JPH0680602A - Fluorine-containing ether oligomer and its production - Google Patents

Abstract

PURPOSE:To provide a production process for a novel fluorinecontaining ether oligomer of a low molecular weight which bears a trifluoromethyl group in the molecule as well as phenyl ether, alkyl-substituted phenyl ether or aryl- substituted alkyl ether on the other end, and is useful as a lubricant or a modifier for polymer materials. CONSTITUTION:A novel fluorine-containing ether oligomer of the formula: H(O-(CF3)CH-CH2)-nO-(CH2)m-R<1> (R<1> is phenyl or alkyl-substituted phenyl; m is 0 to 4; n is 2 to 100 on the average), for example. The oligomer can be prepared by polymerization of trifluoropropylene oxide in the presence of an alkali metal hydroxide, an alkali alkoxide and phenol, an alkyl-substituted phenol or an aromatic substituted phenol and termination of the polymerization by addition of an acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluorine-containing ether oligomer useful as a lubricating oil, a modifier for a polymer material, or an intermediate for a functional material, and a method for producing the same. More specifically, it is obtained by polymerizing an alkali metal hydroxide or an alkali metal alkoxide with trifluoropropylene oxide in the presence of phenol, an alkyl-substituted phenol or an aromatic-substituted alcohol, and one end thereof is phenyl ether, alkyl-substituted phenyl ether or aromatic. The present invention relates to a fluorinated ether oligomer of a substituted alkyl ether and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Trifluoropropylene oxide polymer is a chemically stable polyether having a trifluoromethyl group and has unique physical properties. Therefore, it is used as a lubricant, paint, adhesive, modifier, etc. It is useful. The present inventors previously found a novel substance, trifluoropropylene oxide oligomer, having an alkyl ether at both ends or one end, but it was disclosed in Japanese Patent Application No. 04-14363.
4), highly heat-stable, compatible phenyl ether, alkyl-substituted phenyl ether, or aromatic-substituted alkyl ether-terminated trifluoropropylene oxide oligomer is not known.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have studied a method for obtaining a fluorine-containing ether oligomer suitable for use as a lubricating oil, a modifier for polymer materials, etc., and as a result, have found that an alkali metal hydroxide or an alkali metal alkoxide is used. And phenol, alkyl-substituted phenol or by polymerizing trifluoropropylene oxide in the presence of an aromatic substituted alcohol, and by using an acid as a polymerization terminator,
It was found that a novel trifluoropropylene oxide polymer having a phenyl ether, an alkyl-substituted phenyl ether or an aromatic-substituted alkyl ether at one end can be selectively obtained, and that optically active trifluoropropylene oxide is used as a raw material unit. It was found that an optically active trifluoropropylene oxide polymer useful as a functional material can be obtained by the above-mentioned method, and further, the molecular weight of the polymer can be controlled by adjusting the amount of alkali or alkoxide used with respect to trifluoropropylene oxide. Has reached the present invention.

[0004]

The fluorine-containing ether oligomer of the present invention has the following general formula: It is represented by. Here, R ¹ is a phenyl group or an alkyl-substituted phenyl group, m = 0 to 4, and n is 2 to 100 on average.
And has a structure in which one end is a phenyl ether, an alkyl-substituted phenyl ether, or an aromatic-substituted alkyl ether.

The phenyl group and alkyl-substituted phenyl group of R ¹ are phenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-propylphenyl, 4-sec-butylphenyl, 4-tert-.
Butylphenyl, 3,4-dimethylphenyl, 4-isopropyl-3-methylphenyl and the like can be mentioned.

The type of the substituent R ¹ and m and n can be freely selected depending on the use of the fluorine-containing ether oligomer.

In the general formula [I], since the carbon of --CH-- is an asymmetric carbon, by using an optically active trifluoropropylene oxide as a raw material monomer, a fluorine-containing ether oligomer which is an optically active substance can be obtained. It can be manufactured. The present invention includes such an optically active fluorinated ether oligomer.

The structure of the fluorine-containing ether oligomer of the present invention has a proton NMR ( ¹ H-NMR), infrared absorption spectrum (IR), ¹³ C-NMR, and glass transition point (T).
It can be identified by g).

For example, in the general formula (1), R ¹ = C ₆ H
₅ , m = 0, and the average value of n is 5.4, the fluorinated ether oligomer exhibits the following physical properties.

(1) ¹ H-NMR (FIG. 1) The following signals are observed. _{7.4~6.8ppm (C 6 H 5) 5.6ppm} (OH) 4.6~3.9ppm (CH, CH 2)

(2) ¹³ C-NMR (FIG. 2) The following signals are observed. 159 ppm (d) 132 to 118 ppm (e) 130 ppm (c) 122 ppm (b) 115 ppm (a) 79 to 77 ppm (h) 72 to 70 ppm (g) 66 ppm (f) These signals are represented by the following structural formula [3]. It is based on the chemical shift of carbon atoms in. From this, it is understood that this compound has a CF ₃ group and a polyether structure in which the terminal is phenyl ether.

(3) IR (FIG. 3) 3450, 2950, 2900, 1600, 1490,
1460, 1370, 1260, 1100, 1040,
Absorption was observed at 880, 750 and 690 cm ^-1 , which confirms the presence of alcohol and phenyl groups.

(4) Tg -44 ° C

[0014] The molecular weight can be determined as a peak molecular weight in GPC (polystyrene equivalent values), further ¹
From H-NMR, the relational expression (a + b) between the peak integration ratio and the degree of polymerization in the following formula [4]: c = 3n: 5 (where a and c are the peak integration values of the following methine, methylene, and phenyl groups, respectively) From the number average molecular weight M
n and the degree of polymerization n of trifluoropropylene oxide.

It should be noted that trifluoropropylene oxide ([α] =-8.6 °, (C =
2.1, THF)), the resulting polymer becomes an optically active substance with optical rotation [α] =-11.0 ° and (C = 1.1, THF).

In the general formula (1), R ¹ = C ₆ H
₅ , the fluorine-containing ether oligomer having an average value of 2.6 with m = 1 has the following physical properties.

(1) ¹ H-NMR (FIG. 4) The following signals are recognized. _{7.4~7.2ppm (C 6 H 5) 5.5ppm} (OH) 4.6ppm (CH 2 benzyl) 4.4~3.6ppm (TFPO derived CH, CH ₂₎

(2) ¹³ C-NMR (FIG. 5) The following signals are observed. 143 to 138 ppm (d) 132 to 118 ppm (h) 128.5 ppm (b) 128 ppm (a, c) 79 to 77 ppm (g) 74 ppm (e) 72 to 68 ppm (f) These signals are represented by the following structural formula [ 5] based on the chemical shift of carbon atoms. From this, it can be seen that this compound has a CF ₃ group and has a polyether structure in which the terminal is benzyl ether.

(3) IR (FIG. 6) 3350, 2900, 1580, 1450, 1370,
1260, 1100, 910, 840, 740, 690
Absorption is observed at cm ⁻¹ , which confirms the presence of alcohol and phenyl groups.

(4) Tg -60 ° C

[0021] The molecular weight can be determined as a peak molecular weight in GPC (polystyrene equivalent values), further ¹
From H-NMR, the relational expression (a + b) between the peak integration ratio and the degree of polymerization in the following formula [6]: c: d = 3n: 2: 5.
(However, a, b, c and d are respectively the peak integral values of the following methine, methylene, methylene and phenyl groups) and are determined as the number average molecular weight Mn and the degree of polymerization n of trifluoropropylene oxide.

It should be noted that optically active trifluoropropylene oxide ([α] =-8.6 °, (C =
2.1, THF)), the resulting polymer becomes an optically active substance with an optical rotation [α] = − 6.1 °, (C = 1.0, THF).

The fluorine-containing ether oligomer of the present invention is prepared by polymerizing an alkali metal hydroxide or an alkali metal alkoxide with trifluoropropylene oxide in the presence of phenol, an alkyl-substituted phenol or an aromatic-substituted alcohol, and terminating the polymerization with an acid. It can be manufactured.

Trifluoropropylene oxide used as a monomer in the method of the present invention is a compound represented by the following formula [2]: Bromotrifluoroacetone obtained by brominating trifluoroacetone is reduced with lithium aluminum hydride and bromotrifluoroisopropyl alcohol is treated with caustic soda, or trifluoropropylene is oxidized with a microorganism (Japanese Patent Publication No. 61-147
No. 98, JP-A No. 61-202697) and the like.

By using optically active trifluoropropylene oxide as a raw material monomer, a fluorine-containing ether oligomer which is an optically active substance can be produced. The trifluoropropylene oxide obtained by the oxidation of trifluoropropylene is optically active and therefore suitable for producing an optically active oligomer.

The alkali metal hydroxide or alkali metal alkoxide (hereinafter sometimes simply referred to as alkali or alkoxide) used in the present invention is a hydroxide such as sodium hydroxide or potassium hydroxide, or sodium, potassium or rubidium. , Cesium, etc., such as methoxide,
Examples include ethoxide, propoxide, butoxide and the like.

In the present invention, the molecular weight of the fluorinated ether oligomer produced can be controlled by the amount of alkali or alkoxide used. That is, if the amount of the alkali or alkoxide used with respect to the monomer trifluoropropylene oxide is increased, the molecular weight of the resulting oligomer decreases, and conversely, by reducing the amount of the alkali or alkoxide used, an oligomer with a high molecular weight can be obtained. it can. Therefore, the molecular weight can be easily controlled by adjusting the amount of alkali or alkoxide used. This is also one of the features of the present invention.

The amount of alkali or alkoxide used is preferably 0.5 to 100%, particularly 1 to 50%, based on the monomer, and can be appropriately selected according to the target molecular weight.

The phenol, alkyl-substituted phenol or aromatic substituted alcohol used in the present invention is phenol, p-cresol, 4-ethylphenol, 4-isopropylphenol, 4-propylphenol, 4-sec-butylphenol, 4-tert. −
Butylphenol, 3,4-dimethylphenol, 4-
Alkyl-substituted phenols such as isopropyl-3-methylphenol, benzyl alcohol, phenethyl alcohol, 3-phenyl-1-propanol, 4-phenyl-
Aromatic substituted alcohols such as 1-butanol, 3,4-dimethylbenzyl alcohol, 4-methyl-phenethyl alcohol and 4-isopropylbenzyl alcohol can be mentioned.

The amount of phenol, alkyl-substituted phenol or aromatic-substituted alcohol used is 1 to 2 times mol, particularly 1 to 1.2 times mol of the alkali or alkoxide.
ol is preferred.

The polymerization may be carried out without solvent or in the presence of an organic solvent. Ethers such as 1,2-dimethoxyethane are suitable as the solvent. Polymerization temperature is-
20-100 degreeC, especially 0-50 degreeC are preferable.

The polymerization reaction is stopped by adding an acid. Examples of the acid used for stopping the reaction include hydrochloric acid, sulfuric acid, acetic acid and the like.

After the reaction is completed, the reaction is stopped with an acid,
The fluorinated ether oligomer is obtained by washing with water, distilling off the solvent and drying under reduced pressure.

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 Trifluoropropylene oxide (TFPO) obtained by oxidizing trifluoropropylene with a microorganism according to the method described in JP-B-61-14798 was dried with Molecular Sieve 4A. A thermometer, a cooling tube, and a calcium chloride tube were attached to a dried three-necked flask, and 10 ml of 1,2-dimethoxyethane dried with molecular sieve 4A and 2.29 g (24 mmol) of phenol were added and dissolved by stirring. A water bath was added, and 1.52 g (24 mmol) of potassium hydroxide ground in a mortar was put into this and mixed with stirring. To this, 10.0 ml of the dried TFPO (11
7 mmol) was added and stirred, and the temperature rose from about 30 minutes and reached 40 ° C. after 1 hour. Bath in a water bath to keep the system temperature at 25-45 ° C, continue stirring, and add TFP.
Twenty-four hours after the addition of O, 27 ml of 1N-HCl was added to stop the reaction. The reaction was dissolved in ether, washed with water several times and then dried over Na ₂ SO ₄ . The solvent was distilled off, and the residue was vacuum dried at room temperature to obtain 15.0 g of a colorless transparent liquid fluorinated ether oligomer.

According to the analysis results of ¹ H-NMR, infrared absorption spectrum, and ¹³ C-NMR with a yield of 98%, ^one end having a CF ₃ group and each having an OH group and an OC ₆ H ₅ group at the end. It was found to be a polyether of phenyl ether.

The peak molecular weight by GPC (Shode
x KF-80M x 2) is a polystyrene converted value of 2.
It was 2 × 10 ³ , and Mw / Mn = 1.07 determined by GPC. In addition, Mn calculated from the sum of methine and methylene of ¹ H-NMR and the peak integration ratio of the phenyl group was 7.0 × 1.
0 ² , the average degree of polymerization n of TFPO was 5.4. Further, M obtained from the result of acetylation of OH and quantitative analysis
n was 7.2 × 10 ² . The results are shown in Table 1.

[0037]

[Table 1]

Example 2-3 TFPO was polymerized in the same manner as in Example 1 except that the amounts of KOH and phenol added were changed to those shown in Table 1 to obtain an oligomer. The results are also shown in Table 1.

Example 4 A thermometer, a cooling tube, a dropping funnel and a calcium chloride tube were attached to a dried three-necked flask, and the same procedure as in Example 1 was performed.
2-dimethoxyethane 10 ml and potassium hydroxide 3.8
1 g (59 mmol) was added, 6.0 ml (59 mmol) of benzyl alcohol purified by distillation under reduced pressure was added on a water bath, and the mixture was stirred and mixed. To this, 10.0 ml of the same TFPO as in Example 1 was added from a dropping funnel so that the system temperature became 25-40 ° C. Twenty-three hours after the first addition of TFPO, 65 ml of 1N-HCl was added and stirred to stop the reaction. The reaction product was dissolved in ether, washed with water, an aqueous solution of sodium carbonate and water in this order, further washed with water several times, and then dried over Na ₂ SO ₄ . The solvent was distilled off, and the residue was vacuum dried at room temperature to obtain 17.4 g of a colorless transparent liquid fluorinated ether oligomer.

According to the analysis results of ¹ H-NMR, infrared absorption spectrum and ¹³ C-NMR with a yield of 90%, it has a CF ₃ group and an OH group and an OCH ₂ C ₆ H ₅ group at the ends, respectively. It was confirmed to be a polyether of benzyl ether at one end.

Further, the peak molecular weight by GPC (Shode
x KF-80M x 2) is 8.
It was 3 × 10 ² and Mw / Mn = 1.07. Also, ¹
Mn calculated from the sum of methine and methylene derived from TFPO in H-NMR and the peak integration ratio of the phenyl group was 4.0 × 1.
0 ² , the average degree of polymerization n of TFPO was 2.6. Further, M obtained from the result of acetylation of OH and quantitative analysis
n was 3.8 × 10 ² . The results are shown in Table 2.

[0042]

[Table 2]

Example 5-6 TFPO was polymerized in the same manner as in Example 4 except that the amounts of KOH and benzyl alcohol added were changed to the amounts shown in Table 2.
An oligomer was obtained. The results are also shown in Table 2.

[0044]

INDUSTRIAL APPLICABILITY The present invention has a low molecular weight compound having a trifluoromethyl group in the molecule, a phenyl ether, an alkyl-substituted phenyl ether or an aromatic-substituted alkyl ether at one end and an alcohol at one end. It is a novel fluorine-containing ether oligomer and is useful as a lubricant, a polymeric material modifier, or an intermediate for functional materials. Further, this novel fluorine-containing ether oligomer can be obtained in a high yield by the method of the present invention, and its molecular weight can be freely controlled, so that it has great utility value as a method for obtaining products for various above-mentioned uses.

[Brief description of drawings]

FIG. 1 is a proton NMR spectrum of a fluorinated ether oligomer (A) having a phenyl ether at one end and an OH group at one end according to the present invention.

FIG. 2 ¹³ C of the above fluorine-containing ether oligomer (A)
-NMR spectrum

FIG. 3 is an infrared absorption spectrum of the above fluorine-containing ether oligomer (A).

FIG. 4 is a proton NMR spectrum of a fluorinated ether oligomer (B) of the present invention having a benzyl ether at one end and an OH group at one end.

FIG. 5 C of the above fluorine-containing ether oligomer (B) ¹³
-NMR spectrum

FIG. 6 is an infrared absorption spectrum of the above fluorine-containing ether oligomer (B).

Claims (4)

[Claims] 1. The following formula [1] (In the formula, R ¹ is a phenyl group or an alkyl-substituted phenyl group, m is 0 to 4, and n is 2 to 100 on average.) A fluorine-containing ether oligomer. 2. The fluorine-containing ether oligomer according to claim 1, which is an optically active substance. 3. A trifluoropropylene oxide represented by the following formula [2] in the presence of an alkali metal hydroxide or an alkali metal alkoxide and phenol, an alkyl-substituted phenol or an aromatic-substituted alcohol. 3. The method for producing a fluorinated ether oligomer according to claim 1, wherein the polymerization is terminated and the polymerization is stopped by adding an acid. 4. The amount of alkali or alkoxide used relative to trifluoropropylene oxide is increased when a low molecular weight oligomer is produced, and the amount of alkali or alkoxide used is reduced when a high molecular weight oligomer is produced. The method for producing a fluorine-containing ether oligomer according to claim 3, wherein the molecular weight is controlled by