether compound, and a method for producing the same.

Since the novel high-purity compound of the present invention is an alicyclic compound, it is a composition that can give a cured product excellent in optical transparency and light resistance as compared with an aromatic compound. It becomes a curable composition raw material for optical materials that exhibits excellent physical, thermal, and electrical properties derived from crosslinking by reaction.
The diallyl ether compound, which is the target substance, can be derived into a hydrogenated bisphenol A epoxy compound that is useful industrially, particularly as an electronic material, by further oxidation. Currently, the highest purity is obtained by hydrogenating a condensate of bisphenol A and epichlorohydrin. However, in this method, the total chlorine content contains 200 to 500 ppm of chlorine. For example, in electronic material applications, chlorine causes a decrease in electrical insulation. In particular, the precursors of the present invention are useful in the recent demand for high-purity liquid epoxy resins with extremely small amounts of impurity chlorine due to technological innovations in the fields of electronics and high-performance paints. Moreover, since the present product is a condensate using epichlorohydrin, it is not monodispersed but has a distribution, and therefore has a high viscosity. Monodispersion of the distribution is desired in terms of lowering the viscosity. In this respect, it is very useful in that the monodispersed precursor of the present invention can be synthesized.

FIG. 1 shows an infrared spectrum of the compound 2,2-bis (4-hydroxycyclohexyl) propanediallyl ether compound of the present invention. FIG. 2 is a diagram showing a ¹ H-NMR spectrum of the compound 2,2-bis (4-hydroxycyclohexyl) propanediallyl ether compound of the present invention. FIG. 3 is a diagram showing a ¹³ C-NMR spectrum of the compound 2,2-bis (4-hydroxycyclohexyl) propanediallyl ether compound of the present invention. FIG. 4 shows an infrared spectrum of the compound 2,2-bis (4-hydroxycyclohexyl) propanedimethallyl ether compound of the present invention. FIG. 5 is a diagram showing a ¹ H-NMR spectrum of the compound 2,2-bis (4-hydroxycyclohexyl) propanedimethallyl ether compound of the present invention. FIG. 6 is a diagram showing a ¹³ C-NMR spectrum of the present compound 2,2-bis (4-hydroxycyclohexyl) propanedimethallyl ether compound.

  The novel high-purity compound of the present invention is represented by the above chemical formula (1), has a chlorine content of 100 ppm or less, and an allyl etherification rate at both ends of 95% or more. -It is represented by the bis (4-hydroxycyclohexyl) propane diallyl ether compound (A) and the above chemical formula (2), the chlorine content is 100 ppm or less, and the methallyl etherification rate at both ends is 95% or more. The 2,2-bis (4-hydroxycyclohexyl) propane dimethallyl ether compound (B) is characterized. That is, it is characterized in that impurities which are allyl etherified or methallyl etherified only at one end contain 5% or less, preferably 3% or less.

  2,2-bis (4-hydroxycyclohexyl) propane diallyl ether compound (A) and 2,2-bis (4-hydroxycyclohexyl) propane dimethallyl ether compound (B) which are the compounds of the present invention [hereinafter 2,2, -Bis (4-hydroxycyclohexyl) propanediallyl ether compound (A) and 2,2-bis (4-hydroxycyclohexyl) propanedimethallyl ether compound (B) were converted to 2,2-bis (4-hydroxycyclohexyl) propanedi (meta ) The allyl ether compound may be abbreviated. In addition, allyl and methallyl are sometimes collectively referred to as (meth) allyl. 2,2-bis (4-hydroxycyclohexyl) propane [alias: hydrogenated bisphenol A]) that is commercially available as an industrial raw material can be used.

  Commercially available hydrogenated bisphenol A is usually a mixture of conformers in which the hydroxyl group is in the equatorial position or the axial position, and the equatorial position is more stable in terms of thermal energy and has a higher content. Equatorial / axial is approximately 7/3. These can also be separated by recrystallization. When an etherification reaction is carried out using an allyl halide, these stereoisomers are etherified while being retained.

  In the production of the 2,2-bis (4-hydroxycyclohexyl) propanedi (meth) allyl ether compound which is a compound of the present invention, for example, a non-reactive ether solvent (E) such as diethylene glycol dimethyl ether is used as an essential component. Bisphenol A hydride and alkali metal hydroxide (D) are stirred and dispersed in the mixture, and allyl halide (C) such as allyl chloride and methallyl chloride is added dropwise in the range of 40 to 90 ° C. to further increase the reaction efficiency. In order to raise, it is preferable to perform the etherification reaction of a hydroxyl group and an allyl halide in two stages.

    As the first stage reaction, hydrogenated bisphenol A is prepared by reacting 1 to 1.5 moles of allyl chloride or methallyl chloride with alkali metal hydroxide (D) with respect to 1 mole of hydrogenated bisphenol A. The (meth) allyl etherified product is liquefied. Subsequently, water is added to the reaction product to dissolve the generated sodium chloride, and the aqueous layer (lower layer) is removed. As a second-stage reaction, 1 to 1.5 moles of allyl chloride or methallyl chloride and alkali metal hydroxide (D) are added to the remaining organic layer (upper layer) again, and the reaction is performed in a high yield. A highly etherified 2,2-bis (4-hydroxycyclohexyl) propane di (meth) allyl ether compound is obtained. Increasing the reaction efficiency means promoting the alcoholation, which is the rate-limiting step of the etherification reaction. The hydroxyl group is activated by liquefaction, and solids are removed by once removing a large amount of water and sodium chloride. It is considered that the solid surface of the alkali metal hydroxide is renewed and is easily converted to an alcoholate.

  When the 2,2-bis (4-hydroxycyclohexyl) propanedi (meth) allyl ether compound of the present invention is produced, both ends of the hydroxyl group of the raw material hydrogenated bisphenol A must be allyl etherified. In order to make this allyl etherification rate 95% or more, preferably 97% or more, it is necessary to use a non-reactive ether solvent (E) as a solvent.

  Non-reactive ether solvents (E) for that purpose include ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), glymes such as tetraethylene glycol dimethyl ether (tetraglyme), tetrahydrofuran ( THF), and diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, and tetrahydrofuran are preferred. From the viewpoints of solubility of hydrogenated bisphenol A and removability after reaction, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether are more preferable.

  Examples of the alkali metal hydroxide (D) used in this reaction include solids of sodium hydroxide, potassium hydroxide and lithium hydroxide, preferably sodium hydroxide and potassium hydroxide, more preferably water. Sodium oxide. These solid alkali metal hydroxides may be used alone or as a mixture of two or more. These solid alkali metal hydroxides may be in the form of granules, flakes, or powders. The size is preferably 1 to 5 mm in diameter for granular materials, 0.5 to 3 cm square for flakes, and preferably 30 to 100 μm for powders, but the present invention is not limited thereto. Granularity is preferable for the handling of workers.

  The reaction temperature is usually 40 ° C to 90 ° C, preferably 60 to 80 ° C, more preferably 70 to 80 ° C. If it is less than 40 ° C., the reaction proceeds very slowly and is not efficient. When the temperature exceeds 90 ° C., corrosion may occur even if the material of the container is SUS316L having good durability.

The reaction is preferably performed in an inert gas atmosphere such as nitrogen (oxygen concentration is preferably 100 ppm or less). The order of mixing and charging hydrogenated bisphenol A, non-reactive ether solvent (E), (meth) allyl chloride (C), and solid alkali metal hydroxide (D) It is preferable to mix the solvent, disperse the solid alkali metal hydroxide, repeat decompression at room temperature and substitution with an inert gas such as nitrogen, and then drop (meth) allyl chloride dropwise under reduced pressure.
In the method of mixing hydrogenated bisphenol A, non-reactive ether solvent, and (meth) allyl chloride, and finally mixing and adding solid alkali metal hydroxide, (meth) allyl chloride bumps suddenly with the heat of dissolution of the alkali metal. Or the etherified product is easily colored.

  Water is added to the reaction mixture after the first stage reaction to dissolve and separate excess alkali metal hydroxide and product salt. After liquid separation, a solid alkali metal hydroxide is further added to the organic layer, and after substitution with nitrogen, (meth) allyl chloride is added dropwise under reduced pressure to complete the reaction at 70-80 ° C. in about 6-8 hours.

  Water is again added to the reaction mixture after the second stage reaction to dissolve and separate the excess alkali metal hydroxide and the generated salt. After liquid separation, an alkali adsorbent is added to the organic layer, and preferably the non-reactive ether solvent, excess (meth) allyl chloride and water are distilled off at 70 to 120 ° C. under reduced pressure (preferably −85 KPaG or less). After leaving, by filtration, a highly etherified 2,2-bis (4-hydroxycyclohexyl) propanedi (meth) allyl ether compound can be obtained in a high yield.

The alkali adsorbent (F) to be introduced into the organic layer after the second-stage liquid separation is, for example, synthetic magnesium silicate (for example, “KYOWARD 600” manufactured by Kyowa Chemical Industry Co., Ltd.), synthetic aluminum silicate (for example, “KYO” Word 700 ": the same as above), hydrotalcites (for example," KYOWARD 2000 ": the same as above), activated clay (for example," Galleon Earth ": the same as above)) and the like, preferably synthetic magnesium silicate.
A diatomaceous earth filter aid (for example, “Radiolite”: the same as above) may be used together with these adsorbents. The addition amount of the alkali adsorbent is preferably 0.1 to 2.0% by weight with respect to the organic layer after the liquid separation. The temperature at which the non-reactive ether solvent, excess (meth) allyl chloride and water are distilled off is preferably 70 to 120 ° C, more preferably 90 to 115 ° C. When the distillation temperature is 70 ° C. or higher, a practical distillation rate is obtained, and when it is 120 ° C. or lower, the non-reactive ether solvent can be efficiently recovered and can be recycled. The pressure is preferably −85 KPaG or less, more preferably −95 KPaG or less. When it is −85 KPaG or less, a practical distillation rate can be obtained.

  The chlorine content in the compounds (A) and (B) of the present invention is 100 ppm or less, preferably 50 ppm. By reducing the chlorine content, it can be used for electronic materials.

If necessary, a known phase transfer catalyst (G) may be used for this reaction.
Preferred examples of the phase transfer catalyst (G) include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, and the like, and more preferably quaternary ammonium salts. Examples of the quaternary ammonium salt include tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, trioctylammonium chloride, n-laurylpyridinium chloride. Etc. are included. The quaternary phosphonium salt includes, for example, tetraethylphosphonium chloride, dimethyldicyclohexylphosphonium bromide, and triphenylmethylphosphonium iodide. Quaternary arsonium salts include, for example, tetramethylarsonium chloride, tetraethylarsonium bromide, and tetraethylarsonium hydroxide.
The amount of addition when these phase transfer catalysts are added to the reaction system of the present invention is preferably 0.5% by weight or less, more preferably 0.2% by weight or less, based on hydrogenated bisphenol A. Particularly preferred is 0.1% by weight or less. When the amount is 0.5% by weight or less, there is no significant coloring and a practical reaction rate can be obtained. There is no particular limitation on the mixing method and timing, but it is preferable to add before the reaction.

  According to the production method of the present invention, 2,2-bis (4-hydroxycyclohexyl) propanedi (meth) allyl ether, which has few unreacted hydroxyl groups and is efficiently allyl etherified and has few impurities, is industrially produced. Can be manufactured. Further, 2,2-bis (4-hydroxycyclohexyl) propanedi (meth) allyl ether obtained by the practice of the present invention is used as an intermediate to a silicone modifier or an epoxy resin, and is used in electrical / electronic materials and paint fields. It is particularly useful as an intermediate for resins used in the adhesive field and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Below, a part shows a weight part.

<Chlorine content measurement method>
Reaction solution A: 2.67 g of sodium methylate 28% methanol solution is precisely weighed, 110 ml of methanol and 405 ml of acetone are added to make it uniform, and 1 ml of bromophenol blue indicator is added.
10 g (S) of the sample is weighed in a 100 ml beaker, and the reaction solution A is added with a 50 ml hole pipette and stirred with a stirrer for 10 minutes. About 10 drops of nitric acid are added thereto, and titration is performed with a 0.0025 mol / L silver nitrate standard solution using a potentiometric automatic titrator (for example, AT-500 automatic titrator manufactured by Kyoto Electronics Co., Ltd.) (Aml). The same operation is performed for the blank (Bml), and calculation is performed according to the equation (1).
Chloride ion content (ppm) = {(AB) × 2.5 × 35.5 × f} / S Formula (1)
Where f: titer of ammonium thiocyanate titration solution, S: sample collection amount (g)

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this.

Example 1
In a 1 L simple pressurized reactor with a content outlet at the bottom, 240 g (1.0 mol) of hydrogenated bisphenol A (manufactured by Shin Nippon Rika Co., Ltd., Rikabinol HB), 240 g of diethylene glycol dimethyl ether, granular sodium hydroxide 60 g (1.5 mol) and 2 g of a 50% aqueous solution of benzyltrimethylammonium chloride were mixed, replaced with nitrogen while stirring and dispersing, and 114.8 g (1.5 mol) of allyl chloride at 30 to 40 ° C. under reduced pressure. Was dripped. After dropping, the temperature was gradually raised while observing the pressure, and the reaction was carried out at 80 ° C. for 8 hours. 320 g of water was added to the reaction solution, stirred for 10 minutes and allowed to stand for 20 minutes, and then the lower layer (aqueous layer) was separated and removed. The remaining upper layer was a uniform light yellow liquid.
This upper layer was again mixed with 60 g (1.5 mol) of granular sodium hydroxide and 2 g of a 50% aqueous solution of benzyltrimethylammonium chloride. The mixture was stirred and dispersed, followed by nitrogen substitution, and allyl chloride at 30-40 ° C. under reduced pressure. 114.8 g (1.5 mol) was added dropwise. After dropping, the temperature was gradually raised while observing the pressure, and the reaction was carried out at 80 ° C. for 10 hours. 320 g of water was added to the reaction solution, stirred for 10 minutes and allowed to stand for 20 minutes, and then the lower layer (aqueous layer) was separated and removed. To the upper layer (organic layer), 2.5 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) as an alkali adsorbent was added, and after removing the solvent at 120 ° C. under reduced pressure, the filtrate was filtered and 2,2-bis A (4-hydroxycyclohexyl) propane diallyl ether compound was obtained.
The yield was 310 g, which was a high yield of 97% with respect to the theoretical yield of 320 g in terms of the raw material hydrogenated bisphenol A. The analytical value of the chlorine content was 5.4 ppm. The hydroxyl value was 10.4, and the etherification rate of the hydroxyl group was 97.8% from the hydroxyl value 467 of the raw material hydrogenated bisphenol A. The obtained 2,2-bis (4-hydroxycyclohexyl) propane diallyl ether compound was subjected to infrared spectrum, ¹ H-NMR, and ¹³ C-NMR analysis.

1 to 3 show the infrared spectrum, ¹ H-NMR spectrum, and ¹³ C-NMR spectrum.
Infrared spectrum: 2925, 2860, 1650 (C = C), 1454, 1369, 1350, 1127, 1077, 1030, 993, 915 cm ^−1
1 H-NMR (CDCl ₃ , 300 MHz): δ 5.90 (m, 2H), 5.25 (dd, 2H), 5.12 (dd, 2H), 4.00-3.93 (d, 4H) 3.58-3.18 (m, 2H), 2.1-1.7 (m, 8H), 1.5-0.9 (m, 10H), 0.7 (s, 6H)
¹³ C-NMR (CDCl ₃ , 300 MHz): δ 135.7, 115.8, 78.0, 72.3, 68.5, 43.5, 36.4, 32.7, 24.8, 20.5

Example 2
2,2-bis (4-hydroxycyclohexyl) propane dimethallyl ether could also be produced by the same synthesis method by changing allyl chloride to methallyl chloride, and had a chlorine content of 7.5 ppm. The hydroxyl value was 8.4, and the etherification rate of the hydroxyl group from the hydroxyl group 467 of the raw material hydrogenated bisphenol A was 98.2%. Infrared spectrum, ¹ H-NMR, and ¹³ C-NMR analysis were performed.

4 to 6 show the infrared spectrum, ¹ H-NMR spectrum, and ¹³ C-NMR spectrum of 2,2-bis (4-hydroxycyclohexyl) propanedimethallyl ether. Infrared spectrum: 2925, 2860, 1650 (C = C), 1442, 1356, 1341, 1100, 1087, 1030, 971, 893 cm ^−1
1 H-NMR (CDCl ₃ , 300 MHz): δ 4.92 (s, 2H), 4.81 (s, 2H), 4.02-3.83 (d, 4H), 3.58-3.18 ( m, 2H), 2.1-1.65 (m, 8H), 1.7 (s, 6H), 1.5-0.9 (m, 10H), 0.7 (s, 6H)
¹³ C-NMR (CDCl ₃ , 300 MHz): δ 143.1, 111.4, 77.8, 71.8, 65.8, 43.4, 33.6, 33.6, 32.8, 30.7 , 25.0, 20.6, 19.5

Comparative Example The first-stage reaction was attempted in the same manner by replacing the diethylene glycol dimethyl ether used in the Examples with toluene.
However, hydrogenated bisphenol A partially dissolved in toluene at 80 ° C., but the alkali metal hydroxide did not migrate to the organic layer. Also, the phase transfer catalyst benzyltrimethylammonium chloride was not effective and the reaction did not proceed. Hydrogenated bisphenol A was recovered as a solid.

Since the novel high-purity compound of the present invention is an alicyclic compound as described above, it is a composition that can give a cured product that is superior in optical transparency and light resistance compared to an aromatic compound. Furthermore, it can be used as a raw material for a curable composition for optical materials exhibiting excellent physical, thermal and electrical properties derived from crosslinking by reaction with SiH groups.
Furthermore, by oxidizing the novel high-purity compound of the present invention, it can be derived into a hydrogenated bisphenol A epoxy compound that is useful industrially, particularly as an electronic material. In particular, the current product obtained by hydrogenating the condensate of bisphenol A and epichlorohydrin contains 200 to 500 ppm of chlorine, whereas the high purity obtained in this production. Those that can participate in the precursor can be substantially free of chlorine. Accordingly, chlorine can be used for electronic materials that cause a decrease in electrical insulation.
In addition, due to recent technological innovations in the fields of electronics and high-performance paints, there is an increasing demand for high-purity liquid epoxy resins with extremely low impurity chlorine, and the compounds of the present invention have a monodisperse molecular weight distribution. In terms of low viscosity, it is useful as a highly pure liquid epoxy resin or a modified product thereof.

Claims (4)

2,2-bis (4-hydroxycyclohexyl) propane diallyl ether represented by the following chemical formula (1), having a chlorine content of 100 ppm or less and an allyl etherification rate of both ends of 95% or more Compound (A).

2,2-bis (4-hydroxycyclohexyl) propane dimetallized by the following chemical formula (2), having a chlorine content of 100 ppm or less and a methallyl etherification rate of both ends of 95% or more Ruether compound (B).

  In a method for obtaining a di (meth) allyl ether compound by using a hydrogenated bisphenol A as a precursor to carry out a desalting reaction using an allyl halide (C) and an alkali metal hydroxide (D). The method for producing a di (meth) allyl ether compound according to claim 1 or 2, wherein a solvent (E) is used.   The method for producing a di (meth) allyl ether compound according to claim 3, wherein the non-reactive ether solvent (E) is at least one selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetrahydrofuran.

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