JPH07145098A - Alkoxyl group-containing compound - Google Patents

Abstract

PURPOSE:To obtain the subject new compound which is useful as an electron donor in the Ziegler catalyst exhybiting high polymerization activity and high stereoregularity. CONSTITUTION:2-(t-Butyl)-1-ethoxy-3-methoxypropane. This compound is prepared by reduction of ethyl 3-methoxy-2-(t-butyl)propionate with lithium aluminum hydride or the like, to obtain 3-methoxy-2-(t-butyl)propan-1-ol, then with ethyl halide in a protonic or polar solvent in the presence of alkali metal or alkali metal hydride and purification of the product by destillation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel alkoxyl group-containing compound useful as an electron-donating compound for a Ziegler catalyst and having two bulky substituents and two different ether moieties.

[0002]

It is well known to use a compound having an ether bond as an electron-donating compound for a Ziegler catalyst. In particular, it is also known that a polymer having high stereoregularity can be produced by using a compound having two ether groups in the molecule (JP-A-3-29430).
2). However, when the conventionally proposed ether compound is used, the polymerization activity does not always satisfy the present industrial requirements. On the other hand, although the detailed reason is unknown, in order to improve the performance of the catalyst, (1) the electron-donating compound has a substituent having large steric hindrance in the molecule (2) ether group of the electron-donating compound It is known that it is important that one of them is an ethoxy group (JP-A-2-2896).
04). Recently, the substituent at the 2-position of a 1,3-dialkoxypropane compound derivative, which is one type of ether compound, has a secondary carbon group (2,2-diisobutyl-1,3-dimethoxypropane, 2-isopentyl-2-isopropyl). -1,3-dimethoxypropane etc.) has been reported (JP-A-2-256633). However, it was difficult to synthesize a 1,3-dialkoxypropane compound derivative in which the substituent at the 2-position was a tertiary carbon group because of the steric hindrance of the substituent. A method for synthesizing a mixed alkoxyl group-containing compound having particularly bulky substituents and different ether moieties is not known at present. Therefore, it has been desired to develop a novel compound having a bulky substituent in the molecule and two substituents having different ether moieties.

[0003]

The present invention is to provide a novel alkoxyl group-containing compound having a bulky substituent group, which exhibits high activity and high stereoregularity as an electron-donating compound for a Ziegler catalyst. . Particularly, it is to provide an alkoxyl group-containing compound having a tertiary carbon group as a substituent and two substituents each having a different ether moiety.

[0004]

The above-mentioned object has been achieved by a novel alkoxyl group-containing compound having a bulky substituent and two substituents each having a different ether moiety. The name of this compound is 2- (t-butyl) -3-ethoxy-1-methoxypropane (2- (t-butyl) -3-ethoxy-1-meth
oxypropane) with a boiling point of 95-96 ℃ / 50 mmHg. This compound can be confirmed by ¹ H-NMR, ¹³ C-NMR, GC-MS and the like. For example, when the compound is analyzed using ¹ H-NMR, (1) the signal of the hydrogen atom bonded to the carbon atom directly bonded to the oxygen atom in the ethoxy group at δ = 3.31 to 3.45 ppm (2 ) Signal of hydrogen atom bonded to carbon of methoxy group at δ = 3.22 ppm (3) Signal of hydrogen atom located at 2nd position of propane skeleton at δ = 1.40 ~ 1.42 ppm (4) At δ = 1.08 ~ 1.12 ppm Signal of hydrogen atom bonded to methyl group of ethoxy group (5) A signal of hydrogen atom bonded to carbon atom of methyl group of t-butyl group was observed at δ = 0.87 ppm. In addition, in the analysis using ¹³ C-NMR, 71.30, 68.74, 66.04, 58.49, 48.37, 31.78, 28.4
Signals were observed at 4 and 15.10 ppm. By using this alkoxyl group-containing compound as an electron-donating compound for a Ziegler catalyst, an olefin polymer such as polypropylene having high stereoregularity can be produced with high polymerization activity.

The 2- (t-butyl) -3-ethoxy-1-methoxypropane compound of the present invention can be synthesized by a known method as described below (4th Edition Experimental Chemistry Course 2).
0 organic synthesis II alcohol amine). (1) Synthesis from alcohol compound and halogen compound. 2- (t-butyl) -3-alkoxypropan-1-ol compound and R-X (where X is chlorine, bromine, iodine, paratoluenesulfonic acid, etc.) (2) By dehydration between alcohol compound Synthetic. Thermal or catalytic dehydration reaction between 2- (t-butyl) -3-alkoxypropan-1-ol compound and alcohol compound. For example, 2- (t-butyl) -3-methoxy-1-ol can be reacted in a solvent to obtain a mixed alkoxyl group-containing compound. As the solvent, a protic solvent such as alcohol and a polar solvent such as ether are effective. At this time, sodium, potassium, sodium hydride, potassium hydride or the like can be used as the alkali metal coexisting. Usually, 20 to 2 after addition of the alkyl halide compound
The reaction is carried out at a temperature of 00 ° C for 1 to 24 hours. In this way, an ether body can be obtained as a crude product. Then
The target product can be obtained by subjecting the obtained crude product to distillation purification.

The alkoxyl alcohol compound used as the above raw material can be synthesized by the following reaction. (1) Reduction reaction of the corresponding alkoxy ester compound (
Lithium aluminum hydride, diisobutylaluminum hydride, etc.). (2) Aldol reaction of ether lithium enolate with aldehyde (Y. Weiand R. Bakthavatchalam, Tetrah
edron, Vol. 49, No. 12, 2373-2390 (1993).). The alkoxy ester compound used above can be synthesized by a known method such as a reaction between a corresponding substituted lithium acetate enolate and α-halogenated methyl ether. The ether compound of the present invention, a method for producing the same, a method for preparing a Ziegler catalyst, and a polymerization method will be illustrated by the following examples.

[0007]

【Example】

Example 1 Synthesis of 2- (t-butyl) -3-methoxy-1-methoxypropane Synthesis of ethyl t-butylacetate 500 equipped with magnetic stir bar and Dimroth under nitrogen stream
t-Butyl acetic acid (manufactured by Aldrich) in a 3-necked flask
100 g (0.46 mol), 120 ml of dehydrated ethanol and 6 ml of concentrated sulfuric acid were charged. The contents of the flask were stirred and refluxed for 6 hours. After cooling to room temperature, the reaction mixture was poured into 200 ml of water and neutralized with a saturated sodium hydrogen carbonate aqueous solution.
The solvent layer was separated and dried under sodium sulfate. The solvent was distilled off by atmospheric distillation. Then, distill the target product to 6
0 g was obtained (yield 91%). Boiling point 145-147 ° C / 76
0 mmHg

3-methoxy-2- (t-butyl) propionic acid
Chill synthesis Under a nitrogen stream, use a magnetic stir bar, dropping funnel and jim funnel.
Diisopropylamine in a 500 ml three-necked flask attached
21 g (0.21 mol) and dehydrated tetrahydrofuran 60 m
1 was charged and the contents were cooled with ice. n-Butyl lithium 13
2 ml (0.21 mol) (1.7 Mol / L hexane solution) for 15 minutes
It dripped over time. After the dropping, add the reaction solution to 30 ℃.
Heat and stir for 30 minutes. Then, the contents of the flask are -7
Cooled to 8 ° C. t-Butyl ethyl acetate 28.8 g (0.2 m
ol) and 30 ml of dehydrated tetrahydrofuran for 30 minutes
Then, the mixture was stirred for 30 minutes. Then Chlorome
21.3 g (0.265 mol) of tyl methyl ether and dehydrated ether
30 ml of trahydrofuran was added dropwise over 15 minutes.
Return the contents of the flask to room temperature and pour into 200 ml of dilute hydrochloric acid.
No After extracting 3 times with 100 ml of pentane, sodium sulfate is extracted.
Dried under the ium. Rotary evaporator for solvent
Then, 26.5 g of the target product was obtained by distilling under reduced pressure and distilling under reduced pressure.
(Yield 70%). Boiling point 121 to 123 ° C / 63 mmHg m / e = 189 GC> 9
9% ¹ H-NMR (400 MHz, CDCl₃, TMS) 3.97 (2H, m), 3.50 (1H, t), 3.34 (1H, m), 3.13 (3
H, s), 2.30 (1H, d-d), 1.08 (3H, t), 0.84 (9H, s) ¹³ C-NMR (CDCl₃) 173.52, 71.06, 59.35, 58.47, 55.59, 31.64, 27.80,
13.93 ppm

Synthesis of 3-methoxy-2- (t-butyl) propan-1-ol Under a nitrogen stream, 200 ml of dehydrated diethyl ether and 3.8 ml of lithium hydride hydride were placed in a 500 ml three-necked flask equipped with a magnetic stirrer, a dropping funnel and a Dimroth. g (0.
1 mol) was introduced. The contents of the flask were cooled with ice, and 18.7 g of ethyl 3-methoxy-2- (t-butyl) propionate (.
1 mol) and 50 ml of dehydrated diethyl ether were added dropwise over 30 minutes. After confirming the completion of the reaction by gas chromatography, the content was poured into 100 g of ice acidified with dilute hydrochloric acid, and the mixture was mixed with 100 ml of pentane to 3 times.
Extracted twice. Dried under sodium sulfate. The solvent was distilled off with a rotary evaporator to obtain 16 g of a crude product (yield 99%).

2- (t-butyl) -3-ethoxy-1-methoxy
Method for synthesizing lopan Under a nitrogen stream, a magnetic stirrer, a dropping funnel and a Jimroth are used.
Obtained by the above reaction in a 1000 ml three-necked flask attached
16 g of crude product, 500 ml of dioxane and potassium t-
Add butyrate 13g (0.11 mol) for 30 minutes at room temperature
It was stirred. Then, 23.7 g of ethyl iodide over 30 minutes
(0.15 mol) was added dropwise, and the contents of the flask were heated to reflux for 6 hours.
did. The reaction is complete by gas chromatography
After confirming that the reaction mixture was diluted with 500 ml of diluted hydrochloric acid.
I poured it. It was extracted three times with 100 ml of pentane. Sodium sulfate
Dried under the ium. By rotary evaporator
The solvent was distilled off, and the target compound was distilled off under reduced pressure to give 6.3 g of the desired product.
Obtained (yield 36%). Boiling point 95-96 ℃ / 50mmHg m / e = 174 GC> 99% ¹ H-NMR (400 MHz, CDCl₃, TMS) 3.381 (4H, m), 3.224 (3H, s), 1.411 (1H, t), 1.101 (3
H, t), 0.866 (9H, s)¹³C-NMR (CDCl₃) 71.30, 68.74, 66.04, 58.49, 48.37, 31.78, 28.44, 1
5.10

Method for preparing Ziegler catalyst In a 300 ml round-bottomed flask sufficiently dried under a nitrogen stream, 5 g of diethoxymagnesium and 2- (t-butyl) -1-
1.48 g of ethoxy-3-methoxypropane and 25 ml of methylene chloride were added. The contents of the flask were stirred under reflux for 1 hour and then the suspension was pumped into 200 ml of room temperature titanium tetrachloride. The temperature was gradually raised to 110 ° C. and the reaction was carried out with stirring for 2 hours. After the reaction was completed, the precipitated solid was separated by filtration, and 11
It was washed 3 times with 200 ml of n-decane at 0 ° C. Titanium tetrachloride (200 ml) was newly added and reacted at 120 ° C. for 2 hours. After the reaction was completed, the precipitated solid was separated by filtration and n-decane 200 m
It was washed 3 times with 1, and washed with hexane at room temperature until no chloride ion was detected with n-hexane.

Polymerization of Propylene Into a 1.5 liter stainless steel autoclave, 3.5 mg of the solid component produced by the above method, 5.4 mg of thexyltrimethoxysilane, 91 mg of triethylaluminum were added, and then 340 g of propylene and 0.03 g of It was filled with hydrogen. The temperature of the autoclave was raised and the internal temperature was kept at 70 ° C. After 1 hour, the content gas was released to terminate the polymerization. As a result, 130 g of polypropylene powder was obtained. MF
R was 3.8 g / 10 min and boiling xylene solubles was 2.2%.

[0013]

As described above, it is possible to provide a novel alkoxyl group-containing compound having a bulky substituent as an electron-donating compound of a Ziegler catalyst and having two substituents each having a different ether moiety.

[Brief description of drawings]

FIG. 1 2- (t-butyl) -3-ethoxy produced in Example 1
The ¹ H-NMR chart of 1-methoxypropane compound.

FIG. 2 2- (t-butyl) -3-ethoxy produced in Example 1
¹³ C-NMR chart of -1-methoxypropane compound.

Claims (1)

[Claims] 1. 2- (t-butyl) -1-ethoxy-3
-Methoxypropane compounds.