JPH0198624A - Production of polyether - Google Patents

Abstract

PURPOSE:To obtain a narrow-MW distribution polyether in good yields, by performing the polymerization through ring opening in the presence of boron trifluoride and water in producing a polyether by polymerizing tetrahydrofuran or a mixture thereof with an alkylene oxide through ring opening. CONSTITUTION:A polyether is produced by polymerizing tetrahydrofuran or a mixture thereof with a copolymerizable alkylene oxide through ring opening. Said ring opening polymerization is performed in the presence of boron trifluoride and water. It is possible to increase further effects such as an increased product yield and the formation of a narrowed MW distribution, by performing said ring opening polymerization in the presence of clay in addition to boron trifluoride and water. They are usually used in such a ratio that about 0.1-10% boron trifluoride, about 0.05-3% water and about 0.1-10% clay are present based on the weight of the polyether.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to a method for producing polyether.

[Prior Art] Conventionally, tetrahydrofuran (abbreviated as THF) or T1
(Tin tetrahydride, aluminum chloride, boron fluoride, sulfuric acid-acetic anhydride, fluoro[1 sulfuric acid, acid-activated bleaching earth (montmorillon) using a mixture of F and other alkylene oxides (abbreviated as AO) as catalysts. There is a technique for producing polyether by ring-opening polymerization using a Lewis acid such as (e.g. Japanese Patent Application Laid-Open No. 57-80337, U.S. Pat. No. 4,127).
, 513 and U.S. Pat. No. 4,228,272, W.).

[Problems to be Solved by the Invention] However, in this method, the molecular weight distribution ωW/MN) tends to be wide, for example, from 1.5 to 2.0. Moreover, if the conversion rate of THF is lower than that, the product yield will be poor.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive studies on a method for producing a polyether with a narrow molecular weight distribution that increases the product yield. That is, the present invention provides a method for producing polyether by ring-opening polymerization of a mixture of TI (F or THF and AO copolymerizable with the same) and hydrolyzing it with an alkaline aqueous solution if necessary. (BF3) and a method for producing polyether (first invention) characterized in that the process is carried out in the presence of water, and ring-opening polymerization of THF or a mixture of THF and AO copolymerizable with the same is carried out in the presence of an alkaline aqueous solution if necessary. A method for producing polyether by hydrolysis (second invention) characterized in that ring-opening polymerization is carried out in the presence of [3F3, water and clay].

The THF used in the present invention can be obtained by ring-closing and dehydrating 1,4-butanediol using a known method. Furthermore, unreacted 'I'HF recovered after polymerization and purified by a known method can also be used. The water content of THF is usually 0.03% or less at the level of general commercial products, but it is not necessarily necessary to refine it to this extent, and up to 1% is allowed.

AO includes alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide (abbreviated as EO), propylene oxide (abbreviated as PO), 1,2-11,3-12,3-butylene oxide, and combinations of two or more of these. can be mentioned. Among these, preferred are EOlPO and E
It is a combination of O and PO.

8F3 can be used with BF3 alone, but it is difficult to handle, so BF
3-TI-IF or BF3-water is preferred.

In the present invention, by adding clay in addition to BF3 and water, the effect of increasing the product yield and obtaining a polyether with a narrow molecular weight distribution can be further improved.

Examples of this clay include activated clay, such as one obtained by acid treatment of a raw material containing montmorillonite clay as a main component. The chemical composition of activated clay is usually silicic acid (S 102) 6
0-90%, preferably 70-80%, alumina (A1
203) 5-25%, preferably 9-13%, iron oxide (
Fe203) 1-10%, preferably 4-6%,
MgO) 0.1-5%, preferably 1-2%, lime (C
aO) 0.1-5%, preferably 1-2%. Specifically, there is Galleon Earth [Mizusawa Chemical Co., Ltd.].

When producing polyether, the molar ratio of THF2-AO is usually 100:0 to 1:99, preferably ioo
:o~5:95.

The amount of 8F3 is usually 0.1 based on the weight of the polyether.
-10%, preferably 0.2-5%. BFa is 0
．． If it is less than 1%, the THF conversion rate will be low and it will be difficult to obtain the desired polyether, and if it exceeds 10%, the catalytic effect will not improve.

The amount of water is usually 0°05~ based on the weight of the polyether.
3%, preferably 0.1 & 2.5%. Water is 0.0
If it is less than 5%, it is difficult to control the moisture content, and if it exceeds 3%, the molecular weight becomes small, making it difficult to control the molecular weight.

The amount of clay is usually from 0.1 to 0.1 based on the weight of polyether.
10%, preferably 2-6%. If the clay content is less than 0.1%, the catalytic effect will be small, and if it exceeds 10%, the catalytic effect will not improve.

The amounts of BFg, water, and clay are usually 2 to 90%, preferably 3 to 75%, based on the total weight of BF3, water, and clay. If the amount of BF3 is less than 2%, T
) The conversion rate of IF is low and it is difficult to obtain the desired polyether, 9
Even if it exceeds 0%, the catalytic effect will not improve. Water claws are usually 1
-50%, preferably 1.5-40%. If the amount of water is less than 1%, it is difficult to control the moisture content, and if it exceeds 50%, the molecular weight becomes small, making it difficult to control the molecular weight. The amount of white clay is usually 0 to 95%, preferably 2 to 95%.
%, more preferably 30 to 90%.

If the amount of clay is less than 2%, the catalytic effect will be small, and if it exceeds 95%, the catalytic effect will not improve.

When performing ring-opening polymerization of THF and AO, method of ring-opening polymerization of THF and AO, method of ring-opening polymerization of AO to a polymer of TIIF, method of ring-opening polymerization of AO to a polymer of AO, method of ring-opening polymerization of THF and AO, method of ring-opening polymerization of AO to a polymer of AO,
A method such as ring-opening polymerization of F can be used.

Among these, preferred are a method of ring-opening polymerization of THF and a method of ring-opening polymerization of THF and AO.

The order in which 8F3, water, and clay are added to THF or TIF and AO is not particularly limited, and examples include a method of adding them separately in any order, a method of adding them at the same time, a method of adding them after mixing in advance, and the like.

8F3, the temperature at which water and clay are added to THF is usually 0~
The temperature is 50°C, preferably 10-40°C. If the temperature is lower than 0°C, polymerization initiation will be slow, and if the temperature is higher than 50°C, undesirable side reactions such as coloring will occur.

The reaction temperature is usually -10 to 80°C, preferably 10 to 65°C.
It is °C. If the reaction temperature is less than 110°C, polymerization is slow and is disadvantageous for industrial production. When the reaction temperature is higher than 80°C, the apparent polymerization rate increases, but the polymerization yield decreases. In addition, it is difficult to adjust the molecular weight due to chain transfer reactions, resulting in deterioration of quality such as coloring. The reaction temperature may be adjusted by a conventional method, for example, by cooling the reactor using cooling water.

The reaction time can be varied depending on the amount of BF3, water and clay, reaction temperature, etc., but is usually 1 to 24 hours.
Preferably it is 1 to 10 hours. Even if the reaction time is longer than 24 hours, the polymerization yield will not be improved due to equilibrium polymerization.

The reaction can be carried out at normal pressure or under elevated pressure.

The reaction is usually carried out in an atmosphere of inert gas (such as nitrogen gas).

When the polymerization reaction is completed, the reaction can be stopped by adding an aqueous alkali solution (caustic soda, sodium carbonate, etc.) to neutralize the BF3. Neutralization is simply done at room temperature, heated and mixed, 'J! R
, it is done by doing. Subsequently, the generated neutralized salt can be separated and removed by using an adsorbent such as activated clay, alumina oxide, or magnesium oxide-alumina oxide (synthetic product). Unreacted THF can be recovered by distillation.

The number average molecular weight of the obtained polyether is usually 500 to s.
, ooo, preferably 500 to 6,000, particularly preferably 1.000 to 4.000.

Polyether has the general formula % formula % (1) (wherein A is an alkylene group having 2 to 4 carbon atoms, m is 1 to 1
An integer of 00, n is an integer of 0 to 150. The n oxyalkylene groups may be the same or different.

(2) CH2CH2CH2CH20 and n A○ may be randomly combined, block combined, or a combination thereof.

) can be shown.

[Example] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Parts in Examples are parts by weight. Example I 688 parts (9.56 mol) of THF was charged into a pressurized reactor, 24 parts of BF3-THF complex and 6.8 parts of water were added, and after replacing with N2, It takes 1.5 hours at ~30°C and 1 EO
After adding 44.6 parts dropwise and reacting, it was aged at the same temperature for 0.3 hours, and after neutralization by adding 25 parts of 48% Na011 aqueous solution,
Unreacted THF was distilled off under reduced pressure at ~100°C. 659 parts of polyether glycol was obtained by filtering the alumina oxide through Brecot. The conversion rate of THF at this point was 75%. The molecular weight determined from the hydroxyl value was 2150 (hydroxyl value 52.4). MW/MN is shown in Table-1.

Example 2 [3F3-THF, water, and reaction temperature were changed as shown in Table 1, but the reaction, neutralization, and purification were carried out in the same manner as in Example 1 to obtain polyether glycol. The molecular weight and MW/MN are shown in Table-1.

Example 3 688 parts (9.56 mol) of THF was charged into a pressurized reactor, 30 parts of BF3-T)IF complex, 2.5 parts of water and 40 parts of clay were added, and after N2 substitution, the temperature was 20-30°C. After 1.5 hours of reaction, 144.6 parts of EO was added dropwise and the mixture was aged for 0.3 hours at the same temperature.

After the reaction was completed, unreacted THF was distilled off under reduced pressure at 50 to 100°C. 665 parts of polyether glycol was obtained by precoating with magnesium oxide-alumina oxide (synthetic product, KW-1000 manufactured by Kyowa Chemical Industry Co., Ltd.) and filtering. The conversion rate of T)IF at this time was 76%. The molecular weight determined from the hydroxyl value was 2877 (hydroxyl value 39.0). MN/MN is shown in Table-1.

Examples 4 and 5 Polyether glycols were obtained by reaction and purification in the same manner as in Example 3, except that 8F3-THF, water, clay, and reaction temperature were changed as shown in Table 1. Their molecular weights and MW/MN are shown in Table-1.

Comparative Example I 688 parts (9.56 mol) of THF was poured into a pressurized reactor and acid clay (moisture 0.1%) was dried at 150°C for 4 hours.
) and 28.5 parts of ethylene glycol,
After N2 substitution, it took 24 hours at 20-40℃ and 20
After dropping 2 parts to react, it was aged at the same temperature for 6 hours, and 5 parts
After distilling off unreacted EO and TIIF under reduced pressure at 0 to 100°C, acid clay was removed by filtration to obtain 470 parts of polyether glycol. At this time, Tl(F
The conversion rate was 42%. The molecular weight determined from the hydroxyl value was 1021 (hydroxyl value 110). MW/MN is shown in Table 1ζ.

Comparative Example 2 28.7 parts of ethylene glycol, 3.0 parts of tin tetrahydride, and 688 parts of THF were charged into a pressurized reactor, and after N2 substitution,
202 parts of EO was added dropwise to react at 30 to 40°C over 15 hours.

After the reaction, it was aged for 6 hours at the same temperature, and the unreacted F was distilled off under reduced pressure at 50-100°C. A 5% aqueous solution of I carbonate was added, neutralized, dehydrated, and filtered to give 633 parts. Polyether glycol was obtained. The conversion rate of THF at this time was 59
%Met. Also, the molecular weight determined from the hydroxyl value is 1
380 (hydroxyl value 81). MW/MN is shown in Table-1.

Table-1 Table-1 (continued) Table-1 (continued) The details of the analysis of and EO content are as follows. .

Catalyst 1: BF3-THF complex 2: White clay [Galleon Earth (Mizusawa Chemical Co., Ltd.) Rich: White clay [
Galleon Earth (manufactured by Mizusawa Chemical Co., Ltd.)] was dried at 150° C. for 4 hours to reduce the moisture content to 0.1%.

424 Lead chloride analysis method M'J/MN (molecular weight distribution'): G, P, C (HLC-802UR manufactured by Toyo Soda Co., Ltd.) EO-containing ffi: NMR (XL- manufactured by VARIAN)
300) [Effect of the invention 1. The present invention has a high conversion rate of THF (for example, 60 to 80
%), this is a manufacturing method with a high product yield.

2. The present invention is a manufacturing method that can produce polyether with a narrow molecular weight distribution.

3. The production time of polyether is short in the present invention.

4. In the present invention, the catalyst can be removed by neutralization or by using an adsorbent, and can be carried out with a simple operation without generating almost any waste liquid, unlike the conventional methods of washing with water and liquid separation.

In addition, the collected white clay can be reused or disposed of as is.

5. The present invention can produce polyethers with low molecular weight and low total EO content.

Claims (1)

[Claims] 1. A method for producing a polyether by ring-opening polymerization of tetrahydrofuran or a mixture of tetrahydrofuran and an alkylene oxide copolymerizable with the same, wherein the ring-opening polymerization is carried out in the presence of boron trifluoride and water. A method for producing polyether, characterized by carrying out the following steps: 2. The manufacturing method according to claim 1, wherein the amount of boron trifluoride is 0.1 to 10% based on the weight of the polyether. 3. The amount of water is 0.05~ based on the weight of polyether
3% of the manufacturing method according to claim 1 or 2. 4. In a method for producing a polyether by ring-opening polymerization of tetrahydrofuran or a mixture of tetrahydrofuran and an alkylene oxide copolymerizable with the same, the ring-opening polymerization is carried out in the presence of boron trifluoride, water and clay. Characteristic polyether manufacturing method. 5. The amount of clay is 0.1 to 0.1 based on the weight of polyether
10% of the manufacturing method according to claim 4.