JPH10298172A - Production of alfa-methylene-gamma-butyrolactones - Google Patents

Abstract

PROBLEM TO BE SOLVED: To readily obtain α-methylene-γ-butyrolactones useful as a monomer for a resin from a cheap raw material in high selectivity by carrying out a gas phase catalytic reaction of specific γ-butyrolactones with aldehydes in the presence of a catalyst of a specified composition. SOLUTION: The objective compound of formula II is obtained by carrying out a gas phase catalytic reaction of a raw material containing (A) a γ- butyrolactone of formula I (R<1> to R<4> are each H, a 1-18C alkyl) and capable of having a 1-18C alkyl substituted at β-position and γ-position, and (B) formaldehyde (derivative) in the presence of (C) a catalyst of the composition of the formula Sia Csb Wc Xd Oe [X is Ag, Nb, Mg, Al, Ni, Zn, Mo, Cr, Sb, Ti, or Pt; (a), (b), (c) and (d) are each 100, 0-10, 10-0 and 0-10 respectively; (e) is a number of oxygen atoms satisfying atomic valences of Si, Cs, W and X components].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an α-butyrolactone and an alkyl-substituted γ-butyrolactone (hereinafter referred to as γ-butyrolactones) which are subjected to a gas phase contact reaction with formaldehyde or a formaldehyde derivative (hereinafter referred to as formaldehydes). A process for producing methylene-γ-butyrolactones.

[0002]

2. Description of the Related Art α-methylene-γ-butyrolactones have been studied for a long time because they have physiological activity (Q. Rev. Chem. Soc., 21, 331 (1)
967)). In recent years, the possibility of use as a monomer for resins has been reported (Macromolecules. 12, 54).
6 (1979)), and is also known to have good copolymerization properties with monomers such as methyl methacrylate and styrene (J. Polym. Sci., Polym. C).
hem. Ed, 20, 546 (1979)).

The above document (Macromolecule)
s, 12, 546 (1979)), the Tg of a homopolymer of α-methylene-γ-butyrolactone is 19
Although it is reported to be 5 ° C. and has properties as a heat-resistant polymer, it has not yet been used as a general-purpose polymer because a method for producing an inexpensive monomer has not been established at present.

[0004] Methods for producing α-methylene-γ-butyrolactone have been studied for a long time, and their production methods are also diverse (Angn. Chem. Int. Ed. Eng.
l. , 24, 94 (1985) and Synthetic Organic Chemistry Association, Vol. 39, No. 5, (1981)). The main five synthesis methods known in the literature are as follows.

(1) A method of formylating γ-butyrolactone with a formate in the presence of sodium hydride (NaH), followed by reduction with Raney nickel or the like, followed by dehydration (J. Chem. Soc., Chem. Commu).
n. , 531 (1965)).

(2) A method in which γ-butyrolactone is anionized with a strong base such as lithium diisopropylamine, then reacted with formalin and dehydrated (J. Chem. S.
oc. Chem. Commun. , 1317 (197
2)).

(3) A method of reacting γ-butyrolactone with diethyl oxalate in the presence of sodium ethylate and then reacting with formalin (J. Org. Chem., 4
2, 1180 (1977)).

(4) A method of synthesizing γ-bromomethyl acrylate with formalin by a Reformatsky reaction (J. Med. Chem., 23, 1031)
(1980)).

(5) A method of reacting 1-butyn-4-ol with carbon monoxide in the presence of a palladium catalyst (J. Am. Ch.
em. Soc. , 103, 7520 (1981)).

[0010] However, these methods have the drawback that the production cost is high when applied to industrial production because the steps are complicated and the reagents used are expensive.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing α-methylene-γ-butyrolactone by a simple process using inexpensive raw materials.

[0012]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and found that γ-butyrolactone and formaldehyde are subjected to a gas phase contact reaction in the presence of a catalyst having a specific composition. As a result, they found that the corresponding α-methylene-γ-butyrolactones could be obtained with good selectivity, and completed the present invention.

That is, in the present invention, the β-position and / or the γ-position may be substituted with an alkyl group having 1 to 18 carbon atoms.
- and butyrolactone, the raw material gas containing formaldehyde or formaldehyde derivatives, the general formula _{Si a Cs b W c X d} O e ( respectively in Si, Cs, W and O wherein silicon, cesium, shows tungsten and oxygen, X Is silver, niobium,
It represents at least one element selected from the group consisting of magnesium, aluminum, nickel, zinc, molybdenum, chromium, antimony, titanium and platinum. Where a
= 100, b = 0 to 10, c = 1 to 10, d = 0
And e is the number of oxygen atoms required to satisfy the valence of each component. ) In the presence of a catalyst represented by
Α-methylene-γ characterized by performing a gas phase contact reaction
The present invention relates to a method for producing butyrolactones.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The γ-butyrolactone used as a reaction raw material in the present invention has a γ-position in which the β-position and / or γ-position may be substituted by an alkyl group having 1 to 18 carbon atoms.
-Butyrolactone, which is a compound group represented by the following general formula (I).

[0015]

Embedded image (In the formula, R ^{1 to} R ⁴ each independently represent hydrogen or an alkyl group having 1 to 18 carbon atoms.)

The corresponding α-methylene-γ-butyrolactone obtained by the reaction with formaldehyde is represented by the following general formula (II).

[0017]

Embedded image (In the formula, R ^{1 to} R ⁴ are as defined above.)

Preferred examples of the γ-butyrolactone include γ-butyrolactone, β-methyl-γ-butyrolactone, β-ethyl-γ-butyrolactone, β-propyl-γ-butyrolactone, β-butyl-γ-butyrolactone, β -Pentyl-γ-butyrolactone, β-hexyl-γ-butyrolactone, β-heptyl-γ-butyrolactone, β-octyl-γ-butyrolactone, β-nonyl-γ-butyrolactone, β-decyl-γ-butyrolactone, β-dimethyl -Γ-butyrolactone, β-diethyl-γ-butyrolactone, β-dipropyl-γ-butyrolactone, β-dibutyl-γ-butyrolactone, β-dipentyl-γ-butyrolactone, β-dihexyl-γ-butyrolactone, β-diheptyl-γ -Butyrolactone,
β-dioctyl-γ-butyrolactone, β-dinonyl-
γ-butyrolactone, β-didecyl-γ-butyrolactone, γ-methyl-γ-butyrolactone, γ-ethyl-γ
-Butyrolactone, γ-propyl-γ-butyrolactone, γ-butyl-γ-butyrolactone, γ-pentyl-
γ-butyrolactone, γ-hexyl-γ-butyrolactone, γ-heptyl-γ-butyrolactone, γ-octyl-γ-butyrolactone, γ-nonyl-γ-butyrolactone, γ-decyl-γ-butyrolactone, γ-dimethyl-
γ-butyrolactone, γ-diethyl-γ-butyrolactone, γ-dipropyl-γ-butyrolactone, γ-dibutyl-γ-butyrolactone, γ-dipentyl-γ-butyrolactone, γ-dihexyl-γ-butyrolactone, γ-
Diheptyl-γ-butyrolactone, γ-dioctyl-γ
-Butyrolactone, γ-dinonyl-γ-butyrolactone, γ-didecyl-γ-butyrolactone and the like. In the present invention, the raw material formaldehyde is gaseous or an aqueous formaldehyde solution. Examples of the formaldehyde derivative include hemiacetal of formaldehyde and an alcohol having 1 to 10 carbon atoms, methylal, trioxane, paraformaldehyde and the like. These may be used by mixing with formaldehyde or an aqueous formaldehyde solution.

In the reaction of the present invention, the above-mentioned γ-butyrolactones and formaldehydes are vaporized to obtain a raw material gas. The molar ratio of [gamma] -butyrolactone to formaldehyde in the raw material gas is suitably from 1:20 to 10: 1, and particularly preferably from 1:15 to 5: 1.

Further, the raw material gas may contain oxygen, water, methanol and the like, and may be diluted with an inert gas such as nitrogen and carbon dioxide.

In particular, molecular oxygen has the effect of burning off high-boiling substances adhering to the catalyst, which will be described later, in the reaction process, and maintaining the catalytic activity by maintaining the oxidation-reduction state of the catalyst on the oxidation side. It is preferable to include it in the raw material supply gas. In this case, the content of molecular oxygen is preferably from 0.1 to 10% by volume in the raw material gas. In addition, water, methanol, and the like derived from the raw material of formaldehyde may be contained in the raw material gas, but these do not particularly hinder the reaction.

The starting compounds used for preparing the catalyst used in the present invention include nitrates, carbonates, ammonium salts, halides, oxides and the like of each element, and these can be used in combination. Although the catalyst used in the method of the present invention is effective even without a carrier, magnesium oxide,
It can also be supported on a carrier such as titanium oxide. The supporting method is not particularly limited, but various methods such as an impregnation method, a kneading method, and a coprecipitation method can be used. In the process of the present invention, the catalyst is generally used in a fixed bed, but can also be used in a fluidized bed.

The reaction temperature of the gas phase contact reaction is 200 ° C. to 50 ° C.
It can be selected in the range of 0 ° C.,
0 ° C. is preferred. Space velocity (SV) on the catalyst is 20-2
0000 ml / hr / ml-cat. Can be selected in the range of 2000 to 6000 ml / hr / ml.
-Cat. Is preferable.

[0024]

EXAMPLES The method of the present invention will be described in more detail with reference to examples. In the description, the conversion of γ-butyrolactones and the selectivity of generated α-methylene-γ-butyrolactones are defined as follows.

[0025]

(Equation 1)

[0026]

(Equation 2)

Example 1 2.6 parts (parts by weight, hereinafter the same) of cesium nitrate and 3.5 parts of ammonium paratungstate were added to 200 parts of pure water and mixed while heating. After 100 parts of 20% silica sol was added thereto with stirring, the mixture was heated and evaporated to dryness. The solid obtained is 1
After drying at 20 ° C. for 17 hours, pressure molding is performed, and 50
A material heat-treated at 0 ° C. for 5 hours was used as a catalyst. The composition of the elements other than oxygen in the obtained catalyst (the same applies hereinafter) is Si
This catalyst was charged to a reactor with ₁₀₀ Cs ₄ W ₄ , and 1.9% of γ-butyrolactone and 9.5 of formaldehyde were molar fractions.
%, Water 26.8%, nitrogen 59.9% and oxygen 1.9% at a reaction temperature of 330 ° C. and a space velocity of 2500 ml / h.
r / ml-cat. Supplied with After 30 minutes from the start, the reaction product was collected with ice water and analyzed by gas chromatography. As a result, the conversion was 47.3% and the selectivity was 57.1.
%Met.

The products other than α-methylene-γ-butyrolactone in the reaction product are mainly carbon dioxide, and the produced α-methylene-γ-butyrolactone is distilled under reduced pressure (0.3 mmHg, bp. (55-58 ° C.), and the spectrum data and the like all agreed with the literature values.

In the following examples, the products other than the target product in the reaction products were mainly carbon dioxide.

[Examples 2 to 5] The catalyst of Example 1 was charged into a reactor and operated in the same manner as in Example 1 to react under the raw material composition and reaction conditions shown in Table 1. Rate and selectivity were obtained.

Example 6 Using the catalyst of Example 1, trioxane was used in place of formaldehyde, and the reaction was carried out in the same manner as in Example 1 under the reaction gas composition and reaction conditions shown in Table 1. Was obtained.

Example 7 0.65 parts of cesium nitrate and 3.5 parts of ammonium paratungstate were mixed with pure water 20
0 parts and mixed while heating. After 100 parts of 20% silica sol was added thereto with stirring, the mixture was heated and evaporated to dryness. The obtained solid was dried at 120 ° C. for 17 hours, press-molded, and heat-treated at 500 ° C. for 5 hours in an air stream to use as a catalyst. The composition of elements other than oxygen in the obtained catalyst was Si ₁₀₀ Cs ₁ W ₄ . Example 1 was prepared using this catalyst under the reaction gas composition and reaction conditions shown in Table 1.
The reaction was carried out in the same manner as described above, and the results shown in Table 1 were obtained.

Example 8 3.9 parts of cesium nitrate and 3.5 parts of ammonium paratungstate were mixed with 200 parts of pure water.
And mixed while heating. After 100 parts of 20% silica sol was added thereto with stirring, the mixture was heated and evaporated to dryness. The obtained solid was dried at 120 ° C. for 17 hours, press-molded, and heat-treated at 500 ° C. for 5 hours in an air stream to use as a catalyst. The composition of elements other than oxygen in the obtained catalyst was Si ₁₀₀ Cs ₆ W ₄ . Using this catalyst, a reaction was performed in the same manner as in Example 1 under the reaction gas composition and reaction conditions shown in Table 1, and the results shown in Table 1 were obtained.

Example 9 Using the catalyst of Example 1, γ-valerolactone was used in place of γ-butyrolactone used in Example 1, and the reaction gas composition and reaction conditions shown in Table 1 were used. The reaction was carried out in the same manner to obtain α-methylene-γ-methyl-γ-butyrolactone at the conversion and selectivity shown in Table 1.

Example 10 Using the catalyst of Example 1, γ-undecalactone was used in place of γ-butyrolactone used in Example 1, and the reaction gas composition and reaction conditions shown in Table 1 were used. The reaction was carried out in the same manner as in the above, and α-methylene-γ-heptyl-γ
-Butyrolactone was obtained.

[0036]

[Table 1]

[0037]

According to the present invention, .alpha.-methylene-.gamma.-butyrolactone can be produced from .gamma.-butyrolactone or an alkyl-substituted product thereof by a simple process using inexpensive raw materials.

Claims (1)

[Claims] (1) the β- and / or γ-position has 1 to 1 carbon atoms;
8 and may γ- butyrolactone which may be substituted with an alkyl group, a raw material gas containing formaldehyde or formaldehyde derivatives, the general formula _{Si a Cs b W c X d} O e ( wherein Si, Cs, W and O X represents silver, niobium, and silicon, cesium, tungsten, and oxygen, respectively.
It represents at least one element selected from the group consisting of magnesium, aluminum, nickel, zinc, molybdenum, chromium, antimony, titanium and platinum. Where a
= 100, b = 0 to 10, c = 1 to 10, d = 0
And e is the number of oxygen atoms required to satisfy the valence of each component. ) In the presence of a catalyst represented by
Α-methylene-γ characterized by performing a gas phase contact reaction
-A method for producing butyrolactones.