SU727644A1 - Method of preparing epoxyvinyl ethers - Google Patents

Description

(54) METHOD FOR OBTAINING EPRXIVINYL ETHERS

one

This invention relates to a new process for the preparation of new compounds of epoxyvinyl ethers of the general formula I, -

/

I CHj

where R is (CH2.) i, (CHj), (CH2) -jO (CHi2.) j used to make epoxy resins, mastic, as a solvent.

A known method for producing glycidol vinyloxyethyl ester and similar compounds by reacting oxyalkyl vinyl ethers (vinyl glycol monoethers) with epihalohydrins in the presence of alkali metals, their vinyl oxyalkoxylates or alkalis 1.

The reaction is carried out as follows. 143 g of potassium metal (3.66 mol) was dissolved in 750 g (12.45 mol.) Of isopropyl alcohol, and 201.5 g (2.29 mol) of 2-oxyalkyl vinyl ether (vinyl meno ether of ethylene glycol) were added to this solution. ), this mixture is then gradually poured into 1028 g (11.1 mol) of epichlorohydrin at 46-85 C during

3 hours. The precipitated KCI is separated by filtration and the filtrate is immediately distilled under vacuum of 1 mm Hg. (to prevent further contact of the product with an excess of potassium isopropoxide), condensate is collected in a receiver cooled with dry ice; as a result of the subsequent distillation, glycidol vinyloxyethyl ether is isolated with a yield of 62%.

This method has several disadvantages: low yield of the target product; the use of large quantities (1.5 times the required reaction stoichiometry) of extremely aggressive and highly fire-explosive metallic potassium; the presence of a dangerous and highly non-technological operation for dissolving large quantities of metallic potassium in isopropyl alcohol; distilling the product over an excess of an alkaline inorganic agent, which leads to the oligomerization of a part of the glycosidol vinyloxyethyl ester on the epoxy group and is usually accompanied by emissions and clogging of the distillation system in the distillation distillate; the use of diluted solutions (3-4-fold excess solvent) and a large

an excess of epichlorohydrin (5-fold), resulting in additional energy costs due to unproductive distillation; It is necessary to cool the distillate deeply.

Another known method pbluchoyy viniloksietoksietilovogo glycidol ether 2 by condensing diethylene glycol vinyl monoether with epichlorohydrin taken upon in the equimolar ratio, under the action of potassium hydroxide in the absence of solvent at 20-80 product was isolated by distillation in vacuo (1 mm Hg) after the filtered VSWR The yield of the product is 50% based on alkali, which is taken up with the lack of diethylene glycol monoester and epichlorohydrin (0.4 mol of KOH per 1 mole of reagents). The disadvantages of this method are the low yield of the target product and the complexity of the process technology.

These new compounds, epoxy vinyl ethers of the general formula I, can be obtained in low yield (up to 40%), which is a significant disadvantage of using known methods for the preparation of these new compounds.

The purpose of the invention is to develop a method for producing new compounds, epoxyvinyl esters of general formula I, which simplifies the technology for producing these compounds and ensures a high yield of the target product.

According to the invention, the goal is achieved by the fact that epoxyvinyl ethers of general formula I are obtained by reacting glycidol with the corresponding glycol divinyl ethers at 20-85 ° C, and perfluorobutyric acid or trifluoroacetic acid is used as a catalyst. Preferably, prodes are carried out at a molar ratio of glycidol and glycol divinyl ether, p & 1: 1-6,

In contrast to the known ones, the proposed product provides significantly higher product yields, is absolutely safe, less energy-consuming and easier to process (it avoids both high and low temperatures, does not require solvents, continuous mixing, and complex instrumentation) moreover, it is waste-free and does not produce any wastewater.

The yield of the target product is 85%. The epoxy vinyl ethers obtained are colorless, mobile liquids, the lower members of the series are easily distilled in vacuum.

The elemental analysis data, IR and PMR spectroscopy, confirm the structure of the obtained compounds. In the IR spectra of the products, there are no absorption bands in the region of 33003600 related to hydroxyl, while in the spectrum there is an intense absorption in the region of 820, 960, 1200, 1320, 1605, 1620, 3110 cm and 910, 1250, 3050 cm-due to the vibrations of the double bond and the epoxy group, respectively.

In the PMR spectra of the products, duplicates and quartets of signals are iris-chopped, whose chemical shifts correspond. they are produced by methyl and methynrvam, protons of the acetal fragment. (o, -IN-O)

CH}

Example I, Obtaining 1- (niloxyethoxyethoxy) ethyl glycidol ester,

SNG SnoHs; ngOSNgSNgS) SnoH2Sn-dHj

SNO

0 to a mixture of 24 g (0.15 mol) of divinyl diethylene glycol ether and 1.87 g (0.025 mol) of glycidol, 0.048 g of perfluorobutyric acid is added and kept for 2 hours at 30-40 ° C. Distillation in vacuum gives 5 g ( output

85.3% in the conversion of diethylene glycol divinyl ether 18.8%) 1- (vinyloxyethoxyethoxy) -ethyl glycidol, kip, 110 ° C (1 mm Hg) (, 4503; d | ° - 1.0660; MRD : found 58.52,

calculated 59.25;

Found,%: C 56.54; H 8.98.

Calculated,%: C, 56.89; H 8.62.

IR spectra: 918, 1250, 3060, 850, 968, 1320, 1625, 1640, 3120 cm.

PMR spectrum: 6.41, 1.20 and 4.72 m, d The integrated signal intensity corresponds to 20 protons, which is consistent with the structure attributed to the compound.

P F and m p 2, Preparation of 1- (Vinyloxyethoxy) ethyl glycidol ether,. .

SNG SnOSNgSNaOsnoSNgSn -, SNg SNG about

to 12 g (0.1 mol) of ethylene glycol divinyl ether, 1.95 g (0.026 mol) of glycidol and 0.04 g are added, stirred and heated for 2 hours at .3 dB-40c. Fractionation in vacuo gave 3 g (all at 60.6% for the conversion of ethylene glycol divinyl ether to 33.3%) of glycidol 1- (vinyloxyethoxy) ethyl ether, bp 72c (1 mm Hg); nti ° - 1.44 70; d | -l, 0470; found 47.97, calculated 48.17.

Found,%: C 58.00; H 8.95.

Calculated,%: C 57.45; H 8.51,

IR spectrum: 850, 918, 1208, 1255, 3060, 1325, 1627, 1642, 3120 cm

HMR spectrum: 1.16, 4.67, 6.34 ppm The integrated intensity of the signals in the product spectrum corresponds to 16 protons, which is in full accordance with the structure attributed to the compound. Example 3. Getting - | VIIILOXYPROPOXI) ETHYL ETHY I and glycidol, SNG Sno (CGV BOSNSNG CIS dHj Q 15.1 g (0.124 mol) of 1,3-propylene glycol divinyl ester is mixed with 2.3 g (0.031 mol) of glycidol, added 0.036 g of perfluorobutyric acid is heated at 20–25 ° C for 2 h. The reaction mixture is distilled in vacuo to give 4.5 g (yield 71.7% with divinyl ether 1-3-propylene glycol 27.2%) (Vinyloxy propoxy) ethyl glycidol ether. 82 "C (1 mm from st.); n in-1.4459; d | - 1.0285; found 52.36, calculated 52.81. Found:% 60.16; H 8.99. Calculated,%: C 59.4; H 8.91. IR spectrum: 915, 1250, 3060, 815, 96 0, 1200, 1315, 1610, 3120 CMI PMR spectrum: 1.21, 4.67 and 6.41 ppm Integral signal intensity in the product spectrum corresponds to 18 protons, which is in full agreement with the proposed structure. Example 4. A mixture of 1.48 g (0.02 mol) of glycidol, 10 g (0.13 mol of 1,3-propylene glycol divinyl ester and 0.02 g of trifluoroacetic acid is kept at 30-40 seconds for 2 hours. 2 in a vacuum, 2 g (yield 73.3 g in the conversion of lj-3-propylene glycol divinyl ether 18%) - (vinyloxypropoxy) ethyl glycid ether. Formula of Invention 1. Sporob of obtaining epoxy vinyl ethers of the general formula C% - CHCHaOCHOROCK-CHLj O CHj where R is CH2) 2, or (CH), or (CH2) 20 (CH3) implying that glycidol is reacted with the corresponding divinyl glycol ether at 20–80 ° C in the presence of perfluoromethyl or trifluoroacetic acid as a catalyst. 2. The method according to p. 1, I differ by the fact that the process is at a molar ratio of glycidol and glycol divinyl ether, equal to 1: 1-6. Sources of information taken into account in the examination 1.Patent of Germany 1075594, cl. 12о, 21, published. 1960. 2. US Patent 3245893, cl. 260-348, pub. 1966.

Claims (2)

Claim 1. Disputes for the preparation of epoxy vinyl ethers of the general formula 0¾— CHCHjOCHOROCH- CHj CHj where R is (CH ₂ ) ₂ , or (CH ₂ ) _g , or (CH ₂ ) gO (CH _x ), the key to which is that glycidol is reacted with the corresponding divinyl ether glycol at 20-80 C ⁱⁿ the presence perftormaslyanOy or trifluoroacetic acid as a catalyst. · ' 2. The method of pop. 1, excellent? and the fact that the process is carried out at a molar ratio of glycidol and glycol divinyl ether equal to 1: 1-6.