JPH0623118B2 - Hexafluoropropene oxide oligoether derivative having terminal dimethylcarbinol group and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides the following formula (1): (In the formula, n represents an integer of 1 to 4.) The present invention relates to a novel hexafluoropropene oxide (HFPO) oligoether derivative having a terminal dimethylcarbinol group and a method for producing the same. The compound is a copolymerization component with a polymerizable monomer such as tetrafluoroethylene or vinylidene fluoride, and the heat resistance, chemical stability, non-adhesiveness, water and oil repellency, and melt moldability of a homopolymer of these monomers. The following formula (5) effective for improving (In the formula, n is an integer of 1 to 4.) A synthetic intermediate of a novel HFPO oligoether derivative having a terminal isopropenyl group represented by the following general formula (6) (However, in the formula, n is an integer of 1 to 4 and x is an integer of 0 to 3.) and has excellent heat resistance and low temperature characteristics, water and oil repellency, and antifouling properties with low surface energy. It is useful as a synthetic intermediate for a novel fluorine-containing organosilicon compound.

[Problems to be Solved by Prior Art and Invention]

Traditionally, homopolymers of tetrafluoroethylene and vinylidene fluoride have been widely used in various applications due to their excellent properties, and copolymers copolymerized with various copolymerization components to impart other properties. Although it has found a wide range of fields, it further enhances or imparts the properties of these polytetrafluoroethylene and polyvinylidene fluoride such as heat resistance, chemical stability, non-adhesiveness, water and oil repellency, and melt molding. Is desired.

In addition, ≡Si-O existing on the surface of silica compounded with organic resin, silicone oil compound, silicone rubber, etc.
H-based silica treatment agent, adhesion improver for resists in the production process of various semiconductor devices, surface for imparting water and oil repellency and antifouling property to the glass surface of optical lenses, spectacle lenses, glass appliances, etc. Fluorine-containing organosilicon compound useful as a treatment agent, or good low temperature characteristics, heat resistance,
A novel organopolysiloxane having properties such as water and oil repellency and antifouling property is also desired.

[Means and Actions for Solving the Problems]

The present inventor, as a result of intensive studies to meet the above-mentioned demand, after synthesizing an HFPO oligomer by blowing hexafluoropropene oxide (HFPO) with a metal fluoride-aprotic solvent system, reacting with methanol, and further By reacting a methyl Grignard reagent CH ₃ MgX or by directly reacting the HFPO oligomer with a methyl Grignard reagent, the following formula (1) A novel compound having a terminal dimethylcarbinol group represented by
It has been found that HFPO oligoether derivatives are obtained. And, this compound (1), by dehydrating it, the following formula (5) To obtain a novel HFPO oligoether derivative having a terminal isopropenyl group represented by
(5) is useful for improving the heat resistance, chemical stability, non-adhesiveness, water and oil repellency, melt moldability, etc. of homopolymers of these monomers as a copolymerization component of tetrafluoroethylene and vinylidene fluoride. In addition to discovering that, the compound of formula (5) By reacting a silane represented by (Wherein n is 1 to 4 and x is an integer of 0 to 3), a novel fluorine-containing organosilicon compound is obtained, and the novel compound (6) has reactivity of chlorosilane and properties of fluorocarbon. Is present on the surface of silica compounded with organic resins, silicone oil compounds, silicone rubber, etc. -Based silica treatment agent, adhesion improver for resists in various semiconductor device production processes, surface treatment for imparting water and oil repellency and stain resistance to the glass surface of optical lenses, spectacle lenses, glassware, etc. As well as being effectively used as an agent, it was found that the polysiloxane obtained from the compound has good low-temperature properties, heat resistance, water and oil repellency, and antifouling properties. Was found to be useful as a synthetic intermediate for these novel compounds (5) and (6), and the present invention has been completed.

Therefore, the present invention provides a novel hexafluoropropene oxide oligoether derivative having a terminal dimethylcarbinol group represented by the above general formula (1) and a method for producing the same.

Here, the synthetic scheme of the HFPO oligoether derivative represented by the above formula (1) is as follows.

Oligomerization Esterification Carbinolization First, the oligomerization can be carried out by employing a known method. For example, HFPO of formula (4) is converted to potassium fluoride
(KF), cesium fluoride (CsF) and other metal fluorides-by blowing into an aprotic solvent system at low temperature,
An HFPO oligomeric acid fluoride of the formula (3) can be obtained. In this case, as the aprotic solvent (aprotic polar solvent), for example, diglyme, tetraglyme, tetrahydrofuran (THF), dimethylformamide (DMF), acetonitrile or the like can be used. In addition, for example, in cesium fluoride (CsF) and tetraglyme system, the reaction conditions that maximize the proportion of trimer are:
HFPO / CsF molar ratio 103, CsF / H ₂ O molar ratio 2.83, HFPO feed rate 1.57 g / min, reaction temperature -5 to 0 ° C, reaction time 2
It takes about 16 hours, and the yield is 94 under these reaction conditions.
%, The resulting oligomer distribution is dimer 34%, trimer 5
It is about 2% and tetramer 12%. These oligomeric acid fluorides have a boiling point difference of about 50 ° C. and can be easily separated by rectifying.

In the esterification reaction of (1), the separated oligomeric acid fluoride is dripped into excess methanol under cooling to instantly complete the reaction. Purification / separation can be carried out by pouring into a large excess of water for liquid separation, washing with neutralized water, and distillation.

After the oligomerization of HFPO, this oligomer may be poured into an excess of alcohol, esterified, treated in the same manner, and then rectified to separate into oligomers of the ester of formula (2).

The carbinolation of is carried out by reacting with a Grignard reagent, whereby the
A novel HFPO oligoether derivative (tertiary alcohol) having a terminal dimethylcarbinol group represented by the formula (1) can be obtained.

In this case, the ester of the formula (2) is dissolved in an ethyl ether solution or the like, and this solution is added to the ester of the formula (2) for 2 to 3 times.
1 time, preferably 2.1 to 2.5 times the molar amount of methyl Grignard reagent in a solution prepared in ethyl ether, at a reaction temperature of 0 to
It can be added dropwise at 35 ° C., preferably 20 to 30 ° C., and reacted until the starting ester disappears. When the reaction temperature is 20 to 30 ° C, the reaction is completed in less than 1 hour.

The tertiary alcohol of formula (1) can also be obtained by directly reacting the acid fluoride of formula (3) with a methyl Grignard reagent.

Novel HF with terminal dimethylcarbinol groups of the invention
The PO ether derivative has the following formula (5) (However, n in the formula is an integer of 1 to 4.) It is effective as a synthetic intermediate for a novel HFPO oligoether derivative having a terminal isopropenyl group represented by

To obtain this oligoether derivative of formula (5), the following dehydration reaction In this dehydration reaction, 95% sulfuric acid is used in an amount of 3 to 20 times mol, preferably 4 to 7 times mol, with respect to the tertiary alcohol of the formula (1), and the temperature is 100 to 200 ° C., preferably 130 to The reaction can be performed at 160 ° C. for several hours.

Here, conventionally, the following reaction schemes are known.

′ Carbinol conversion 'dehydration In this case, in the carbinolation reaction of ', a mixed Grignard reagent of methyl and isopropyl is required, and the isopropyl Grignard reagent acting as a reducing agent is required to be 1.5 times or more of the theoretical amount. For the synthesis, the reaction temperature must be controlled sufficiently, and the reaction time also requires a long time of one day or more. Furthermore, in the dehydration reaction of ', it is difficult to dehydrate from the alcohol of (b), and diphosphorus pentoxide and a high temperature of 300 to 400 ° C are required. As described above, the oligoethers (a) and (b) described above have many disadvantages in industrial production, resulting in high production cost.

On the other hand, in the present invention, the novel tertiary alcohol of the present invention can be obtained from the ester of formula (2), but when compared with the conventional case of producing the above-mentioned secondary alcohol of (b), In the production of the tertiary alcohol of the present invention, the isopropyl Grignard reagent is unnecessary, and the reaction temperature can be controlled at room temperature rather than severely, (b)
In the secondary alcohol production, the reaction time is longer than one day and night, whereas in the present invention, the reaction is completed in about 1 hour,
Further, since the tertiary alcohol can be obtained with high selectivity, separation and purification are easy, and therefore, it can be produced very advantageously in industrial production, and the cost can be reduced.

Moreover, the tertiary alcohol of the formula (1) is dehydrated by the following dehydration reaction. However, when dehydrating the conventional secondary alcohol of the formula (b), 3
Although it requires diphosphorus pentoxide at a high temperature of 00 to 400 ° C, it proceeds easily and with high yield by using concentrated concentrated sulfuric acid which is inexpensive at about 150 ° C. The novel oligoether of HFPO having a terminal isopropenyl group can be produced industrially advantageously and is low in cost.

A novel HFPO oligoether having a terminal isopropenyl group represented by the above formula (5) is copolymerized with a homopolymerizable monomer such as tetrafluoroethylene or vinylidene fluoride, and the heat resistance of a homopolymer of these monomers. The chemical stability, non-adhesiveness, water and oil repellency, etc. can be maintained and melt molding can be facilitated.

Also, with the compound of formula (5) By a hydrosilylation reaction with a silane represented by the following general formula (6) (Wherein n is 1 to 4 and x is an integer of 0 to 3), a novel fluorine-containing organosilicon compound is obtained.

In this hydrosilylation reaction, chlorosilane was used in an amount of 1.1 to 1.5 times the molar amount of the compound of the formula (5) in the autoclave and 1 × 10 ^{−5 to} 5 × 10 ⁻³ moles of the platinum catalyst was used. It is preferred to react for ~ 5 days.

This fluorine-containing compound has both the reactivity of chlorosilane and the properties of fluorocarbon, and is present on the surface of silica compounded in organic resins, silicone oil compounds, silicone rubber, etc. -Based silica treatment agent, adhesion improver for resists in various semiconductor device production processes, surface treatment for imparting water and oil repellency and stain resistance to the glass surface of optical lenses, spectacle lenses, glassware, etc. In addition to being effectively used as an agent, the polysiloxane obtained from the compound also has good low-temperature characteristics, and has heat resistance, water / oil repellency, and antifouling properties.

〔The invention's effect〕

As described above, the novel hexafluoropropene oxide oligoether derivative having a terminal dimethylcarbinol group of the present invention is a novel hexafluoropropene group having a terminal isopropenyl group having a useful use represented by the above formula (5). Useful as a synthetic intermediate for oxide oligoether derivatives, and also as a synthetic intermediate for a novel fluorine-containing organosilicon compound having a useful use represented by formula (6) obtained by hydrosilylating the oligoether represented by formula (5) Is.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 In a dry four-necked flask having an inner volume of 3, 36 g (1.5 mol) of shaving magnesium and 20 parts of dried ethyl ether were added.
After charging 0 m, methyl iodide (CH ₃
I) 230 g (1.5 mol) of ethyl ether (300 m)
The solution was added dropwise at a rate of slow reflux over about 4 hours.

Then, after placing this flask in an ice bath and cooling, the following formula 302 g of ester represented by (purity 97%, 0.59 mol)
Of ethyl ether (500 m) was added dropwise from the dropping funnel over 1 hour while maintaining the temperature of the reaction solution at 10 to 20 ° C., and the mixture was further stirred at about 10 ° C. for 1 hour.

Next, the reaction solution was poured into 500 m of cold saturated ammonium chloride, and the solution was acidified with 5N-hydrochloric acid. The lower organic layer of the reaction solution separated into layers was separated, the upper aqueous layer was extracted twice with ethyl ether, and this was combined with the organic layer, and the organic layer was saturated sodium hydrogen carbonate and saturated saline. Was washed in this order and then dried over magnesium sulfate.

Then, the solvent was distilled off, and the obtained reaction product was distilled under reduced pressure to obtain a fraction represented by the following formula at a boiling point of 84 to 85 ° C./32 mmHg. 245 g of tertiary alcohol (purity 97%, yield 79%) was obtained.

This tertiary alcohol was subjected to elemental analysis and GC-MS analysis, and infrared absorption spectrum and ¹ H-NMR spectrum were measured. The results are shown below.

Elemental analysis: GC-MS: m / e (M ⁺ ) molecular weight 510 Infrared spectrum: A chart is shown in FIG. Wavenumber 3640,3 from this chart
A peak derived from the —OH group was observed at 470 cm ⁻¹ . ¹ H-NMR spectrum: Solvent: DMSO-d ₆ / CCl ₄ Internal standard: TMS δ (ppm): 4.27 (s, 1H, -OH) 2.70 (s, 6H, 2 × CH ₃ ) [Reference Example 1] Contents A simple distillation set was assembled in a flask having a volume of 0.5, and 158 g (0.30 mol) of the above tertiary alcohol was added to the flask.
200 g (1.94 mol) of 95% strength sulfuric acid and 0.25 g of t-butylhydroquinone (TBHQ) as a polymerization inhibitor were charged and stirred at 150 ° C. for 4 hours, and then organic substances were distilled off under reduced pressure at the same temperature.

The distilled organic layer was washed with saturated sodium hydrogen carbonate and then with saturated saline, and magnesium sulfate was added to dry it.

This organic layer was distilled to obtain the following formula as a fraction at a boiling point of 147 to 148 ° C. 128 g (yield 85%) of the alkene represented by

This alkene was subjected to elemental analysis and GC-MS analysis, and infrared absorption spectrum and ¹ H-NMR spectrum were measured. The results are shown below.

Elemental analysis: GC-MS: m / e ( M +) molecular weight 492, M-19 473 Infrared spectrum: peaks of 3640,3470Cm ^-1 derived from the OH group disappears, a peak newly based on 1660 cm ^-1 to C = C is It was observed to have occurred. ¹ H-NMR spectrum: Solvent: CCl ₄ Internal standard: TMS δ (ppm): 5.30-5.70 (m, 2H, = CH ₂ ) 1.93 (s, 3H, CH ₃ ) Further, in an autoclave, the above alkene 87.4 g ( 0.178 mol), trichlorosilane 35.0 g (0.25 mol) and n-butanol modification catalyst of chloroplatinic acid (platinum concentration 2.0 wt%) 1.5
0 g (1.50 × 10 ⁻⁴ mol) was mixed and reacted at 110 ° C. for 64 hours (40% conversion by GLC, selectivity 85%). After the reaction is completed, first, atmospheric distillation is performed and the boiling point is 145 to 148 ° C.
44.6 g (alkene of the starting material) was obtained and then distilled under reduced pressure to obtain 40.4 g (yield 36%) of a compound represented by the following formula as a fraction having a boiling point of 86 to 88 ° C./8 mmHg.

The obtained compound was subjected to elemental analysis and GC-MS analysis, and the infrared spectrum and ¹ H-NMR spectrum of this compound were measured. The following results were obtained.

Elemental analysis: GC-MS: m / e 627 (M ⁺ ) IR spectrum: The peak at 1660 cm ^-1 derived from C = C disappeared. ¹ H-NMR spectrum: solvent; CCl ₄ internal standard: TMS δ (ppm); 5.33 (m, 1H, CH), 3.50 (m, 2H, CH ₂ ) 2.70 (m, 3H, CH ₃ ) [Example 2 ] The following formula A solution of 104 g (0.30 mol) of the ester represented by is dissolved in 150 m of ethyl ether to obtain 18 g of magnesium.
(0.75 mol), 115 g (0.75 mol) of methyl iodide, and 150 m of ethyl ether were added dropwise to a CH ₃ MgI solution prepared in the same manner as in Example 1 and reacted for 2 hours at room temperature,
The same treatment and purification as in Example 1 were carried out.

Next, the obtained reaction product is distilled to give a boiling point of 133 to 13
The following formula for the fraction at 5 ° C 84 g (yield 81%) of the tertiary alcohol represented by

This tertiary alcohol was subjected to elemental analysis and GC-MS analysis, and infrared absorption spectrum and ¹ H-NMR spectrum were measured. The results are shown below.

Elemental analysis: GC-MS: m / e (M ⁺ ) 344 Infrared absorption spectrum: A chart is shown in FIG. 3650, 3450c from this chart
A peak derived from —OH was measured at m ⁻¹ . ¹ H-NMR spectrum: Solvent: CCl ₄ Internal standard: TMS δ (ppm): 2.47 (s, 1H, OH) 1.40 (s, 6H, 2 × CH ₃ ) [Reference Example 2] The same apparatus as Reference Example 1 With sulfuric acid of 95% concentration 250
82 g of the tertiary alcohol obtained above to g (2.42 mol)
(0.24 mol) was added, and the mixture was vigorously stirred at 110 to 120 ° C for 5 hours. Then, after distilling, washing, and drying in the same manner, the obtained reaction product is distilled to obtain a fraction represented by the following formula at a boiling point of 96 ° C. 2-methyl-3-trifluoromethyl-4-
Oxa-3,5,5,6,6,7,7,7-octafluoropentene-
173 g (yield 93%) was obtained.

This compound was subjected to elemental analysis and GC-M in the same manner as in Example 1.
S analysis, infrared absorption spectrum and ¹ H-NM
The R spectrum was measured. The results are shown below.

Elemental analysis: GC-MS: m / e ( M +) 326 IR absorption spectrum: peaks of 3650,3450Cm ^-1 derived from the OH group disappears, newly it is observed that peak based on the C = C to 1660 cm ^-1 is generated Was done. ¹ H-NMR spectrum: Solvent: CCl ₄ Internal standard: TMS δ (ppm): 5.30-5.60 (m, 2H, = CH ₂ ) 1.90 (s, 3H, CH ₃ ) Further obtained in autoclave above Compound 65g
(0.20 mol), 35 g (0.25 mol) of trichlorosilane and 0.90 g (9.2 × 10 ⁻⁵ mol) of an n-butanol modification catalyst of chloroplatinic acid (platinum concentration 2.0 wt%) were mixed, and the mixture was heated at 110 ° C.
The reaction was performed for 64 hours (GLC conversion 92%, selectivity 98
%). After the reaction is completed, first, atmospheric distillation is carried out to have a boiling point of 93 to 9
After obtaining 22.0 g of a fraction at 8 ° C. (alkene as a raw material) and then performing vacuum distillation, 47.8 g (yield 50%) of a compound represented by the following formula was obtained as a fraction at a boiling point of 66 to 67 ° C./10 mmHg.

The obtained compound was subjected to elemental analysis and GC-MS analysis, and the infrared spectrum and ¹ H-NMR spectrum of this compound were measured. The following results were obtained.

Elemental analysis: GC-MS: m / e 461 (M ⁺ ) IR spectrum: The peak at 1660 cm ^-1 derived from C = C disappeared. ¹ H-NMR spectrum: solvent; CCl ₄ internal standard; TMS

[Brief description of drawings]

1 and 2 are infrared absorption spectra of the target compounds of Examples 1 and 2, respectively.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08F 299/00 MRS 7442-4J (72) Inventor Shinichi Sato 2-13-1 Isobe, Annaka-shi, Gunma Shin-Etsu Kagaku Kogyo Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Masayuki Oyama 2-13-1, Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (3)

[Claims] 1. The following formula (1) (In the formula, n represents an integer of 1 to 4.) A hexafluoropropene oxide oligoether derivative having a terminal dimethylcarbinol group represented by: 2. The following formula (2) (Wherein n represents an integer of 1 to 4) and a methyl Grignard reagent are reacted to produce a derivative represented by the formula (1) according to claim 1. A method for producing a hexafluoropropene oxide oligoether derivative having a dimethylcarbinol group. 3. The following formula (3) (Wherein, n represents an integer of 1 to 4) and an oligomeric acid fluoride represented by the following formula is reacted with a methyl Grignard reagent to produce a derivative represented by the formula (1). And a method for producing a hexafluoropropene oxide oligoether derivative having a terminal dimethylcarbinol group.