JP2000143567A - Production of polyalkylene glycol-1-alkenyl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for synthesizing a polyalkylene glycol-1-propenyl ether in a good yield, while low controlling by-products. SOLUTION: This method for producing a polyalkylene glycol-1-propenyl ether comprises isomerizing a polyalkylene glycol-2-propenyl ether in the presence of one or more catalysts in an amount of 0.01-50 wt.% based on the polyalkylene glycol-2-propenyl ether at a reaction temperature of 30-200 deg.C. The catalyst is obtained by carrying a noble metal including palladium on a carrier in an amount of 0.05-10 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing polyalkylene glycol-1-alkenyl ether which is extremely effective in the fields of resin raw materials and reactive diluents by isomerizing polyalkylene glycol-2-alkenyl ether.

[0002]

2. Description of the Related Art Generally, alkenyl ether compounds have been known to undergo cationic polymerization, but have recently become industrially useful compounds due to their low skin irritation. Among the alkenyl ether compounds, a method for synthesizing ethylene glycol monopropenyl ether is as follows.
Production method of vinyl-1,3-dioxolane by hydrogen decomposition using lithium aluminum hydride (Method A)
[Can. J. Chem. 1972. 49, 2563.] is known. As a general synthesis method for obtaining a propenyl ether compound, an α, β-unsaturated aldehyde is reacted with an excess of a monohydric alcohol under acidic conditions to synthesize an acetal, and then thermally decomposed in the presence of paratoluenesulfonic acid ( (Method B), or a method of alkali isomerizing the corresponding allyl ether compound (Method C), or a method of isomerizing the corresponding allyl ether compound by using a dichlorotriphosphine ruthenium complex (Method D) (the above BD) Law [J. Polym.
Sci. Part A: Polym. Chem. 1993. 31, 1473.]) is known.

[0003]

However, the above A
The method is industrially unsuitable because lithium aluminum hydride, a water-inhibiting substance, must be used in an equivalent amount to the substrate. In the above method B, when a polyhydric alcohol is used as an alcohol, a cyclic acetal by-product is formed. Since this compound is stable and cannot be thermally decomposed, a desired polyalkylene glycol monopropenyl ether cannot be obtained. Furthermore, in the above-mentioned method C, the hydroxyl group of the corresponding polyalkylene glycol monoallyl ether reacts, and the target substance cannot be obtained. In addition, the above method D is not preferable because the generated polyalkylene glycol monopropenyl ether may be cyclized to form a cyclic acetal due to the Lewis acidity of the complex. The present invention has been made in view of such circumstances, and has a low yield of polyalkylene glycol-1 by suppressing by-products.
A method for synthesizing alkenyl ethers.

[0004]

Means for Solving the Problems The present inventors have made intensive efforts to solve the above problems, and as a result, a side reaction is caused by isomerizing polyalkylene glycol-2-alkenyl ether in the presence of a noble metal-supported catalyst. The present inventors have found that polyalkylene glycol-1-alkenyl ether of high purity can be industrially advantageously obtained at a high selectivity and a high yield by suppressing the formation of a cyclic acetal, and the present invention has been completed. That is, the present invention relates to the following matters. (1) A noble metal containing palladium is added to a carrier in an amount of 0.05 to 10
% Or more of the supported catalyst is represented by the following general formula (I): R ¹ CH ＝ CH—CH ₂ — (OR) n—OH (I) (wherein R is an alkylene group having 2 to 4 carbon atoms) Or a cycloalkylene group having 5 to 12 carbon atoms; R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
Represents an integer. ) To the polyalkylene glycol-2-alkenyl ether represented by the formula (1).
The following general formula (II) wherein the polyalkylene glycol-2-alkenyl ether is isomerized at a reaction temperature of 30 to 200 ° C. at a reaction temperature of 30 to 200% by weight: R ¹ CH ₂ —CH ＝ CH— (OR) n—OH (II) (wherein, R represents an alkylene group having 2 to 4 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms; R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; -10
Represents an integer. A method for producing a polyalkylene glycol-1-alkenyl ether represented by the formula: (2) The above-mentioned (1), wherein the noble metal containing palladium is palladium or at least one noble metal selected from the group consisting of ruthenium, rhodium and platinum and palladium.
3. The method for producing a polyalkylene glycol-1-alkenyl ether according to item 1. (3) The method for producing a polyalkylene glycol-1-alkenyl ether according to the above (1) or (2), wherein 5 to 100% by weight of the noble metal containing palladium is palladium. (4) 250 ° C. in the ammonia adsorption thermal desorption measurement
The polyalkylene glycol according to any one of the above (1) to (3), wherein a carrier from which the amount of ammonia released is 1 mmol / g or less is used.
A method for producing 1-alkenyl ether. (5) In the ammonia adsorption thermal desorption measurement, 250 ° C.
The method for producing a polyalkylene glycol-1-alkenyl ether according to the above (4), wherein a carrier having an amount of desorbed ammonia of 0.3 mmol / g or less is used. (6) The polyalkylene glycol-1-alkenyl ether according to any one of the above (1) to (5), wherein the polyalkylene glycol-2-alkenyl ether is ethylene glycol monoallyl ether or propylene glycol monoallyl ether. Manufacturing method. (7) The above (1) to (6) in which the reaction is carried out in an organic solvent.
The method for producing a polyalkylene glycol-1-alkenyl ether according to any one of the above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Polyalkylene glycol used in the present invention
2-Alkenyl ether is an oxyalkyl alcohol represented by the general formula (I) and having an allyloxy group at an alkyl terminal. In the present invention, the polyalkylene glycol-2-alkenyl ether represented by the general formula (I) is represented by the following general formula (III): R ¹ CH = CH—CH ₂ —OR—OH (III) An alkylene glycol having 2 to 4 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms, and R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The polyalkylene glycol-1-alkenyl ether represented by the general formula (II) is represented by the following general formula (IV): R ¹ CH ₂ —CH ＝ CH—OR—OH (IV) (wherein R represents 2 carbon atoms) Represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms, and R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) It is meant to include ether. The present invention provides an isomerization reaction of the above allyloxy group in the presence of a catalyst to form a terminal at one end.
For producing a polyalkylene glycol-1-alkenyl ether having an alkenyloxy group. As the alkylene group for R in the general formula (I), for example, -C
_{H 2 -CH 2 -, - CH} 2 -CH 2 -CH 2 -, - CH
_{2 CH (CH 3) -,} - (CH 2) 4 -, - CH 2 -C
H ₂ —CH (CH ₃ ) — and the like. Preferably, the -CH _{2
-CH 2 -, - CH 2 CH} (CH 3) - it is used.
As the cycloalkylene group, 1,2 - (- C ₅ H
_{8 -), 1,2 - (-} C 6 H 10 -), 1,2 - (- C 12
H ₂₀ -) is used. Examples of R ¹ include a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

In the isomerization reaction of the present invention, a palladium-containing noble metal-supported catalyst is used. VI as precious metal
Group II metals are suitable, including palladium, and as other metals, ruthenium, palladium, rhodium, platinum may be contained, or palladium alone may be used. Among the noble metal-supported catalysts, those containing 5 to 100% by weight of palladium are more preferable. As a carrier to be used, silica, alumina, silica-alumina, activated carbon, titania, or another inorganic compound is used. Among the above-mentioned inorganic carriers for supporting the catalyst, when a carrier having an amount of ammonia desorbed at 250 ° C. or higher of 1 mmol / g or less is used in the ammonia adsorption temperature-programmed desorption measurement, cyclic acetal formation as a side reaction is caused. Is preferred because it is possible to suppress More preferably, it is preferable to use a carrier in which the amount of ammonia desorbed at 250 ° C. or more is 0.3 mmol / g or less. The amount of the noble metal supported on the carrier is preferably 0.05 to 10% by weight, more preferably 2 to 10% by weight of the total amount of the catalyst. If the loading amount is less than 0.05% by weight,
If the content exceeds 10% by weight, the reaction time may be delayed. The amount of the catalyst to be used is 0.01 to 0.01% of the noble metal-supported catalyst based on the polyalkylene glycol-2-alkenyl ether.
It is preferably 50% by weight, more preferably 1 to 10% by weight. If the amount of the catalyst is less than 0.01% by weight, the reaction time is delayed, and if it exceeds 50% by weight, a side reaction may be induced, which is not preferable.

As the isomerization catalyst used in the present invention, a single catalyst or a plurality of catalysts can be used. In the isomerization reaction in the present invention, the reaction temperature is 30 to 200 ° C, more preferably 80 to 150 ° C. When the reaction temperature is lower than 30 ° C., the reaction is slow. When the reaction temperature is higher than 200 ° C., a cyclic acetal is easily generated as a side reaction, which is not preferable. There is no particular limitation on the reaction pressure, and the reaction may be performed under reduced pressure, normal pressure or increased pressure. As the atmosphere of the reaction system, the reaction is performed in a stream of an inert gas, for example, nitrogen, helium, argon, or the like, and more preferably in a stream of nitrogen. As the post-treatment of the obtained polyalkylene glycol-1-alkenyl ether, only the catalyst may be separated, but if necessary, the catalyst may be separated and then purified by distillation.

[0008] The isomerization reaction in the present invention can also be carried out in an organic solvent. As the organic solvent used, for example, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, dimethoxyethane, methoxyethyl ether, ethers such as tetrahydrofuran,
Ester such as ethyl acetate and butyl acetate, acetone,
Examples thereof include ketones such as methyl ethyl ketone and alcohols such as methanol, ethanol and isopropanol.

[0009]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. The test method is shown below. (1) GC analysis The measurement was performed using a packed column under the following conditions. Column: PEG20M 2m, carrier gas: N _2,
Flow rate 50 ml / min. Injection temperature: 100
° C, detection temperature: 110 ° C, heating program: 80 ° C, 4 minutes, 8 ° C / min (2) ammonia adsorption thermal desorption spectroscopy fully automatic thermal desorption spectrometer TPD-1-AT (Nippon Bell Co., Ltd.) Amount of ammonia desorbed at a temperature of 250 ° C. or higher by the following method (hereinafter referred to as “acid point amount”).
Was measured. The catalyst 70mg helium gas 50 cm ³ /
250 ° C at a rate of 10 ° C / min while flowing at min.
After heating to 250 ° C for one hour,
The temperature was lowered to 50 ° C at a speed of
Ammonia gas is introduced to maintain 0 Torr and 10
For 1 minute, and then vacuum degassing for 1 hour.
Ammonia desorbed at a temperature of not more than ℃ was removed. Next, heating was performed from a temperature of 50 ° C. to 600 ° C. at a rate of 10 ° C./min, and the amount of ammonia (acid point amount) desorbed during the heating was measured.

(Example 1) In a 20 ml SUS autoclave, ethylene glycol monoallyl ether 5.0 was added.
4 g (49.3 mmol) and Pd-C having a metal loading of 5% by weight (NA-t manufactured by N.C.
ype) was charged and reacted at 150 ° C. for 2 hours. The catalyst was filtered off, and the product was analyzed by GC. As a result, ethylene glycol mono-1-propenyl ether was produced at a conversion of 41% and a selectivity of 100%. The E / Z ratio of the propenyloxy group was 26/74. When the acid point amount of the catalyst used in this example was measured, it was 0 mmol / g in terms of ammonia.

(Example 2) In a 20 ml SUS autoclave, ethylene glycol monoallyl ether 5.0 was added.
7g (49.6mmol) and 5% by weight of P
105.9 mg of dC (manufactured by Tanaka Kikinzoku Co., Ltd.) was charged and reacted at 150 ° C. for 1 hour. The catalyst was filtered off and the product was analyzed by GC. The conversion was 94% and the selectivity was 9
At 0%, ethylene glycol mono-1-propenyl ether was formed. The E / Z ratio of the propenyloxy group is 26 /
74. Other products are 2-ethyl-1,3-
Dioxolan. When the acid point content of the catalyst used in this example was measured, it was 3.8 × 10 ^{−2 in} terms of ammonia.
mmol / g.

(Example 3) In a 20 ml SUS autoclave, ethylene glycol monoallyl ether 5.2 was added.
0g (50.9mmol) and 5% by weight of P
d-Al ₂ O ₃ (manufactured by Tanaka Kikinzoku Co., Ltd.) at 108.2
mg, and reacted at 150 ° C. for 1 hour. The catalyst was filtered off, and the product was analyzed by GC.
Ethylene glycol mono-1-propenyl ether was formed at a selectivity of 35%. The E / Z ratio of the propenyloxy group was 40/60. Other products are 2-ethyl-
1,3-dioxolane. When the acid point content of the catalyst used in this example was measured, it was 2.7 in terms of ammonia.
× 10 ^-1 mmol / g.

(Example 4) In a 20 ml SUS autoclave, ethylene glycol monoallyl ether 2.1 was added.
5 g (21.1 mmol) and 5% by weight of P
99.3 mg of dC (manufactured by Tanaka Kikinzoku Co., Ltd.) and 4 ml of toluene were charged and reacted at 150 ° C. for 2 hours. The catalyst was separated by filtration, toluene was removed under reduced pressure, and the product was analyzed by GC. As a result, ethylene glycol mono-1-propenyl ether was produced at a conversion of 100% and a selectivity of 94%. The E / Z ratio of the propenyloxy group was 42/58. The other product was 2-ethyl-1,3-dioxolane. When the amount of acid sites of the catalyst used in this example was measured, it was found to be 3.8 × 10 ⁻² mmol / in terms of ammonia.
g.

Example 5 In a 20 ml SUS autoclave, propylene glycol monoallyl ether was added.
97 g (42.8 mmol) with a metal loading of 5% by weight
Of Pd-C (NA-C
104.5 mg) and reacted at 150 ° C. for 2 hours. The catalyst was filtered off, and the product was analyzed by GC. As a result, propylene glycol mono-1-propenyl ether was produced at a conversion of 48% and a selectivity of 100%. The E / Z ratio of the propenyloxy group was 38/62. When the acid point amount of the catalyst used in this example was measured, it was 0 mmol / g in terms of ammonia.

Example 6 In a 20 ml SUS autoclave, propylene glycol monoallyl ether was added.
108.3 mg of 24 g (45.1 mmol) and Pd-C (manufactured by Tanaka Kikinzoku Co., Ltd.) having a metal loading of 5% by weight were charged and reacted at 150 ° C. for 1 hour. The catalyst was filtered off, and the product was analyzed by GC. As a result, propylene glycol mono-1-propenyl ether was produced at a conversion of 98% and a selectivity of 92%. The propenyloxy group has an E / Z ratio of 3
0/70. Other products are 2-ethyl-4-
Methyl-1,3-dioxolane. When the acid point amount of the catalyst used in this example was measured, it was 3.8 × 10 ⁻² mmol / g in terms of ammonia.

Example 7 In a 20 ml SUS autoclave, propylene glycol monoallyl ether was added.
108 g of Pd-Al ₂ O ₃ (manufactured by Tanaka Kikinzoku Co., Ltd.) containing 84 g (41.7 mmol) and a metal loading of 5% by weight.
2 mg was charged and reacted at 150 ° C. for 1 hour. The catalyst was filtered off and the product was analyzed by GC.
% And selectivity of 40%, propylene glycol mono-1-propenyl ether was produced. E of the propenyloxy group
The / Z ratio was 39/61. The other product was 2-ethyl-4-methyl-1,3-dioxolane. When the acid point amount of the catalyst used in this example was measured, it was 2.7 × 10 ⁻¹ mmol / g in terms of ammonia.

Example 8 In a 20 ml SUS autoclave, propylene glycol monoallyl ether was added.
32 g (37.2 mmol), 95.2 mg of Pd-C (manufactured by Tanaka Kikinzoku Co., Ltd.) with 5% by weight of metal and 4 ml of toluene were charged and reacted at 150 ° C. for 2 hours.
The catalyst was removed by filtration, toluene was removed under reduced pressure, and the product was analyzed by GC. As a result, propylene glycol mono-1-propenyl ether was produced at a conversion of 100% and a selectivity of 92%. The E / Z ratio of the propenyloxy group was 40/60. Other products are 2-ethyl-4-methyl-
1,3-dioxolane. When the acid point content of the catalyst used in this example was measured, it was 3.8 in terms of ammonia.
× 10 ^-2 mmol / g.

Comparative Example 1 Ethylene glycol monoallyl ether 5.3 was placed in a 20 ml SUS autoclave.
1 g (52.0 mmol) and RuCl ₂ (PPh ₃ ) ₃
49.9 mg (prepared separately according to the description in the fourth edition of Experimental Chemistry Course 18, P261) and reacted at 150 ° C. for 2 hours to obtain a pale yellow liquid. The resulting product is GC
Analysis showed that the conversion was 100% and the selectivity was 13%.
The product other than ethylene glycol-1-propenyl ether was 2-ethyl-1,3-dioxolane. The E / Z ratio of the propenyloxy group was 44/56.

[0019]

Industrial Applicability According to the present invention, a polyalkylene glycol-2-propenyl ether isomerized in the presence of a noble metal-supported catalyst to suppress the formation of a cyclic acetal which is a side reaction, thereby achieving high selectivity and high yield. Thus, high-purity polyalkylene glycol-1-propenyl ether can be obtained industrially advantageously, so that it is extremely effective particularly in the fields of resin raw materials and reactive diluents.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Uchida 2nd station in Oita-shi, Oita Prefecture Showa Denko Oita Plant F-term (reference) 4G069 AA03 BC70A BC71A BC72A BC75A CB33 CB41 4H006 AA02 AC14 BA10 BA23 BA24 BA25 BA26 BA56 BA82 BC10 BC32 BC34 GP01 GP02 GP04 GP10 4H039 CA29 CJ10

Claims (7)

[Claims] A precious metal containing palladium is added to a carrier in an amount of 0.0
One or more catalysts loaded with 5 to 10% by weight are represented by the following general formula (I): R ¹ CH ＝ CH—CH ₂ — (OR) n—OH (I) Represents an alkylene group or a cycloalkylene group having 5 to 12 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 1 to 10
Represents an integer. ) To the polyalkylene glycol-2-alkenyl ether represented by the formula (1).
The following general formula (II), wherein the polyalkylene glycol-2-alkenyl ether is isomerized at a reaction temperature of 30 to 200 ° C. using the following weight%: R ¹ CH ₂ —CH ＝ CH— (OR) n —OH (II) (wherein, R represents an alkylene group having 2 to 4 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms; R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Is 1 to 10
Represents an integer. A method for producing a polyalkylene glycol-1-alkenyl ether represented by the formula: 2. The production of polyalkylene glycol-1-alkenyl ether according to claim 1, wherein the noble metal containing palladium is palladium or at least one noble metal selected from the group consisting of ruthenium, rhodium and platinum and palladium. Method. 3. The method for producing a polyalkylene glycol-1-alkenyl ether according to claim 1, wherein 5 to 100% by weight of the noble metal containing palladium is palladium. 4. In the ammonia adsorption thermal desorption measurement,
The amount of ammonia desorbed at 250 ° C or higher is 1 mmol / g
The method for producing a polyalkylene glycol-1-alkenyl ether according to any one of claims 1 to 3, wherein the following carrier is used. 5. In the ammonia adsorption thermal desorption measurement,
0.3mmol of ammonia desorbed at 250 ℃ or more
5. A carrier having a mass of not more than / g is used.
The method for producing a polyalkylene glycol-1-alkenyl ether described in 1 above. 6. The polyalkylene glycol-1-alkenyl ether according to claim 1, wherein the polyalkylene glycol-2-alkenyl ether is ethylene glycol monoallyl ether or propylene glycol monoallyl ether. Production method. 7. The method for producing a polyalkylene glycol-1-alkenyl ether according to claim 1, wherein the reaction is performed in an organic solvent.