JPH10101606A - Production of 1,2-butanediol mono-tertiary-butyl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the formation of a by-product and produce 1,2-butanediol mono-t-butyl ether in good yield under mild conditions by reacting 1,2-butanediol with isobutyolene using a specific resin. SOLUTION: A strongly acidic cation exchange resin is used. A styrene- divinylbenzene copolymer is preferably used as a resin to be a base material and a porous type resin is preferred. Sulfonate groups are preferred as the exchange groups. The cross-linking degree of the ion exchange resin is preferably 1-50%, more preferably 2-20%. The amount of exchange is preferably 0.1-5mequiv./ml, more preferably 0.5-4mequiv./ml. The pore distribution is preferably a porous type in which all the pores are formed of 2,000nm diameter and pores having 15-2,000nm diameter account for at least 50% of the volume thereof, more preferably a highly porous type in which pores having 15-2,000nm diameter account for at least 60% of the volume thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing 1,2-butanediol mono-t-butyl ether with a high yield by reacting 1,2-butanediol with isobutylene. 1,2-butanediol mono-
T-butyl ether is expected to be used for various solvents, detergents and the like.

[0002]

2. Description of the Related Art As a method for producing a 1,2-diol monoalkyl ether, for example, a method in which an epoxide of a corresponding diol is reacted with an alcohol under basic conditions (D. Swern et al., J. Am. Chem. Soc. ,
71, 1152 (1949)).
U.S. Pat. No. 3,317,483 for novel tertiary alkoxy ester addition polymers includes:
A method of etherifying glycol with a tertiary olefin using a cation exchange resin is described as a method for preparing a raw material monomer.

[0003]

However, in the former method, it is difficult to obtain a raw material epoxide,
In addition, there is a problem that it is expensive. On the other hand, in the latter, although there is an example of butylene glycol, only the reaction formula of isobutylene and ethylene glycol is specifically disclosed. No mention is made of the production of 1,2-butanediol mono-t-butyl ether by reaction with 2,2-butanediol, nor the formation of by-products at that time. An object of the present invention is to provide a method for industrially advantageously producing 1,2-butanediol mono-t-butyl ether by reacting 1,2-butanediol with isobutylene.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, mild conditions were obtained by reacting 1,2-butanediol with isobutylene using an ion exchange resin. Below, the diether form 1,2
The inventors have found that 1,2-butanediol mono-t-butyl ether can be obtained with a high yield while suppressing the by-products of -butanediol di-t-butyl ether and diisobutylene, and have completed the present invention. That is, the present invention resides in a method for producing 1,2-butanediol mono-t-butyl ether, which comprises reacting 1,2-butanediol with isobutylene in the presence of a strongly acidic cation exchange resin. Hereinafter, the present invention will be described in detail.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION

(Raw materials, etc.) As 1,2-butanediol used as a raw material in the present invention, not only high-purity but also crude 1,2-butanediol containing impurities can be used. For example, butadiene and acetic acid and molecular oxygen Is reacted using a noble metal-based catalyst, and a reaction product containing the obtained 1,4-diacetoxybutene-2 as a main component and containing 3,4-diacetoxybutene-1 or the like is hydrogenated and then hydrolyzed. Thus, when 1,4-butanediol is produced, crude 1,2-butanediol obtained as a by-product (JP-A-52-1)
No. 33912) is advantageous. The crude 1,2-butanediol usually has a purity of 60 to 99% by weight and contains 1-acetoxy-2-butanol, 2-acetoxy-1-butanol and 1,2-diacetoxybutane as impurities. However, it does not interfere with the etherification reaction.

The raw material isobutylene may be of high purity or a mixture obtained from a so-called butane-butene fraction. In addition, this mixture usually contains 1-butene, 2-butene, normal butane, isobutane, and butadiene in addition to isobutylene. With respect to the strongly acidic cation exchange resin, the base resin is not particularly limited, but usually, a styrene-divinylbenzene copolymer is preferably used. The copolymer includes a porous type and a gel type, but a porous type is preferred. Examples of the exchange group include a sulfonic acid group and a phosphoric acid group, and among them, a sulfonic acid group is preferable.

The degree of crosslinking of the ion exchange resin is from 1 to
50% is preferable, and 2 to 20% is more preferable. The exchange capacity is preferably 0.1 to 5 meq / ml.
5-4 meq / ml is more preferred. Regarding the pore distribution, a porous type in which all pores are formed with a diameter of 2,000 nm and at least 50% of the volume is occupied by pores having a diameter of 15 nm or more and 2000 nm or less, more preferably at least 60% % Is 15nm in diameter
A high-porous type occupied by pores having a size of from not less than 2000 nm is more preferable.

Accordingly, a resin whose appearance is light brown to brownish white and opaque is suitable for the reaction of the present invention. Specific examples of the ion exchange resin suitable for the present invention include RCP
-160M, HPK-55, PK-216 and SK-1
B (manufactured by Mitsubishi Chemical Corporation), MSC-1.88 (manufactured by Dow),
Amberlyst-16 (manufactured by Rohm and Haas) and the like.

(Reaction method) The method of etherifying 1,2-butanediol with isobutylene may be either a batch reaction or a flow reaction. In the case of a flow reaction, a fixed bed or suspension tank is used. Any of the formulas can be used, but among them, the fixed bed flow type is preferred. In the case of a batch reaction, the raw material and the catalyst are charged into a pressure-resistant reactor, and if necessary, pressurized with an inert gas such as nitrogen, and reacted while stirring at a predetermined temperature to obtain the desired 1,2-butanediol mono. A reaction mixture containing -t-butanediol mono-t-butyl ether can be obtained.

[0010] In the case of a flow-type reaction, a reaction mixture containing a target substance can be obtained by filling a pressure-resistant reaction tube with a catalyst, continuously charging raw materials, and reacting at a predetermined temperature. When the reaction is carried out under pressure, the reaction is usually carried out under a flow of an inert gas such as nitrogen, but it is not particularly necessary to carry out the reaction under a gas flow. The molar ratio of 1,2-butanediol to isobutylene is preferably in the range of 1:10 to 10: 1, more preferably 1: 2 to 5: 1. If the molar ratio of isobutylene is high, the production of diethers increases, and if the molar ratio is low, the amount of unreacted 1,2-butanediol increases and the efficiency of purification and the like decreases, which is not preferable.

The reaction temperature is not particularly limited, but is usually 0 to
120 ° C is preferred, and particularly 25 to 100 ° C is more preferred. If the reaction temperature is too low, the reaction rate is slow. On the contrary, if it is too high, the reverse reaction proceeds, and not only is 1,2-butanediol monotertiary butyl ether decomposed, but also side reactions tend to proceed, which is not preferable. The reaction pressure may be normal pressure, but it is preferable to carry out the reaction under pressure in order to keep isobutylene in a liquid state. Usually, the reaction pressure is 1 to 100 kg / c
m ² (0.1 to 10 MPa), preferably 5 to 8
0 kg / cm ² (0.5 to 8 MPa).

The reaction time is not particularly limited in the case of a batch reaction, but is usually 10 minutes to 50 hours, preferably 30 minutes to 10 hours. In the case of a flow reaction, the liquid hourly space velocity of the raw material liquid is usually 0.1 to 20 hr ^-1 , preferably 1 to 20 hr ^-1 .
〜１０10 hr ⁻¹ . After the reaction is completed, in the case of a batch reaction,
Unreacted isobutylene is separated from the reaction mixture, the catalyst is filtered off by a conventional method, and then the desired 1,2 is distilled off.
-Butanediol mono-t-butyl ether can be easily obtained. In addition, unreacted isobutylene and 1,
After the 2-butanediol is collected as it is, it can be reused as a raw material. The conversion of 1,2-butanediol is usually about 20% or more, preferably about 30% or more, and the selectivity is usually about 70% or more, preferably about 80% or more.

[0013]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, 1,2- described below
The butanediol conversion and 1,2-butanediol mono-t-butyl ether selectivity were calculated by the following equations.

[0014]

(Equation 1)

The ion exchange resins used in this embodiment are all H-type resins. Table-A below summarizes the pore distribution of the ion exchange resin determined as follows. The ion exchange resin previously dried under reduced pressure at 80 ° C. for 5 hours was subjected to a pore volume measurement apparatus (trade name: Poisizer 9) manufactured by Shimadzu Corporation.
310) by the mercury intrusion method. The contact angle of mercury at the time of measurement is 141.3 degrees and the surface tension is 480 dyne
s / cm ² was used.

[0016]

[Table 1] Table-A Types of ion exchange resins having a diameter of 2000 nm or less Appearance Total pores formed by pores Ratio of pores having a diameter of 15 nm to 2000 nm in volume SK-1B Light brown transparent 37.8 PK -216 Light brown white opaque 52.3 HPK-55 Brown white opaque 86.6 RCP-160M Brown white opaque 80.5

Example 1 In a stainless steel shaking autoclave having an internal volume of 100 cc, a high-porous cation exchange resin RCP-160M was used.
0.8 g (manufactured by Mitsubishi Chemical Corporation) 1,2-butanediol 2
5 g and 9.0 g of isobutylene were charged, and the nitrogen pressure was 40 k.
The reaction was performed at g / cm ^{2 at} a reaction temperature of 60 ° C. for 4 hours. After completion of the reaction, the reaction solution and the catalyst were separated, and the reaction solution was analyzed by gas chromatography. As a result, the conversion of 1,2-butanediol was 44 mol%, and the selectivity of 1,2-butanediol mono-t-butyl ether was 89.2 mol. %Met.

Example 2 As in Example 1, 0.8 g of a porous cation exchange resin HPK-55 (manufactured by Mitsubishi Chemical Corporation) was charged into a stainless steel autoclave, and the other conditions were the same as in Example 1. The reaction was performed. When the reaction solution was analyzed by gas chromatography, the conversion of 1,2-butanediol was 43 mol% and the selectivity of 1,2-butanediol mono-t-butyl ether was 86.4 mol%.

Example 3 As in Example 1, 0.8 g of a porous cation exchange resin PK-216 (manufactured by Mitsubishi Chemical Corporation) was charged into a stainless steel autoclave, and the other conditions were the same as in Example 1. Was done. The reaction solution was analyzed by gas chromatography to find that the conversion of 1,2-butanediol was 35 mol% and the selectivity of 1,2-butanediol mono-t-butyl ether was 81.3 mol%.

Example 4 As in Example 1, 0.8 g of the cation exchange resin RCP-160M was added to a stainless steel autoclave.
The reaction was carried out under the same conditions as in Example 1 except that 25 g of butanediol and 17.5 g of a butane-butene fraction having the composition shown in Table 1 were charged. The reaction mixture was analyzed by gas chromatography to find that the conversion of 1,2-butanediol was 42 mol% and the selectivity of 1,2-butanediol mono-t-butyl ether was 89.3 mol%.

[0021]

TABLE 1 Isobutylene 46.4 wt% 1-butene 22.6 wt% c-butene 8.0 wt% t-butene 9.7 wt% n-butane 9.2 wt% Isobutane 2.1 wt% % Other 2.0% by weight

Example 5 In Example 1, 30 g of crude 1,2-butanediol having the composition shown in Table 2 (1,2-butanediol component: 25 g) was used instead of 1,2-butanediol. The reaction was carried out under the same conditions as in Example 1 except for charging. At this time, the conversion of 1,2-butanediol was 46%,
Butanediol mono-t-butyl ether selectivity88.
It was 1 mol%.

[0023]

TABLE 3 1,2-butanediol 81.9% by weight 1,2-diacetoxybutane 0.2% by weight 1-acetoxy-2-hydroxybutane 1.2% by weight 2-acetoxy-1-hydroxy Butane 11.8% by weight Others 4.9% by weight

Example 6 A cation exchange resin RCP-160M was placed in a stainless steel reaction tube having an inner diameter of 12 mm (effective sectional area of 1.005 cm ² ).
0 cc, reaction pressure 60 kg / cm ² , reaction temperature 7
At 3 ° C., 27 cc / hour of isobutylene (0.28 mol / hour), 104 cc / hour of 1,2-butanediol (1.
(15 mol / h) and nitrogen at a flow rate of 5 NL / h to carry out the reaction. The product liquid 24 hours after the start of the reaction was analyzed by gas chromatography to find that the conversion of 1,2-butanediol was 27 mol% and that of 1,2-butanediol mono-
The t-butyl ether selectivity was 79.3 mol%.

Example 7 In Example 6, instead of 1,2-butanediol, crude 1,2-butanediol having the composition shown in Table 2 was added at 104 cc / hour (1,2-butanediol component: 0 .9
The reaction was carried out under the same conditions as in Example 6, except that the reaction was fed at 5 mol / hour). At this time, the conversion of 1,2-butanediol was 25%, and the selectivity for 1,2-butanediol mono-t-butyl ether was 70.7 mol%.

Example 8 As in Example 1, a gel type cation exchange resin SK-1B (manufactured by Mitsubishi Chemical Corporation) was placed in a stainless steel autoclave.
The reaction was carried out under the same conditions as in Example 1 except for charging 8 g. When the reaction solution was analyzed by gas chromatography, the conversion of 1,2-butanediol was 17 mol%,
2-butanediol mono-t-butyl ether selectivity 7
1.6 mol%.

[0027]

According to the method of the present invention, by reacting 1,2-butanediol with isobutylene in the presence of a cation exchange resin, the secondary reaction of 1,2-butanediol di-t-butyl ether can be carried out under mild conditions. Suppress the raw, high yield 1,
2-butanediol mono-t-butyl ether can be produced.

Claims (4)

[Claims] 1. A method for producing 1,2-butanediol mono-t-butyl ether, comprising reacting 1,2-butanediol with isobutylene in the presence of a strongly acidic cation exchange resin. 2. The ion exchange resin, wherein all pores are formed by pores having a diameter of 2000 nm or less, and at least 50% of the volume thereof has a diameter of 15 nm to 2000 nm.
The method according to claim 1, wherein an ion exchange resin occupied by pores of nm or less is used. 3. As a raw material 1,2-butanediol,
1,4-diacetoxybutene obtained by reacting butadiene with acetic acid and molecular oxygen using a noble metal catalyst.
The method according to claim 1, wherein the reaction product containing 2 and 3,4-diacetoxybutene-1 is hydrogenated and then hydrolyzed, and then crude 1,2-butanediol obtained by distillation is used. . 4. The method according to claim 1, wherein a butane-butene fraction is used as the starting material isobutylene.