KR970002468B1 - A process for the preparation of glycidyl-2-propenyl ether - Google Patents

Abstract

0.01 to 5 mole part of ruthenium(triphenylphosphate) chloride by aryl glycidyl ether is used as catalyst at the temperature ranged of 100 to 130 degree Celsius to yield glycidyl-2-prophenyl ether of general formula(I). In general formula(I), R represents alkyl, groups selected from aromatic or CO, X and Y represent CH3 respectively. X and Y can be same groups.

Description

Method for preparing glycidyl-2-propenyl ether

The present invention relates to a low molecular weight curable substance used as a diluent in epoxy resins, and more particularly, to a method for producing glycidyl-2-propenyl ether.

In general, epoxy resins among thermosetting resins are excellent in mechanical properties, electrical insulating properties, adhesiveness, molding processability, and the like, and are selected and used in various ways depending on the purpose or purpose.

In the epoxy resin art, a diluent is widely used to lower the viscosity of the epoxy resin and to selectively change the properties of the cured resin to develop an epoxy resin having excellent chemical, thermal and electrical physical properties.

Typically, the diluent is classified as having three properties: basically, (i) non-reactive properties of epoxy, (ii) reactive and epoxy-containing groups, and (iii) reactive and non-epoxy groups. Can be.

The diluents used in the epoxy resin industry, which are mainly used in the non-reactive system, include styrene, dibutyl phthalate, styrene, and phenol. Etc. are used.

Recently, the materials used as the diluents of epoxy resins tend to use reactive and epoxy group-containing properties among the above three properties, and those which contain reactive and non-epoxy functional groups.

Reactive diluents having such characteristics include glycidyl-2-propenyl ether, and the preparation method thereof is prepared by J. Chem. J. Chem. Soc., 2969, 1965.

However, the manufacturing method by Cunningham, etc. consists of six stages of multi-step reactions, and the final yield is only about 20% or less, and the development of the manufacturing method is required.

Therefore, the present invention solves the problem of the method for preparing glycidyl-2-propenyl ether prepared through a complicated step known in the art to provide a method for preparing glycidyl-2-propenyl ether in a simple process. The purpose is.

In addition, the aim is to increase the yield to about 95% by a simple method according to the present invention.

Hereinafter, the present invention will be described in detail.

In the preparation of glycidyl-2-propenyl ether of the following structural formula (I), rutium (triphenyl phosphate) chloride [Ru (PPh ₃ ) Cl] 0.01 to 5 of allyl glycidyl ether A method for producing glycidyl-2-propenyl ether, characterized in that the reaction is carried out at a constant temperature using an amount of mol% as a reaction catalyst.

[Formula 1]

Wherein R is a group selected from alkyl, aromatic or CO groups, X and Y are H or CH 3, and may be the same or different.

Hereinafter, the present invention will be described in more detail.

That is, the present invention reacts at a constant temperature using an amount of 0.01 to 5 mol% of ruthenium (triphenylphosphate) chloride [Ru (PPh3) Cl] as a reaction catalyst with respect to allyl glycidyl ether of the following formula (II) To prepare glycidyl-2-propenyl ether of formula (I).

[Formula 2]

In the above formula, R, X and Y are the same as in formula (I).

The amount of ruthenium (triphenylphosphate) chloride [Ru (PPh ₃ ) Cl] to be used as the reaction catalyst as the catalyst is suitably 0.01 to 5 mol% based on the allylglycidyl ether of the formula (II). Do. If the amount is less than 0.01 mol%, there is almost no effect of acting as a reaction catalyst, and if the amount is more than 5 mol%, the effect that contributes to the reaction no longer occurs.

In addition, the reaction temperature is suitably 100 to 130 ° C. When the reaction temperature is less than 100 ℃ in the above, the reaction proceeds slowly, in the case of more than 130 ℃ temperature range the catalyst component is decomposed may not proceed any more.

Glycidyl-2-propenyl ether of the formula (I) produced by the production method according to the present invention is compared with the manufacturing process that goes through a complicated multi-stage (six-step) manufacturing step known by conventional Cunningham et al. It consists of a simple reaction step of a single step, and also, compared to the yield (about 20%) of the conventional known production method, the production method according to the present invention showed an effect obtained in an excellent yield (about 95%).

Hereinafter, the present invention will be described in detail with reference to the following Examples.

Example 1

Preparation of Glycidyl-2-propenyl Ether

10 g of allylglycidyl ether and 84 mg of ruthenium (triphenylphosphate) chloride [Ru (PPh ₃ ) Cl] are placed in a 100 ml three-necked flask equipped with a magnetic stirrer, thermometer and reflux condenser, followed by nitrogen gas. It reacted under the atmosphere of. The reaction mixture was reacted for 5 hours while maintaining the temperature at 130 ° C. in the oil bath. The product was triturated under vacuum of 1.0 mm Hg to give 9.5 g of the title compound.

The reaction progress was monitored by CH ₂ proton and CH proton of the double bond in each allyl group at 5.2 and 5.9 ppm using ¹ H-NMR. Over time, the 5.2 and 5.9 ppm bands disappeared and the new vinyl ether protons appeared at 4.4, 4.8, 5.9 and 6.2 ppm, respectively.

Characteristics of the product

Boiling Point: 45 ℃ (1.0mmHg)

Elemental Analysis:

Experimental value (%): C; 63.12, H; 8.84

Theoretical value (%): C; 62.75, H; 8.93

Example 2

Preparation of Glycidyl-2-propenyl Ether by Catalyst Reuse

To recycle the catalyst, 20 ml of toluene and 10 g of allylglycidyl ether as the polymer and the amount of the Ru catalyst (0.05 mol% relative to allylglycidyl ether) supported by a polymer were used. -Placed in a neck flask and reacted under nitrogen atmosphere for 10 hours. After the reaction was completed, the scavenger was removed by filtration, and the organic solvent was evaporated to give crude glycidyl-2-propenyl ether (yield: 70%).

Example 3

Photopolymer Preparation of Glycidyl-2-propenyl Ether

Reactivity test of the glycidyl-2-propenyl ether obtained in Example 1 was prepared by mixing 0.5 mole% of the monomer with (4-decyloxyphenyl) phenyl iodonium hexafluoroantimonate as an initiator. UV curing process was performed with a 300W UV lamp. Spinning time was 0.5 seconds to 1 second using a conveyor. The polymer obtained was formed into a thin film.

Example 4

10 g of allylglycidyl ether was placed in a 100 ml 3-neck flask, and 0.3 g of trifluoroborate diethyl ether (BF ₃ · OEt ₂ ) was added slowly through a syringe at 0 ° C. under vigorous stirring. After 30 minutes, the reaction temperature was increased to room temperature, followed by further 1 hour of reaction. As the reaction proceeded, the viscosity of the reaction solution became high and turned yellow. The reaction mixture was washed with 1% caustic soda and dried.

The obtained polymer was identified as polyethylene oxide containing 95% allyl group by ¹ H-NMR spectroscopy. The polymer obtained was then isomerized using Example 1 to obtain a polyethylene oxide containing 2-propenyl group having 100% yield.

Example 5

The copolymer of polyethylene oxide and polyethylene polyethylene oxide containing 2-propenyl group was carried out similarly to Example 4 at -10 ° C.

[Test Example]

Real-time Infrared Measurement

The reaction rate and% conversion of glycidyl-2-propenyl ether to polymer were measured by real-time infrared spectroscopy. The measurement was carried out by dissolving 0.5 mol% (4-decyloxyphenyl) phenyl idonium hexafluoro antimonate as a catalyst in glycidyl-2-propenyl ether at room temperature in the air and placing it between polyethylene films.

For the calculation of the reaction rate is Rp / [Mo] = ([conversion] t ₂ - [conversion] t ₁₎ and / (t ₂ -t ₁₎ a was applied, Rp / [Mo] values t ₁ = 20 cho t ₂ = the carbon results conducted at 80 seconds the reaction speed of the carbon-carbon double bond was 0.46, epoxy groups had an 0.59. The sample was radiated at a UV intensity of 20 mW / cm 2, and the polymerization rate was calculated as the ratio of increase and decrease in absorbance of 850 cm ⁻¹ and 1.670 cm ⁻¹ (2-propenyl ether group) and time. In 300 seconds, the consumption of the double bond was converted to 76.4% and the epoxy group to 77.2%. The polymerized polymer was insoluble in general organic solvents and was found to be a crosslinked polymer.

Claims (2)

0.01-5% mole of ruthenium (triphenylphosphate) chloride [Ru (PPh ₃ ) Cl] to allylglycidyl ether in the preparation of glycidyl-2-propenyl ether of the following formula (I) A method for producing glycidyl-2-propenyl ether, characterized in that the reaction is carried out at a constant temperature using an amount as a reaction catalyst. [Formula 1] Wherein R is a group selected from alkyl, aromatic or CO groups, X and Y are H or CH ₃ , and may be the same or different. The method for producing glycidyl-2-propenyl ether according to claim 1, wherein the reaction temperature used for catalysis is in the range of 100 to 130 ° C.