JPS6048942A - Production of diol - Google Patents

Abstract

PURPOSE:To produce a diol useful as a raw material of polyurethane, polyester resin, etc., with little production of by-products, by reacting bisphenol A with a specific amount of an alkylene oxide in a specific amount of water in the presence of an alkali catalyst under mild condition. CONSTITUTION:A diol is produced from a bisphenol A-alkylene oxide adduct obtained by the addition of 1mol of bisphenol A with >=2mol of an alkylene oxide. The above reaction is carried out by reacting 1mol of bisphenol A with essentially 2mol of the alkylene oxide (preferably a C2-4 alkylene oxide) at about 100-150 deg.C in a mixture of water (about 5-50wt%, preferably about 8-40wt% based on the bisphenol A) and an alkali catalyst (preferably an alkali metal hydroxide), or by reacting 1mol of bisphenol A with about 1-2mol of an alkylene oxide, dehydrating the product, and reacting the product with the alkylene oxide until the objective diol is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diols comprising bisphenol A-alkylene oxide adducts.

Diols obtained by adding alkylene oxide to bisphenol A, that is, 2,2-bis(4'-hydroxyphenyl)propane, are compounds represented by the following formula [1], and are compounds such as polyurethane resins and polyesters. It is used as a raw material for resins and other synthetic resins, as a lubricant, and for other purposes.

H3 R: Alkylene group with carbon a2-4 m, n: an integer of 1 or more The method of adding alkylene oxide to bisphenol A is usually obtained by dissolving bisphenol A in a solvent and reacting the alkylene oxide in the presence of a catalyst. It will be done. It is also possible to directly react alkylene oxide with bisphenol A without a solvent, but since the melting point of bisphenol A is approximately 155-156°C, it is necessary to raise the reaction temperature, and the reaction conditions are severe and by-products are also produced. easy. Solvents that can dissolve bisphenol A, such as toluene, hydrocarbons, alcohols, and organic solvents such as ketones, are used as solvents, but the solvents are flammable, the recovery of the solvent is complicated, and the solvent It is difficult to achieve sufficient economic efficiency due to reasons such as the difficulty in sufficiently recovering . Moreover, alcohols are alkylene oxide reactive, and it is not possible to selectively react only bisphenol A with alkylene oxide.

The present inventor investigated a method of reacting alkylene oxide with bisphenol A, and found a method of reacting a specific amount of alkylene oxide in the presence of a catalyst using a specific amount of water as a medium. It is insoluble, and water cannot be considered a solvent in the usual sense in the present invention. Also, like alcohols, water is reactive with alkylene oxides and tends to produce alkylene glycols and even polyalkylene glycols as by-products. However, according to the method of the present invention, it is surprising that the by-products of alkylene glycols and polyalkylene glycols are not produced. It was confirmed that there were almost no such cases. Moreover, the reaction temperature is below the melting point of bisphenol A, and the reaction can be carried out under milder conditions than in a reaction without a solvent. The present invention is a method having the above characteristics, that is, a method for producing diols consisting of bisphenol A-alkylene oxide adducts in which 2 or more moles of alkylene oxide are added to 1 mole of bisphenol A. Bisphenol A1 is added to a mixture of water of about 5 to 50% by weight based on A and an alkali catalyst at a temperature of about 100 to 150°C.
mol of alkylene oxide, or reacting 1 mole of bisphenol A with about 1 mole or more to less than 2 moles of alkylene for dehydration, and then reacting the alkylene oxide until the desired product is formed. It's only 1% that it reacts! : Bisphenol A
- A method for producing diols comprising alkylene oxide additives.

It is.

The method of the present invention is a one-stage method in special cases, and a two-stage method in other cases. A special case is a compound where m=n=1 in the above formula (1) (i.e., 2,2-bis(4'-hydroxyalkoxyphenyl)propane).
So, if this is produced by only the first reaction, 0
That is, bisphenol A, 5 to bisphenol A
50 parts of water and a mixture of alkaline catalyst and about 1
This is a method in which substantially 2 moles of alkylene oxide are reacted with 1 mole of bisphenol A at a temperature of 00 to 150°C. In other cases, even if the desired product is a compound of the formula [D with m=n==1, the method involves reacting alkylene oxide in two stages. Like this 1
The reason for the step or two-stage method is that in the method of the present invention, it is necessary to react only up to 2 moles of alkylene oxide per mole of bisphenol A in the first stage. If the reaction amount of alkylene oxide exceeds 2 moles, the amount of by-products such as alkylene glycol will increase. However, as long as the amount of alkylene oxide in the reaction does not exceed 2 moles, there is no risk that by-products such as alkylene glycol will be produced even if water is present at a ratio of approximately 50% by weight to bisphenol A. It has been confirmed that there is almost no reaction. The lower limit of the reaction amount of alkylene oxide in the first stage is about 1 mole of alkylene oxide per 1 mole of bisphenol A. The reason for this is that if the amount of alkylene oxide added to bisphenol A is too small, the viscosity of the reactant after dehydration will be extremely high, making it difficult to carry out the addition reaction of alkylene oxide in the second stage reaction. Therefore, the amount of alkylene oxide added in the first stage is approximately 1 mole per mole of bisphenol A.

In particular, the lower limit is about 1.2 mol.

The amount of water used is about 5 to 50% by weight based on bisphenol 8; if it is less than this range, the reaction temperature needs to be raised, and there is no big difference from the reaction without solvent. In addition, if the amount exceeds this range, by-products such as alkylene glycol are likely to be rapidly generated. The preferred amount of water used is about 8 to 40% by weight based on bisphenol A.

As mentioned above, bisphenol A is insoluble in water;
Even under the reaction temperature, bisphenol A is hardly dissolved in water. Therefore, bisphenol A is in a dispersed state in water, and in order to have good contact with alkylene oxide, bisphenol A must be in the form of a fine powder. It is preferable to use As an alkali catalyst,
Customary alkaline catalysts which promote the addition reaction of alkylene oxides to hydroxyl groups are suitable, in particular alkali metal compounds such as potassium hydroxide, sodium hydroxide,
potassium carbonate.

Alkali metal hydroxides such as sodium carbonate, potassium alcolade, and sodium alcolade are preferred. The amount used is not particularly limited, but it is suitably 0.1 to 1 weight percent relative to bisphenol A.

The reaction temperature is about 100-150°C, preferably about 100-140°C unless the water is near the lower end of the above range.

After the first stage reaction is completed, dehydration is carried out. Usually, dehydration by vacuum dehydration is appropriate. When carrying out the second stage reaction, if this dehydration is not carried out sufficiently, residual water will result in a large amount of by-products such as alkylene glycol. Therefore, when performing the second stage reaction, it is preferable to dehydrate until the residual amount of water becomes 2 parts by weight or less, especially 1 part by weight or less, based on the product.

Except for the special cases mentioned above, the second stage reaction is carried out.

In the second stage reaction, the alkylene oxide may be reacted directly with the product of the first stage, or the reaction can be carried out by adding a catalyst. Particularly in order to obtain a target product with a high molecular weight, it is preferable to add a catalyst, and it is also possible to further add a catalyst during the second stage reaction. Further, when the catalyst is added as an aqueous solution, it is preferable to add it before dehydration and remove this water at the same time. The reaction temperature in this second stage is not limited to the reaction temperature in the first stage, but can be carried out at a temperature of about 100 to 130°C.

After reacting the alkylene oxide until the desired product is obtained, purification etc. are carried out in a usual manner to obtain the desired formula (1
A compound represented by 1 is obtained.

In the compound represented by the formula, the lower limit of m and n is 1
However, there is no particular upper limit. That is, even if a compound has a molecular weight close to 10,000, it can be used as a raw material for polyurethane resin, and m+n may be about 200 or more.

As the alkylene oxide, an alkylene oxide having 2 to 4 carbon atoms is suitable, and ethylene oxide and propylene oxide are particularly preferred.

In addition, two or more types of alkylene oxides can be used in combination, and in that case, two or more types of alkylene oxides can be mixed and/or
Or they can be reacted sequentially. For example, in the first stage, a mixture of ethylene oxide and propylene oxide is reacted, ethylene oxide is reacted first and then propylene oxide is reacted (up to 2 moles per mole of habisphenol A in total), or vice versa. be able to. Similarly, in the second stage reaction, two or more alkylene oxides can be mixed or reacted sequentially. The type and combination of alkylene oxides can also be changed between the first and second stage reactions.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

Example-1 Bisphenol A228Of (1 mol),
NaOH6,8? After adding distilled water 2282°C and raising the temperature to 130°C, propylene oxide 1160°C was added while maintaining the temperature at 130°C. (2 mol) was introduced at the same temperature, 1.5
After holding for a certain period of time, volatile components were distilled off under reduced pressure. The OH value of the obtained polyol was 3281 ngKOH/1. Note that the amount of NaOH catalyst is based on the weight of the finished polyol, and the same applies to the following Examples and Comparative Examples.

Example-2 In the same manner as in Example-1, 2 moles of ethylene oxide was reacted per mole of bisphenol A instead of propylene oxide.

The OH value of the obtained polyol was 358 qKOH/2.

Example-3 Bisphenol A11401 (1 mol),
After charging 114 v of NaOH 3,4f distilled water and raising the temperature to 130°C, 5 aoy (2 moles) of propylene oxide in the first stage was introduced while maintaining the temperature. After aging for 1.5 hours, Na0HC79 was further charged and volatile components were distilled off under reduced pressure. Subsequently, the second stage propylene oxide 2320y (8 mol) was completely introduced at 130T. After aging for 2 hours, unreacted propylene oxide was distilled off under reduced pressure.

The OH value of the obtained polyol was 141 ++yKOH/
It was 1.

Comparative Example-1 In the same manner as in Example-3, 2 moles of first-stage propylene oxide were reacted per 1 mole of bisphenol A. 1.5
After aging for a period of time, NaOH was further charged, and 8 mol of propylene oxide in the second stage was immediately reacted without performing a vacuum degassing operation.

The OH value of the obtained polyol was 187 to KOH/1.

Example 4 A polyol was synthesized in the same manner as in Example 3, except that the amount of distilled water was changed from 1141 to 2282.

The obtained polyol had an OI value of 1459 KOH/litre.

Comparative Example 2 A polyol was synthesized in the same manner as Comparative Example 1 by changing the amount of distilled water from 114f to 2281.

The OH value of the obtained polyol was 2091119KOF (
/2.

Example 5 A polyol was synthesized in the same manner as in Example 4 using ethylene oxide in place of propylene oxide.

Comparative Example 3 A polyol was synthesized in the same manner as Comparative Example 2 using ethylene oxide instead of propylene oxide.

Example-6 Bisphenol AI 140r (1 mol) was added to the reactor.
, 228f of NaOH2,9y distilled water and 140℃
After raising the temperature to , the first stage of propyleneoxy)-2901F (1 mol) was introduced while maintaining the temperature. After aging for 1.5 hours, 5.1f NaOH was further charged and the volatile components were distilled off under reduced pressure. Next, the second stage of propylene oxide 2
6102 (9 mol) was introduced. After aging for 2 hours,
Unreacted propylene oxide was distilled off under reduced pressure. The OH value of the obtained polyol was 145 to KOH/f.

Comparative Example 4 In the same manner as in Example 6, 1 mol of first-stage propylene oxide was reacted with 1 mol of bisphenol A. 1.5
After aging for several hours, NaOH was further charged and the second stage propylene oxide 9
Mol was reacted.

The OH value of the obtained polyol was 218 KOH/1.

The above results are summarized in Table-1.

According to the results of Examples 1 and 2, in a reactor containing up to 2 moles of alkylene oxide per mole of bisphenol A, the actual OH
It can be seen that the value and the calculated OH value match extremely well. The results of Comparative Examples 1 to 4 are as follows.
It can be seen that by carrying out the dehydration operation under reduced pressure before introducing the alkylene oxide in the second stage, the measured value and the calculated value of the OH value are in good agreement.

Claims (1)

[Scope of Claims] 1. A method for producing bisphenol A-alkylene oxide adduct color diols in which 2 moles or more of alkylene oxide is added to 1 mole of bisphenol A, reacting substantially 2 moles of alkylene oxide per mole of bisphenol A with a mixture of about 5 to 50 parts by weight of water and an alkaline catalyst at a temperature of about 100 to 150°C; A method for producing diols comprising a bisphenol A-alkylene oxide adduct, which comprises reacting and dehydrating about 1 to less than 2 moles of alkylene oxide, and then reacting the alkylene oxide until a desired product is produced. 2. The method according to claim 1, wherein the alkylene oxide is an alkylene oxide having 2 to 4 carbon atoms.