JPH02311439A - Hexafluoropropene oxide oligoether derivative having isopropenyl group on terminal and its production - Google Patents

Abstract

NEW MATERIAL:The hexafluoropropene oxide oligoether derivative having terminal isopropenyl group and expressed by formula I (n is 1 to 4). EXAMPLE:The compound of formula II. USE:Useful as a component to be copolymerized with a polymerizable monomer such as tetrafluoroethylene or vinylidene fluoride to improve the heat-resistance, chemical stability. non-tackiness, water and oil-repellency, melt-formability, etc., of the homopolymer of the above monomer. It is also useful as a synthetic intermediate for a novel fluorine-containing organic silicon compound expressed by formula II and having excellent heat resistance, low temperature characteristics and stainproofing property such as water and oil repellency and low surface energy. PREPARATION:The compound of formula I can be produced by dehydrating a hexafluoropropene oxide oligoether derivative having terminal dimethylcarbinol group and expressed by formula III. The dehydration reaction is carried out at 100-200 deg.C in the presence of snlfuric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a terminal group represented by the following formula (1) % formula % (1) (where n is an integer from 1 to 4). The present invention relates to a novel hexafluoropropenoxide (HFPO) oligoether derivative having a propenyl group and a method for producing the same. The compound is used as a copolymerization component with polymerizable polymers such as tetrafluoroethylene and vinylidene fluoride to improve the heat resistance, chemical stability, non-adhesiveness, water and oil repellency of homopolymer polymers of these polymers. , is effective for improving melt moldability and the like. In addition, the following formula (
6) (However, in the formula, n is an integer of 1 to 4, and It is useful as an intermediate for the synthesis of novel fluorine-containing organosilicon compounds having specific properties.

[Prior art and problems to be solved by the invention] Conventionally, homopolymers of tetrafluoroethylene and vinylidene fluoride have been widely used for various purposes due to their excellent properties, and they have also been used to impart other properties. Copolymers copolymerized with various copolymer components have found a wide range of applications, but in addition, the heat resistance, chemical stability, non-adhesiveness,
It is desired to enhance or impart properties such as water and oil repellency and further melt moldability.

In addition, silica present on the surface of organic resins, silicone oil compounds, silicone rubber, etc.
-OH group silica treatment agent, adhesion improver for resists etc. in the production process of various semiconductor devices, optical lenses,
A fluorine-containing organosilicon compound useful as a surface treatment agent for imparting water repellency, tΩ oil resistance, and stain resistance to the glass surfaces of eyeglass lenses, glassware, etc., or a fluorine-containing organosilicon compound with good low temperature properties, heat resistance, and 18 water tθ oil resistance. There is also a demand for new organopolysiloxanes having properties such as antifouling and antifouling properties.

[Means and effects for solving the problem] In order to meet the above-mentioned demands, the present inventor conducted intensive studies and found that hexafluoropropene oxide (HFPO) is a metal fluoride.
By injecting with abrotix solvent system) I
After synthesizing the FPO oligomer, methanol is reacted, and Grignard reagent C)1. By reacting with MgX, a novel HFPO oligoether derivative having a terminal dimethyl carbinol group represented by the following formula (2)% can be obtained; further, by dehydrating this, the following formula ( 1) A novel HFP having a terminal isopropenyl group represented by the formula %(11)
It has been found that O oligoether derivatives can be obtained.

This new compound (11) is a copolymerization component of tetrafluoroethylene and vinylidene fluoride. It was found that this method is useful for improving etc.

Furthermore, by reacting this compound of formula (1) with a silane represented by (C)Iz) This novel compound (6) has both the reactivity of chlorosilane and the properties of fluorocarbon, and is suitable for organic resins and silicone oil compounds. and EES+ OH group silica treatment agent present on the silica surface blended into silicone rubber, etc.
Effectively used as an adhesion improver for resists, etc. in the production process of various semiconductor devices, and as a surface treatment agent to impart 18 water, T8 oiliness and antifouling properties to the glass surfaces of optical lenses, eyeglass lenses, glassware, etc. On the other hand, it was found that the polysiloxane obtained from the compound has good low-temperature properties, heat resistance, water repellency, oil repellency, and stain resistance. ) It was discovered that the compound is also effective as a synthetic intermediate for the compound of the formula, and the present invention was completed.

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

(1) Oligomerization (5101FPO) (5101FPO) (5101FPO) (5101FPO) (2) Esterification (2) Carbinolization F-(CFChO)-CF-C-CH3 (2) Dehydration First, the oligomerization (3) can be carried out using known methods. For example, by blowing the HFPO of (5) 2 into a metal fluoride-abrotic solvent system such as potassium fluoride (KF) or cesium fluoride (CsF) at low temperature, the formula 〇〇PPO oligomer of (4) Acid fluoride proboscis can be obtained. In this case, examples of the aprotic solvent (aprotic polar solvent) include diglyme, tetraglyme, and tetrahydrofuran (THF).
), dimethylformamide (DMF), acetonitrile, etc. can be used. For example, in the case of cesium fluoride (CsF)/tetraglyme system, the reaction conditions that maximize the proportion of trimers are liver PO/Cs
Molar ratio of F 103, molar ratio of CsF/1lzo 2.83
, HFPO supply rate 1.57 g/min, reaction temperature -5 to 0°C, reaction time about 216 hours. Under these reaction conditions, the yield was 94%, the oligomer distribution was 34% dimer, The proportion is about 52% trimer and 12% tetramer. These oligomeric acid fluorides have a boiling point difference of about 50° C. and can be easily separated by rectification.

The esterification reaction (2) is completed instantly by dropping the separated oligomeric acid fluoride into excess methanol under cooling. Purification and separation can be carried out by pouring into a large excess of water to separate the liquid, neutralizing it, washing it with water, and then distilling it.

Note that, after oligomerization of IFPO, the oligomers can be poured into excess alcohol to be esterified, treated in the same manner, and then rectified to separate the oligomers of the esters of formula (3).

The carbinolization ((2)) is carried out by reacting with a Grignard reagent, and thereby a novel tertiary alcohol of formula (2) can be obtained.

In this case, dissolve the ester of formula (3) in an ethyl ether solution, etc., and add this solution to the ester of formula (3).
3 times, preferably 2.1 to 2.5 times the molar amount of methyl Grignard reagent is added dropwise to a solution prepared in ethyl ether at a reaction temperature of 0 to 35°C, preferably 20 to 30°C,
The reaction can be continued until the raw ester disappears. At a reaction temperature of 20-30°C, the reaction is completed in less than 1 hour.

Note that the tertiary alcohol of formula (2) can also be obtained by directly reacting the acid fluoride of formula (4) with a methyl Grignard reagent.

Dehydration (2) is to dehydrate the tertiary alcohol of formula (2), thereby synthesizing the target compound of the present invention of formula (1). In this dehydration reaction, the tertiary alcohol of formula (2) is using 3 to 20 times the mole, preferably 4 to 7 times the mole of 95% sulfuric acid, at a temperature of 100 to 200°C, preferably at 130°C.
The reaction can be carried out at a temperature of ~160°C for several hours.

Here, the following reaction scheme is conventionally known.

■'Carbinolization 0H ■'Dehydration (a) In this case, the carbinolization reaction of ■' requires a mixed Grignard reagent of methyl and isopropyl, and moreover, the isopropyl Grignard reagent acting as a reducing agent has a theoretical amount of 1. In addition, in order to selectively synthesize the desired product, the reaction temperature must be sufficiently controlled, and the reaction time also requires a long time, lasting more than one day and night. Furthermore, in the dehydration reaction of
Requires high temperatures. In this way, the above (al, (b
) oligoethers have many disadvantages in industrial production, leading to high production costs.

In contrast, in the present invention, from the ester of formula (3) to (2)
A tertiary alcohol of the formula can be obtained, but compared to the conventional case of producing a secondary alcohol of the above-mentioned (bl), the tertiary alcohol according to the present invention does not require an isopropyl Grignard reagent, and The reaction temperature is not strictly controlled and can be carried out at room temperature (while the production of BL secondary alcohol requires a reaction time of more than one day and night, in the present invention the reaction is completed in about one hour; Since a tertiary alcohol can be obtained with good selectivity, separation and purification is easy, and therefore, it can be produced very advantageously in industrial production, and costs can be reduced.

Moreover, the tertiary alcohol of formula (2) undergoes the following dehydration reaction:
When dehydrating the conventional secondary alcohol of formula ('b), 3
The process of the present invention can be carried out easily and in high yield using inexpensive concentrated sulfuric acid at about 1,50°C, whereas it requires niline pentoxide at a high temperature of 00 to 400°C. (A novel HFP with a terminal isopropenyl group of formula 11
Oligoethers of O can be produced industrially advantageously and at low cost.

Novel HFPO with terminal isopropenyl group of the present invention
The oligoether is copolymerized with homopolymerizable monomers such as tetrafluoroethylene and vinylidene fluoride, and
The heat resistance and chemical stability of homopolymers of these monomers,
It maintains non-stick properties, 1Ω water and oil repellency, and can be easily melt-molded.

Moreover, this compound of formula (1) and (CH,).

)I5iC1:+-x By performing a hydrosilylation reaction with the silane represented by The novel fluorine-containing organosilicon compound shown below is obtained.

This hydrosilylation reaction is carried out using the formula (1) in an autoclave.
1.1 to 1.5 times the mole of chlorosilane is used with respect to the compound of
It is preferable to use molar amount and 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 used as a silica treatment agent with esiOH groups present on the silica surface that is blended into organic resins, silicone oil compounds, silicone rubber, etc., and various semiconductor devices. It is also effectively used as an adhesion improver for resists, etc. in the production process of products, and as a surface treatment agent for imparting water repellency, F8 oiliness, and stain resistance to the glass surfaces of optical lenses, eyeglass lenses, glassware, etc. On the other hand, polysiloxanes obtained from acid compounds have good low-temperature properties, as well as heat resistance, water and oil repellency, and stain resistance.

〔Effect of the invention〕

As explained above, the novel hexafluoropropene oxide oligoether derivative having a terminal isopropenyl group represented by formula (1) of the present invention is a novel low-cost oligoether derivative that can be industrially advantageously produced. ,
In addition, it not only has a wide range of uses in itself, but also the above (6)
) It is also useful as a synthetic intermediate for the novel fluorine-containing organosilicon compound represented by the formula.

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

[Example 1] After charging 36 g (1.5 mol) of magnesium shavings and 200 g of dried ethyl ether into a dry four-loaf flask with an internal volume of 31, methyl iodide (
C) A solution of 230 g (<1.5 mol) of 1,1) in ethyl ether (3001n1) was added dropwise at a rate of slow reflux over about 4 hours.

Next, this flask was placed in an ice bath and after cooling, 302 g (purity 97%, 0.59 mol) of ester represented by the following formula % was dissolved in ethyl ether (500 m2). fl While maintaining the temperature of the entire reaction solution at 10 to 20°C, it 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 made acidic with 5N hydrochloric acid.

Of the reaction solution separated into layers, the lower organic layer was separated, the upper aqueous layer was extracted twice with ethyl ether, this was combined with the organic layer, and the organic layer was extracted with saturated sodium bicarbonate,
The mixture was washed with saturated brine and then dried over magnesium sulfate.

Next, the solvent was distilled off, and the resulting reaction product was distilled under reduced pressure to obtain 245 g of tertiary alcohol with a boiling point of 84 to 85° C./32 mL of 11 g of the following formula: 245 g of tertiary alcohol with a concentration of 97%.

A yield of 79% was obtained.

Elemental analysis and GC-MS analysis were performed on this tertiary alcohol, and infrared absorption spectrum and 'I(-
NMR spectra were measured. The results are shown below.

Elemental analysis: CHF calculated value -%) 25.90 1.38 63
．． 31 Actual value (%) 25.58 1.41
Calculated value as 63.02 CzF+JJi GC-MS: m/e (M') Molecular weight 510 Infrared spectrum: A peak derived from -0) 1 group was observed at a wave number of 3640.3470 cm.

'H-NMR spectrum: Solvent: DMSO-db/CCl4 Internal standard:
TMSδ (ppm): 4.27 (s, IH,
-01 l) 2.70 (s, 611,2
0 mol), 200 g (1,94 mol) of 95% strength sulfuric acid
and monobutylhydroquinone (TB) as a polymerization inhibitor.
tlQ) 0.25 g was charged and stirred at 150°C for 4 hours, and then the 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 brine, and then dried by adding magnesium sulfate.

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

Elemental analysis and GO-MS analysis were performed on this alkene, and infrared absorption spectrum and l) I-NMR
The spectrum was measured. The results are shown below.

Elemental analysis: CHF Calculated value ″(%) 26°85 1.02 65.6
3 Actual value (%) 26.59 1.08 6
Calculated value GC- as 5.51 rate CIIF17850□
IIs: m/e (M') molecule 1492. M-19473 infrared absorption spectrum: A chart is shown in FIG. From the chart in Figure 1, 014
It was observed that the peak at 3640.3470 cm-' derived from the group disappeared, and a new peak based on C=C appeared at 1660 cm-'.

'H-NMR spectrum: Solvent: CCI! 4 Internal standard: TMSδ (21m
) 2 5.30-5.70 (m, 2H,"'C
Hz) 1.93 (s, 3H, CI,) C Reference Example I] In an autoclave, 87.4 g (0,1
78 mol), trichlorosilane 35.0 g (O425
1.50 g (1,50XIO
-'mol) were mixed and reacted at 110°C for 64 hours (
(conversion rate 40%, selectivity 85% by GLC).

After the reaction is complete, first distill at atmospheric pressure to obtain a boiling point of 145-148.
44.6g of a fraction (alkene as a raw material) was obtained and then distilled under reduced pressure. As a result, 40.4g of a compound represented by the following formula was obtained as a fraction with a boiling point of 86-88°C/8 mHg (yield: 3
6%) was obtained.

CF: +CFzChOCFChOCF CHC1(z
The obtained compound of SiC7!3 was subjected to elemental analysis and GC-
When this compound was subjected to MS analysis and the infrared spectrum and 'H-NMR spectrum were measured, the following results were obtained.

Elemental analysis: C110IF Calculated value゛(%) 21.05 0.96 16.95
51.46 Actual value (%) 2'2.21 0.89
16.52 51.30 CzCl 3F17H60
□Calculated value as Si GC-MS: m/e 6
27(M'') IR spectrum; The peak at 1660<em>-' derived from C=C disappeared.

'H-NMR spectrum: Solvent i CCl a Internal standard*: TMSδ (pp
m) ; 5.33 (m, IH, CH), 3.5
0(m, 2H, C) 12) 2.70(m, 38.CH3
) [Example 2] A solution obtained by dissolving 104 g (0.30 mol) of the ester represented by the following formula % in 150 mf of ethyl ether was mixed with 18 g (0.75 mol) of magnesium and 115 g of methyl iodide ( 0
, 75 mol) into a ClC11J solution prepared in the same manner as in Example 1 using 150mj' of ethyl ether,
After reacting at room temperature for 2 hours, it was treated and purified in the same manner as in Example 1.

Next, the obtained reaction product was distilled and the boiling point was 133-13
84 g (yield: 81%) of a tertiary alcohol represented by the following formula % (3) was obtained as a fraction at 5°C.

Elemental analysis and GC-MS analysis were performed on this tertiary alcohol, and infrared absorption spectrum and 'H-
NMR spectra were measured. The results are shown below.

Elemental analysis: CHF calculated trade%) 27.92 2.05 60
．． 72 Actual value (%) 27.51 2.01
60.58* CaFzl (calculated value G as 70□
C-MS: m/e (M'') 344 Infrared absorption spectrum: A peak derived from -OH was measured at 3650.3450 cm-'.

'H-NMR spectrum: Solvent: CC1, Internal standard: l: TMSδ (ppm)
: 2.47 (s, LH, 0H) 1.40 (s, 6
H,2xCII:+) Then, using the same apparatus as in Example 1, 82 g (0.24 mol) of the tertiary alcohol obtained above was added to 2.50 g (2.42 mol) of 95% strength sulfuric acid.
was added and strongly stirred at 110 to 120°C for 5 hours.Then, after distillation, washing, and drying in the same manner, the obtained reaction product was distilled, and the following formula was obtained as a fraction at a boiling point of 96°C. 2-Methyl-3-trifluoromethyl-4- with the formula %
173 g (yield: 93%) of oxa-3,5,5,6,6,7,7,7-octafluoropentene was obtained.

This compound was subjected to elemental analysis and GC in the same manner as in Example 1.
-MS analysis was conducted, and an infrared absorption spectrum and a 'H-NMR spectrum were also measured. The results are shown below.

Elemental analysis: CHF Calculated value 9 (%) 29.47 1.55 6
4.08 Actual value (%) 29.3i 1.5
8 64.00 C, F1. ++, calculation as 0 (
Direct GC-MS: m/e (M") 326 infrared absorption spectrum: The chart is shown in Figure 2. From this chart, the peak at 3650.3450 cm-' derived from the OH group disappeared,
It was observed that a new peak based on C=C was generated at 1660 cm-'.

'II-NMR spectrum: Solvent: CC1, Internal standard: TMS δ (ppm): 5.30-5.60 (m, 2t
l, -CL) 1.90 (S, 3H, CH3) [Reference Example 2] In an autoclave, 65 g of the compound obtained above (0,2
0 mol), 35 g (0,25 mol) of trichlorosilane and 0.90 g (9,2x 10-'
mol) and reacted at 110°C for 64 hours (GL
C, conversion rate 92%, selectivity 98%). After the reaction was completed, fraction 22, Og (raw material alkene) with a boiling point of 93 to 98 °C was first distilled at normal pressure, and then distilled under reduced pressure, resulting in the following formula as a fraction with a boiling point of 66 to 67 °C/10 snHg. 47.8 g (yield 50%) of the compound was obtained.

CFi c)+3 CFiCP, CF20CF-CH-CH2-3iC! !
3 The obtained compound was subjected to elemental analysis and GC-MS analysis, and the infrared spectrum and ')l of this compound were
-N? When the IR spectrum was measured, the following results were obtained.

Elemental analysis: ClIC77F Calculated value (%) 20.82 1.31 23.04
45.28 Actual value (%) 20.65 1.33
22.95 45.02 pieces CeCl-3Fl +H6
Calculated value GC-MS as 0Si: m/e 4
61(M') IR spectrum: The peak at 1660 cm-' derived from C=C disappeared.

'H-NMR spectrum: ? Vehicle: CCl4 Internal standard: T gate S δ (ppm); 5.66 (m, IH, CH-)
, 3.80 (m, 2H, CHz-).

2.83 (m, 3t1.CH:+)

[Brief explanation of the drawing]

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

Claims (1)

[Claims] 1. The terminal isoform represented by the following formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, in the formula, n is an integer from 1 to 4.) Hexafluoropropene oxide oligoether derivative having a propenyl group. 2. Hexa having a terminal dimethyl carbinol group represented by the following formula (2) ▲ Numerical formulas, chemical formulas, tables, etc. ▼... (2) (In the formula, n represents an integer from 1 to 4.) A method for producing a hexafluoropropene oxide oligoether derivative having a terminal isopropenyl group, which comprises dehydrating a fluoropropene oxide oligoether derivative to obtain a derivative represented by the formula (1) according to claim 1.