Method for preparing ligand for polyketone polymerization catalyst

Abstract

The present disclosure provides a method for preparing ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine), a ligand for a polyketone polymerization catalyst, under mild conditions with high purity and high yield. Therefore, the preparation method of the present disclosure can be easily applied to mass production.

Claims

1. A method for preparing a compound represented by the following Formula 1, comprising a step (S1) of reacting a compound represented by the following Formula 2 with a compound represented by the following Formula 3 in the presence of a base which is sodium tert-butoxide or potassium tert-butoxide: ##STR00007##

2. The method of claim 1, wherein the base is sodium tert-butoxide.

3. The method of claim 1, further comprising a step (S2) of recrystallizing the compound of Formula 1 obtained in the above step (S1) using a crystallization solvent.

4. The method of claim 3, wherein the recrystallization solvent is selected from the group consisting of methylene chloride, methanol, water, acetone, and mixtures thereof.

5. The method of claim 4, wherein the recrystallization solvent is a mixed solvent of methylene chloride and methanol.

6. The method of claim 5, wherein the volume ration of methylene chloride to methanol is 1:3 to 1:20.

7. The method of claim 3, wherein the recrystallization step is carried out at a temperature of 0 C. to 10 C.

8. The method of claim 3, wherein the bulk density of the compound of Formula 1 is 0.40 g/ml or higher.

Description

MODE FOR INVENTION

(1) Hereinafter, preferred examples will be described for a better understanding of the present disclosure. However, the following examples are provided for illustrative purpose only and are not intended to limit the scope of the present disclosure.

(2) Moreover, unless otherwise stated, the reagents and solvents mentioned below were purchased from Sigma-Aldrich Korea, and .sup.31P and .sup.1H NMR were recorded on an Oxford NMR 300 MHz spectrometer (Varian Mercury Instrument).

PREPARATION EXAMPLES: PREPARATION OF REACTANTS FOR ALKYLATION REACTION

Preparation Example 1: Preparation of bis(2-methoxyphenyl)phosphine (Formula 2)

(3) Bis(2-methoxyphenyl)phosphine oxide (1 kg, 3.78 mol) synthesized by Grignard reaction of phosphorus trichloride and 2-bromoanisole was dissolved in 25 L of acetonitrile, and then triethylamine (1.2 kg, 11.35 mol) was added thereto at an internal temperature of 20 C. to 25 C. Then, trichlorosilane (1.5 kg, 11.35 mol) was added thereto while maintaining the internal temperature below 45 C. The resulting mixture was stirred at an internal temperature of 65 C. to 70 C. for 2 hours and then cooled. After the completion of cooling, the reaction was terminated with 25% sodium hydroxide, followed by phase separation. The organic phase was dried over anhydrous sodium sulfate and then concentrated. The concentrated residue was recrystallized with anhydrous ethanol to yield the target compound (0.82 kg, 88.0%).

(4) .sup.1H NMR (CDCl.sub.3): 7.20-7.40 (m, 4H), 6.60-6.80 (m, 4H), 5.56 (s, 0.5H), 4.80 (s, 0.5H), 3.79 (s, 6H)

(5) .sup.31P NMR(CDCl.sub.3): 70

Preparation Example 2: Preparation of 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane (Formula 3)

(6) 2,2-(bromomethyl)propane-1,3-diol (1 kg, 3.8 mol) was dissolved in 4 L of methylene chloride under a nitrogen atmosphere. 2,2-dimethoxypropane (596 g, 5.7 mol) was added thereto and cooled to an internal temperature of 0 C. to 5 C. Concentrated sulfuric acid (7 g, 18.8 mmol) was added thereto while maintaining the internal temperature and then stirred for 5 hours at an internal temperature of 0 C. to 5 C. The resulting mixture was washed with an aqueous solution of sodium hydrogen carbonate twice and then with water. Then, the resulting mixture was dried over anhydrous sodium sulfate, and then the solvent was concentrated under reduced pressure to yield the target compound (1.11 kg, 96.4%).

(7) .sup.1H NMR (CDCl.sub.3): 3.79 (s, 4H), 3.57 (s, 4H), 1.41 (s, 6H)

Comparative Example: Preparation of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) according to the preparation method of WO 2015/009061

(8) Bis(2-methoxyphenyl)phosphine (1 kg, 4.06 mol) prepared in Preparation Example 1 and dimethylsulfoxide (11 kg) were placed in a reaction vessel under a nitrogen atmosphere, sodium hydride (60%) (0.33 kg, 8.12 mol) was added thereto at room temperature, and the resulting mixture was stirred for 1 hour.

(9) A mixed solution of 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane (736 g, 2.84 mol) prepared in Preparation Example 2 and dimethylsulfoxide (5.5 kg) was slowly added thereto and stirred for 2 to 4 hours.

(10) After the completion of the reaction, 2 L of methanol was slowly added to terminate the reaction, and then 10 L of toluene and 10 L of water were added, followed by phase separation. The organic phase was washed with water twice and then dried over anhydrous sodium sulfate, followed by concentration.

(11) The residue was recrystallized with methanol to yield ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) (0.42 kg, 32.9%, 98.0% or higher (.sup.31P-NMR purity)).

(12) .sup.1H NMR (CDCl.sub.3): 7.26-7.16 (m, 8H), 6.87-6.75 (m, 8H), 3.92 (s, 4H), 3.70 (s, 12H), 2.51 (d, 4H), 1.44 (s, 6H)

(13) .sup.31P NMR(CDCl.sub.3): 46.04

Examples: Preparation of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) According to the Preparation Method of the Present Disclosure

Example 1: Alkylation Reaction Using Sodium Tert-Butoxide

(14) Bis(2-methoxyphenyl)phosphine (1 kg, 4.06 mol) prepared in Preparation Example 1 and dimethylsulfoxide (11 kg) were placed in a reaction vessel under a nitrogen atmosphere, sodium tert-butoxide (0.47 kg, 4.87 mol) was added thereto at room temperature, and the resulting mixture was stirred for 1 hour.

(15) A mixed solution of 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane (736 g, 2.84 mol) prepared in Preparation Example 2 and dimethylsulfoxide (5.5 kg) was slowly added thereto and stirred for 2 to 4 hours.

(16) After the completion of the reaction, 10 L of toluene and 10 L of water were added, followed by phase separation. The organic phase was washed with water twice and then dried over anhydrous sodium sulfate, followed by concentration.

(17) The residue was recrystallized with methanol to yield ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) (1.08 kg, 84.0%, 98.0% or higher (.sup.31P-NMR purity)).

(18) .sup.1H NMR (CDCl.sub.3) and .sup.31P NMR(CDCl.sub.3): the same as the Comparative Example.

Example 2: Alkylation Reaction Using Potassium Tert-Butoxide

(19) Bis(2-methoxyphenyl)phosphine (1 kg, 4.06 mol) prepared in Preparation Example 1 and dimethylsulfoxide (11 kg) were placed in a reaction vessel under a nitrogen atmosphere, potassium tert-butoxide (0.55 kg, 4.87 mol) was added thereto at room temperature, and the resulting mixture was stirred for 1 hour.

(20) A mixed solution of 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane (736 g, 2.84 mol) prepared in Preparation Example 2 and dimethylsulfoxide (5.5 kg) was slowly added thereto and stirred for 2 to 4 hours.

(21) After the completion of the reaction, 10 L of toluene and 10 L of water were added, followed by phase separation. The organic phase was washed with water twice and then dried over anhydrous sodium sulfate, followed by concentration.

(22) The residue was recrystallized with methanol to yield ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) {0.89 kg, 69.5%, 98.0% or higher (.sup.31P NMR purity)}.

(23) .sup.1H NMR (CDCl.sub.3) and .sup.31P NMR(CDCl.sub.3): the same as the Comparative Example.

Example 3: Recrystallization for Improvement of Bulk Density

(24) 1 kg of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) crystals prepared in Example 1 were completely dissolved in 1.5 L of methylene chloride, and then 7 L of methanol was added thereto while maintaining an internal temperature of 0 C. to 5 C. The resulting mixture was stirred for 1 hour while maintaining the internal temperature of 0 C. to 5 C. and filtered to yield ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) with a bulk density of 0.40 g/ml or higher (0.9 kg, 90.0%, 0.55 g/ml).