JPH0623121B2 - Hexafluoropropene oxide oligoether derivative having terminal isopropenyl 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 is an integer of 1 to 4.) A novel hexafluoropropene oxide (HFPO) oligoether derivative having a terminal ylpropenyl group represented by: and a method for producing the same. The compound, as a copolymerization component with a polymerizable monomer such as tetrafluoroethylene or vinylidene fluoride, is heat-resistant, chemically stable, non-adhesive, water- and oil-repellent, melt-molded by a homopolymer of these monomers. It is effective for improving the sex. Also, the following 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- present on the surface of silica compounded with organic resin, silicone oil compound, silicone rubber, etc.
OH-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 the Grignard reagent CH ₃ MgX, the following formula (2) A novel compound having a terminal dimethylcarbinol group represented by
By obtaining an HFPO oligoether derivative and further dehydrating it, the following formula (1) It was found that a novel HFPO oligoether derivative having a terminal isopropenyl group represented by is obtained.

And, this novel compound (1), tetrafluoroethylene, as a copolymerization component of vinylidene fluoride, heat resistance of the homopolymerization polymer of these monomers, chemical stability,
It has been found that it is useful for improving non-adhesiveness, water and oil repellency, melt moldability and the like.

Furthermore, the compound of formula (1) By reacting a silane represented by
(6) (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. While being effectively used as an agent, on the other hand, it was found that the polysiloxane obtained from the compound has good low-temperature properties, heat resistance, water and oil repellency, and antifouling properties. The compound of formula is (6)
The inventors have found that the compound of the formula is also effective as a synthetic intermediate, and have completed the present invention.

Accordingly, the present invention provides a novel hexafluoropropene oxide oligoether derivative having a terminal isopropenyl 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 dehydration First, the oligomerization can be carried out by employing a known method. For example, HFPO of formula (5) 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 (4) 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) / tetraglyme system, the reaction condition that maximizes the proportion of trimer is
HFPO / CsF molar ratio 103, CsF / H ₂ O molar ratio 2.83, HFPO
At a feed rate of 1.57 g / min, a reaction temperature of -5 to 0 ° C., and a reaction time of about 216 hours.
The distribution of the produced oligomers is about 34%, the dimers are 34%, the trimers are 52%, and the tetramers are 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 performed by pouring into a large excess of water for liquid separation, neutralization, washing with water, and distillation.

After the oligomerization of HFPO, the oligomer may be poured into excess alcohol, esterified, treated in the same manner, and then rectified to separate each oligomer of the ester of formula (3).

The carbinolation of is carried out by reacting a Grignard reagent, whereby a novel tertiary alcohol of the formula (2) can be obtained.

In this case, the ester of the formula (3) is dissolved in an ethyl ether solution or the like, and this solution is added to the ester of the formula (3) 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 the formula (2) can be obtained by directly reacting the acid Grignard reagent of the formula (4) with a methyl Grignard reagent.

The dehydration of (3) dehydrates the tertiary alcohol of the formula (2), and the target compound of the present invention of the formula (1) is synthesized by this dehydration reaction. 95% sulfuric acid 3 to 20 times mol, preferably 4 to 7 times mol, temperature 100 to 200 ° C, preferably 130 to 160 ° C
The reaction can be carried out for several hours under the conditions described above.

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, from the ester of the formula (3),
Although a primary alcohol can be obtained, the tertiary alcohol according to the present invention does not require an isopropyl Grignard reagent and the reaction temperature is higher than that in the conventional production of the secondary alcohol (b). Can be carried out at room temperature rather than severely, and the reaction time of the secondary alcohol production of (b) requires one day or more, whereas in the present invention, the reaction is completed in about 1 hour, and Since the tertiary alcohol can be obtained with good efficiency, separation and purification are easy, and therefore, the production can be very advantageous in industrial production, and the cost can be reduced.

Moreover, the tertiary alcohol of the formula (2) is the following dehydration reaction. However, when dehydrating the conventional secondary alcohol of the formula (b), 3
While it requires diphosphorus pentoxide at a high temperature of 00 to 400 ° C., it proceeds easily and in high yield by using inexpensive concentrated sulfuric acid at about 150 ° C.
The novel oligoether of HFPO having the terminal isopropenyl group of the formula (1) can be produced industrially advantageously and is low in cost.

The novel HFPO oligoether having a terminal isopropenyl group of the present invention is copolymerized with a homopolymerizable monomer such as tetrafluoroethylene or vinylidene fluoride, and the heat resistance and chemical stability of the homopolymer of these monomers. , Non-adhesiveness, water repellency and oil repellency can be maintained, and melt molding can be facilitated.

Also, with the compound of formula (1) 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 is used in an autoclave in an amount of 1.1 to 1.5 times the amount of the compound of the formula (1), and platinum catalyst of 1 × 10 ^{−5 to} 5 × 10 ⁻³ moles is used.
It is preferable to react at 80 to 150 ° C. for 1 to 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 properties, 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 isopropenyl group represented by the formula (1) of the present invention is a low-cost novel oligoether derivative which can be industrially produced advantageously. In addition to having a wide range of uses per se, it is also useful as a synthetic intermediate for the novel fluorine-containing organosilicon compound represented by the above formula (6).

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 internal volume of 3, 36 g (1.5 mol) of shaving magnesium and 2 parts of dried ethyl ether were added.
After charging 00 ml, methyl iodide (CH ₃
I) 230 g (1.5 mol) of ethyl ether (300 ml)
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 302g of ester (purity 97%, 0.59mol)
While maintaining the temperature of the reaction solution at 10 to 20 ° C, the ethyl ether (500 ml) solution of was added dropwise from the dropping funnel over 1 hour, and further stirred at about 10 ° C for 1 hour.

Next, the reaction solution was poured into 500 ml 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: peaks derived from the —OH group were observed at wave numbers 3640 and 3470 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 ) Then, with an internal volume of 0.5 Assemble the simple distillation set in the flask, and put 158 g (0.30
Mol), 200 g (1.94 mol) of 95% strength sulfuric acid and 0.25 g of t-butyl hydroquinone (TBHQ) as a polymerization inhibitor.
Was charged, and the mixture was stirred at 150 ° C. for 4 hours, and then organic matter was 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

The 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 absorption spectrum: A chart is shown in FIG. From the chart in Fig. ¹ , the peaks at 3640 and 3470 cm ^-1 originating from the OH group disappeared, and a new 1660c
It was observed that there was a peak at m ^-1 based on C = C. ¹ H-NMR spectrum: Solvent: CCl ₄ Internal standard: TMS δ (ppm): 5.30 to 5.70 (m, 2H, = CH ₂ ) 1.93 (s, 3H, CH ₃ ) [Reference Example 1] The above alkene in an autoclave 87.4 g (0.178 mol),
Trichlorosilane 35.0 g (0.25 mol) and chloroplatinic acid n-butanol modification catalyst (platinum concentration 2.0% by weight) 1.50 g
(1.50 × 10 ⁻⁴ mol) were mixed and reacted at 110 ° C. for 64 hours (GLC conversion 40%, selectivity 85%). After completion of the reaction, first, atmospheric distillation was carried out to obtain 44.6 g of a fraction having a boiling point of 145 to 148 ° C (alkene as a raw material), and then distillation under reduced pressure was carried out, and a fraction having a boiling point of 86 to 88 ° C / 8 mmHg was represented by the following formula 40.4 g (yield 36%) of the compound was obtained.

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 obtained by dissolving 104 g (0.30 mol) of the ester represented by in 150 ml of ethyl ether was added with 18 g of magnesium.
(0.75 mol), 115 g (0.75 mol) of methyl iodide and 150 ml 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 peak derived from -OH was measured at 3650 and 3450 cm ^-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 ) Then, using the same apparatus as in Example 1, To 250 g (2.42 mol) of 95% sulfuric acid was added 82 g (0.24 mol) of the tertiary alcohol obtained above, and the mixture was vigorously stirred at 110 to 120 ° C for 5 hours. Next, after distilling, washing and drying in the same manner, the obtained reaction product is distilled to obtain a boiling point of 9
The following formula for the fraction at 6 ° 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-in the same manner as in Example 1.
MS analysis, infrared absorption spectrum and ¹ H-
The NMR spectrum was measured. The results are shown below.

Elemental analysis: GC-MS: m / e (M ⁺ ) 326 Infrared absorption spectrum: A chart is shown in FIG. Derived from this chart OH groups 3650,3450cm peaks ^-1 disappeared, new 1660 cm ^-1
It was observed that a peak based on C = C was generated at. ¹ H-NMR spectrum: Solvent: CCl ₄ Internal standard: TMS δ (ppm): 5.30 to 5.60 (m, 2H, = CH ₂ ) 1.90 (s, 3H, CH ₃ ) [Reference Example 2] In the autoclave, above 65 g (0.20 mol) of the obtained compound, 35 g (0.25 mol) of trichlorosilane and an n-butanol modification catalyst of chloroplatinic acid (platinum concentration 2.0% by weight)
Mix 0.90 g (9.2 x 10 ^-5 mol) and mix at 110 ° C for 64
Reaction was carried out for a time (GLC conversion 92%, selectivity 98
%). After completion of the reaction, first, atmospheric distillation is carried out to give a boiling point of 93 to 98.
After obtaining 22.0 g of a distillate at a temperature of ℃ (alkene as a raw material) and then performing vacuum distillation, 47.8 g of a compound of the following formula (yield 50%) was obtained as a distillate 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 δ (ppm); 5.66 (m, 1H, ), 3.80 (m, 2H, CH ₂ =), 2.83 (m, 3H, CH ₃ )

[Brief description of drawings]

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

Claims (2)

[Claims] 1. The following formula (1) (In the formula, n is an integer of 1 to 4.) A hexafluoropropene oxide oligoether derivative having a terminal isopropenyl group represented by: 2. The following formula (2) (In the formula, n represents an integer of 1 to 4.) A hexafluoropropene oxide oligoether derivative having a terminal dimethylcarbinol group represented by the formula is dehydrated to obtain the derivative represented by the formula (1). A process for producing a hexafluoropropene oxide oligoether derivative having a terminal isopropenyl group, which comprises: