JP2003012662A - Oxetane ring-bearing 2,2-bis(4hydroxyphenyl) hexafluoropropane derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cationically polymerizable new oxetane ring-bearing 2,2-bis(4-hydroxyphenyl)hexafluoropropane derivative, and to provide a method for producing the derivative. SOLUTION: The objective oxetane ring-bearing 2,2-bis(4-hydroxyphenyl) hexafluoropropane derivative is obtained by reaction between 2,2-bis(4- hydroxyphenyl)hexafluoropropane, an alkaline agent, and a 3-alkyl-3- chloromethyl oxetane or 3-chloromethyl oxetane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring capable of cationic polymerization and a method for producing the same. The photocurable or thermosetting composition containing the 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative has a low refractive index, transparency, water repellency, oil repellency, heat resistance, and curing. Used as paints and coatings, adhesives, lenses, etc., to give a cured product with excellent properties and mechanical properties.

[0002]

2. Description of the Related Art Oxetane compounds are compounds that have been receiving attention in recent years as monomers capable of photoinitiated cationic polymerization or curing, and many monofunctional and polyfunctional oxetane compounds have been reported. For example, Pure Appl.Che
m., A29 (10), pp.915 (1992) and Pure Appl. Chem., A30 (2
& 3), pp.189 (1993) describes a method for synthesizing various oxetane derivatives.

Japanese Patent Laid-Open No. 2000-191652 discloses that
An oxetane compound represented by formula (2) is disclosed.

[0004]

[Chemical 2] (In the formula (2), R is a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group,
It is a furyl group or a thienyl group, and the substituent R _f has the formula C _n F
_2n-1 , a monovalent fluorine-containing group represented by the formula C _n F _2n H or the formula C _n F _{2n + 1} (n in each formula is an integer of 2 to 12) and having a repeating number m is an integer of 1 to 10. )

Japanese Patent Publication No. 11-500422 discloses a mono-substituted fluorinated oxetane monomer, but does not describe a 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring. Oxetane compounds described in these publicly known documents have a low glass transition temperature, and sometimes the heat resistance of the obtained cured product is insufficient, and the water absorption is rather large, and the electrical properties of the obtained cured product are insufficient. Therefore, use may be restricted depending on the conditions.

[0006]

DISCLOSURE OF THE INVENTION The present invention has solved the above-mentioned problems, that is, 2,2-bis having a novel oxetane ring having a high glass transition temperature, a low water absorption and a low refractive index. A (4-hydroxyphenyl) hexafluoropropane derivative and a method for producing the same are provided.

[0007]

In order to solve the above problems, the 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring according to claim 1 is represented by the formula (1). It has a structural formula:

[0008]

[Chemical 3] (In the formula (1), R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

A method for producing a 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring according to claim 2 is 2,2-bis (4-hydroxyphenyl) hexafluoropropane, an alkaline agent. And 3-alkyl-3-chloromethyloxetane or 3-chloromethyloxetane.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring of the present invention includes 2,2-bis (4-hydroxyphenyl) hexafluoropropane, an alkaline agent and 3
It is obtained by reacting -alkyl-3-chloromethyloxetane or 3-chloromethyloxetane.

2,2-bis (4-hydroxyphenyl)
Hexafluoropropane is one in which all the hydrogen atoms of the two methyl groups of bisphenol A are replaced by fluorine atoms.

The alkaline agent is a component for condensing 2,2-bis (4-hydroxyphenyl) hexafluoropropane and 3-alkyl-3-chloromethyloxetane or 3-chloromethyloxetane by dehydrochlorination reaction. , Alkali metal hydroxides, alkali metal hydrides, alkali metals and the like can be used. Specific examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Usually, an aqueous solution or a solid solution having a concentration of 5 to 60% by mass is used, but a concentration of 40 to 50.
A mass% aqueous solution is preferable. Specific examples of the alkali metal hydride include sodium hydride and potassium hydride, and specific examples of the alkali metal include sodium and potassium. The amount of the alkaline agent used is preferably 1 to 4 times equivalent, and preferably 1 to 2 times equivalent, based on the equivalent number of the phenolic hydroxyl group of 2,2-bis (4-hydroxyphenyl) hexafluoropropane. Is more preferable.

As 3-alkyl-3-chloromethyloxetane or 3-chloromethyloxetane, those produced by a known method can be used (JP-A-10-2.
No. 04071, JP-A-10-212228,
Japanese Patent Publication No. 11-500422).

2,2-bis (4-hydroxyphenyl)
The reaction of hexafluoropropane, the alkaline agent and 3-alkyl-3-chloromethyloxetane or 3-chloromethyloxetane can be carried out under the condition of carrying out a normal dehydrochlorination reaction. Reaction temperature is 80-150
C. is preferable, and 100 to 120.degree. C. is more preferable. The reaction time is preferably 3 to 50 hours, more preferably 4 to 12 hours, depending on the reaction temperature and the presence or absence of a phase transfer catalyst described later.

2,2-bis (4-hydroxyphenyl)
The reaction of hexafluoropropane, an alkaline agent and 3-alkyl-3-chloromethyloxetane or 3-chloromethyloxetane can shorten the reaction time when a phase transfer catalyst is added. As the phase transfer catalyst, a known phase transfer catalyst (for example, W.
P. Weber, G .; W. Co-authored by Gokel, Iwao Tabushi,
Takatani Nishitani's joint translation "Phase Transfer Catalyst", those described in Kagaku Dojin, etc.) can be used. Among them, organic 4th
Primary ammonium salts and phosphonium salts are preferred. Specific examples include tetra-n-butylammonium bromide, benzyltriethylammonium bromide, trioctylmethylammonium chloride, tetra-n-butylphosphonium chloride, trioctylethylphosphonium bromide and tetraphenylphosphonium chloride. The amount of phase transfer catalyst used is 2, 2
A molar ratio of 0.1 based on the phenolic hydroxyl group of bis (4-hydroxyphenyl) hexafluoropropane
-30% is preferable, and 1-10% is more preferable. If the amount used is too small, the effect of smoothing the reaction is not sufficient, and if the amount is too large, it may be economically wasteful and the purity of the product may deteriorate.

The above reaction can be carried out using a solvent, and in particular, the method using an aromatic hydrocarbon solvent is
The reaction can proceed smoothly. Among the aromatic hydrocarbon solvents, benzene, toluene, xylene and the like are preferably used.

After the reaction, the organic phase was cooled to room temperature,
Alternatively, the organic solid matter is taken out, washed with water and desolvated to obtain a desired 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring represented by the above formula (1). . The derivative is
Nuclear magnetic resonance spectrum (hereinafter referred to as NMR) Specifically, it is a novel compound whose structure can be confirmed by 1H-NMR, 13C-NMR and 19F-NMR. R ^{1 in} formula (1)
And R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a methyl group or an ethyl group is particularly preferable.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 A glass 100 ml four-necked round bottom flask equipped with a stirrer, a thermometer, a dehydration tube and a condenser was charged with 16.8 g of 2,2-bis (4-hydroxyphenyl) hexafluoropropane. (0.05 mol) and 4-chloromethyl-3-ethyloxetane 40.4 g (0.30 mol) were added with stirring, and 48% by mass of potassium hydroxide aqueous solution 12.3.
g (0.105 mol) was added dropwise from the dropping funnel over 10 minutes.
Tetrabutylammonium bromide as a catalyst here.
After adding 65 g, raise the temperature to reflux (about 110 ° C),
The mixture was reacted for 6 hours under reflux.

After completion of the reaction, the reaction solution was cooled to room temperature, transferred to a separating funnel, 100 g of toluene and 100 ml of pure water were added, and well stirred. After separating the organic phase and the aqueous phase, the organic phase was washed with 100 ml of pure water three more times. Toluene and 3-chloromethyl-3-ethyloxetane in the organic phase were removed under reduced pressure to obtain a solid product. The product was purified by recrystallization to give 16.5g of white solid. White solid has a melting point of 1
The temperature was 29.7 ° C, and the purity determined by gas chromatographic analysis was 99.9%. The yield after the reaction was 93%.

From the results of the NMR analysis shown below, the product is 2,2-bis [4-having a structure represented by the formula (3).
(1-Ethyl-3-oxetanyl) methoxyphenyl]
It was confirmed to be hexafluoropropane.

1 H-NMR (heavy acetone solvent) measurement result: δ (p
pm) J (Hz); a; 0.96 (t J = 7.5Hz), b; 1.89 (q J = 7.5H)
z), c; 4.22 (s), d; 4.45 (d J = 32Hz d J = 5.9Hz), g and h; 7.
08〜7.36 (m) 13C-NMR (heavy acetone solvent, 1H irradiation) measurement result: δ (pp
m); a; 8.39, b; 27.40, c; 71.30, d; 77.87, e; 43.79, f;
160.52, g; 115.17, h; 132.22, i; 126.03, j; 64.50 (m),
k; 119.17 to 131.81 19 F-NMR (heavy acetone solvent) measurement result: δ (ppm); -64.6
7

[0023]

[Chemical 4]

[0024]

The novel 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring can be obtained from easily available raw materials. The photocurable or thermosetting composition containing the 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring of the present invention has a low refractive index, transparency, water repellency, oil repellency, and Since it gives a cured product having excellent heat resistance, curability and mechanical properties and low water absorption, it can be used for paints and coating materials, adhesives, lenses and the like. In particular, the effect of giving a cured product with excellent heat resistance and low water absorption is
It is considered to be derived from 2,2-bis (4-hydroxyphenyl) hexafluoropropane residue.

Claims (2)

[Claims] 1. A 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative having an oxetane ring represented by the formula (1). [Chemical 1] (In the formula (1), R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 2. An oxetane ring characterized by reacting 2,2-bis (4-hydroxyphenyl) hexafluoropropane, an alkaline agent and 3-alkyl-3-chloromethyloxetane or 3-chloromethyloxetane A method for producing a 2,2-bis (4-hydroxyphenyl) hexafluoropropane derivative.