JPH0912707A - Process for producing cyclodextrin polyether - Google Patents

Abstract

(57) [Summary] [Structure] 10 to 50 parts by weight of water and cyclodextrin 1
To 100 parts by weight of the mixture, 0.1 to 1 of the alkali metal compound is added.
This is a method for producing a cyclodextrin-based polyether by adding 0 part by weight and reacting 150 parts by weight or more of alkylene oxide. [Effect] The cyclodextrin-based polyether of the present invention can be reacted with a polyisocyanate compound to form a polyurethane resin. This polyurethane resin can be expected to have an inclusion function, and can be effectively used for functional polyurethanes such as adsorbents and separators.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a cyclodextrin type polyether, which is used as a raw material for a functional polyurethane foam having the ability to include various chemical substances.

[0002]

BACKGROUND OF THE INVENTION Cyclodextrin is a useful substance having a cavity in the molecule and capable of including various chemical substances. However, cyclodextrin is a powder having a high melting point and is hardly dissolved in the solvent normally used for urethane. Further, the compatibility with polyols for urethane is extremely poor. On the other hand, as a method of using cyclodextrin as an additive, for example, as disclosed in JP-A-6-329752, a method of adding a polyol to adjust the reactivity has been known.

[0003]

However, the conventional method of adding cyclodextrin as an additive is
Since cyclodextrin is an insoluble and infusible powder, it was settled and separated in the polyol and could not be used in a non-solvent system compounding composition. It is an object of the present invention to improve the solubility of cyclodextrin and to provide a polyether which can be easily handled like conventional urethane raw materials.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned conventional problems, the present inventor has found that if cyclodextrin is modified by a special method, the cyclodextrin becomes liquid. The present invention has been completed. That is, in accordance with the present invention, a cyclodextrin-based poly (ethylene glycol) obtained by adding 0.1 to 10 parts by weight of an alkali metal compound to a mixture of 10 to 50 parts by weight of water and 100 parts by weight of cyclodextrin and reacting 150 parts by weight or more of alkylene oxide. A method of making an ether is provided. The cyclodextrin used in the present invention is synonymous with cycloamylose, which is obtained by enzymatically cyclizing starch, and the glucose unit is mainly 6-8. In addition to cyclodextrin, it may contain by-products at the time of production such as maltose and oligosaccharides.

In the present invention, 100 parts by weight of cyclodextrin and 10 to 50 parts by weight of water are used. If the amount of water is less than 10 parts by weight, the initial reaction of the alkylene oxide is heterogeneous, which is not preferable. As the cyclodextrin used in the present invention, it is convenient to use liquid cyclodextrin. The industrialized liquefied product is sold, for example, by Nippon Food Processing Co. under the trade name of Celldex CH. Celldex C
H is cyclodextrin 75% containing by-products and water 25
% Mixture. The cyclodextrin used in the present invention can be used in combination with other initiators, for example, glycerin, alkanolamines, aromatic amines and the like, if necessary. The alkali metal compound used in the present invention is, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide or the like. The alkylene oxides used in the present invention are ethylene oxide and propylene oxide. It is preferable to add 0.1 to 10 parts by weight of the alkali metal compound to the mixture of 110 to 150 parts by weight of the mixture of water and cyclodextrin, and to mix 150 parts by weight or more of the alkylene oxide. If the amount of the alkali metal compound is less than 0.1 part by weight, the cyclodextrin cannot be liquefied,
If it exceeds 10 parts by weight, the reaction rate of the alkylene oxide becomes too fast, which is not preferable. If the blending amount of the alkylene oxide is less than 150 parts by weight, the cyclodextrin is not sufficiently liquefied, and the compatibility of the obtained polyether with general polyols is not preferable.

The amount of alkylene oxide blended needs to be changed depending on the performance of the polyurethane produced. For hard resins, eg for rigid foams, the amount of alkylene oxide should be low, for soft resins, eg for flexible foam, the amount of alkylene oxides should be eg 10
It is necessary to add more than 00 parts by weight.

The reaction of the alkylene oxide of the present invention can be carried out under the same conditions as the addition reaction of the alkylene oxide used in the production of a usual polyether polyol for urethane. The reaction can be carried out at 100 to 150 ° C. using a pressure reactor usually used for producing polyether. After the completion of the reaction, unreacted alkylene oxide is removed, the alkali metal compound is neutralized with an acid such as acetic acid or hydrochloric acid, and the neutralized product is removed by filtration or an adsorbent if necessary.

The cyclodextrin type polyether obtained in the present invention has a hydroxyl group capable of reacting with an isocyanate group. The content of hydroxyl group varies depending on the amount of alkylene oxide compounded, but the hydroxyl value is 50 to 1000 mg.
It is KOH / g. After production, the cyclodextrin-based polyether obtained by the present invention can be added with other resins, additives, etc., if necessary. Examples of other resins include polyols for polyurethane, and examples of additives include antioxidants, inorganic and organic fillers, and antistatic agents.

[0009]

According to the present invention, cyclodextrin can be made into a polyether having excellent compatibility. The cyclodextrin-based polyether obtained by the present invention can be reacted with a polyisocyanate compound to form a polyurethane resin. This polyurethane resin can be expected to have an inclusion function, and can be effectively used for functional polyurethanes such as adsorbents and separators.

[0010]

EXAMPLES The present invention will be described in more detail by way of examples and application examples, but the present invention is not limited to these. In the examples and the like, all “parts” mean “parts by weight”.

Example 1 100 parts of liquid cyclodextrin (Celldex CH-30, manufactured by Nippon Shokuhin Kogyo Co., Ltd., cyclodextrin / water = 75/25 parts) and 1.0 part of caustic potash were placed in a 1 liter stainless steel pressure-resistant reactor. Charge, purge with nitrogen, 10
After heating at 0 ° C for 1 hour, 200 parts of propylene oxide was added to 1
It was introduced at 20 to 140 ° C over 10 hours. 5 at the same temperature
After the reaction for a while, 1.9 parts of acetic anhydride was added,
It was treated at a temperature of 30 ° C. and a reduced pressure of 30 mmHg for 1 hour. 298 parts of a brown transparent liquid was obtained. The viscosity was 430 cP / 25 ° C., the hydroxyl value was 880 mgKOH / g, and the water content was 0.35%. This product and urethane polyether AM-30
When mixed with 2 (produced by Asahi Denka Co., Ltd., glycerin-based polyether, molecular weight 3000) in a ratio of 1/1, they were compatible with each other. When Celldex CH-30 and AM-302 were mixed at a ratio of 1/1, they were incompatible with each other, and white turbid separation occurred.

Example 2 The same reactor as in Example 1 was charged with 100 parts of Celldex CH-30 (same as in Example 1) and 0.5 parts of caustic potash, purged with nitrogen and heated at 100 ° C. for 2 hours, 400 parts of propylene oxide were introduced at 120-140 ° C over 15 hours. Post-reaction was carried out at the same temperature for 2 hours, 1.0 part of acetic anhydride was added, and the mixture was treated at 80 ° C. under reduced pressure of 20 mmHg for 1 hour. 501 parts of a brown transparent liquid were obtained. Viscosity 2
The content was 30 cP / 25 ° C, the hydroxyl value was 550 mgKOH / g, and the water content was 0.23%. When this product and urethane polyether AM-302 (the same as in Example 1) were mixed at a ratio of 1/1, they were compatible with each other.

Example 3 The same reactor as in Example 1 was charged with 100 parts of Celldex CH-30 (same as in Example 1) and 0.5 parts of caustic potash, purged with nitrogen and heated at 100 ° C. for 2 hours, 100 parts of propylene oxide were introduced at 110-120 ° C over 4 hours. Triethanolamine (Kishida chemistry, reagent)
Charge 75 parts, 120 parts propylene oxide 400 parts
Introduced at ~ 130 ° C over 15 hours. Post-react at the same temperature for 2 hours, add 1.0 part of acetic anhydride, and
It was treated under a reduced pressure of 20 mmHg for 1 hour. 664 parts of a brown transparent liquid were obtained. The viscosity was 270 cP / 25 ° C., the hydroxyl value was 560 mgKOH / g, and the water content was 0.29%. When this product and urethane polyether AM-302 (the same as in Example 1) were mixed at a ratio of 1/1, they were compatible with each other.

Application Example 1 14.6 parts of cyclodextrin type polyether obtained in Example 2, polyether for urethane, Sannix F
A-909 (manufactured by Sanyo Chemical Industries, hydroxyl value 28 mg KOH
/ G) 7.3 parts, tap water 0.29 parts, silicon foam stabilizer (SZ-1932, made by Nippon Emulsifier) 0.07 parts and D
ABCO33LV (manufactured by Sankyo Air Products, amine-based catalyst) 0.29 parts is mixed, and diphenylmethane diisocyanate-based polyisocyanate (Millionate MR20) is mixed.
0, made by Nippon Polyurethane Industry Co., Ltd.) 27.5 parts and added 2
Mix at 30C for 30 seconds, transfer to a 500 ml cup and foam. Cream time 35 seconds, rise time 1 minute 5
Foaming was completed in 0 seconds. A uniform hard foam having an expansion ratio of 15 times was obtained.

Application Example 2 18.2 parts of cyclodextrin type polyether obtained in Example 3, 0.18 part of tap water, silicone foam stabilizer (SZ
-1932, manufactured by Nippon Emulsifier) 0.09 parts and DABC
0.36 parts of O33LV (same as Application Example 1) is mixed, 31.1 parts of diphenylmethane diisocyanate-based polyisocyanate (same as Application Example 1) is added, and at 25 ° C., 2
Mix for 5 seconds, transfer to a 500 ml cup and foam.
Foaming was completed with a cream time of 30 seconds and a rise time of 1 minute. A uniform hard foam having an expansion ratio of 10 times was obtained.

Claims (1)

[Claims] 1. A mixture of 10 to 50 parts by weight of water and 100 parts by weight of cyclodextrin, and 0.1 parts of an alkali metal compound.
A process for producing a cyclodextrin-based polyether, which comprises reacting alkylene oxide with 150 parts by weight or more by adding 10 parts by weight to 10 parts by weight.