JPH06329752A - Polyol composition for polyurethane - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in the control of reaction by adding a specified amount of a cyclodextrin to a polyol. CONSTITUTION:The composition excellent in the control of reaction is obtained by adding 0.1-5.0wt.% cyclodextrin (e.g. alpha-cyclodextrin composed of 6 glucose units or theta-cyclodextrin composed of 13 glucose units) to a polyol (e.g. polyether polyol or polycarboante polyol). Although a method of neutralizing with an acid or an alkali is conventionally known as a method for controlling the catalysis of a synthesis catalyst in a polyether polyol or a metal catalyst in the polymerization of a polyester polyol, it has been difficult to control their catalysis. According to this process, the control of the catalyst in the polyol is easy, and the prepolymer obtained by reacting a polyol composition with an organic polyisocyanate has excellent long-term stability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyol composition for polyurethane excellent in reaction control. More specifically, it relates to a polyol composition for polyurethane which is excellent in reaction control by adding cyclodextrin to the polyol.

[0002]

2. Description of the Related Art Conventionally, a method of neutralizing with an acid or an alkali is known to control the catalytic ability of a synthetic catalyst in a polyether polyol or a metal-based catalyst in the polymerization of a polyester polyol. It was

[0003]

In the conventional neutralization method, it is difficult to control the reaction because the reaction is greatly affected by a slight excess due to the reason that the acid acts as a negative catalyst for the urethanization reaction. There was a problem. We have
As a result of diligent studies to solve such conventional problems, the inventors have found that addition of cyclodextrin to the polyol can improve the problem, and have completed the present invention.

[0004]

That is, the present invention relates to a polyol composition for polyurethane, characterized in that 0.1 to 5.0% by weight of cyclodextrin is added to the polyol.

As the polyol used in the present invention, polyether polyol, polycarbonate polyol or polyester polyol having a molecular weight of 200 to 10,000 produced by a known method using a known material can be used. Examples of the polyether polyol include a polymerization product of tetrahydrofuran, propylene oxide and ethylene oxide, a copolymer thereof, or a graft polymer of a vinyl monomer.

Examples of the polycarbonate polyol include aliphatic diols or alicyclic diols such as 1,6-hexanediol and 1,4-cyclohexanedimethanol, and cyclic carbonates such as dialkyl carbonates or diaryl carbonates or ethylene carbonates. It is obtained by the transesterification reaction of.

As the polyester polyol, a molecular weight of 500 produced from a polyhydric alcohol and a polycarboxylic acid is used.
~ 5000 can be used. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol, 3-methylpentanediol, cyclohexanedimethanol, glycerin, trimethylolpropane and the like. Examples of polycarboxylic acids include succinic acid, adipic acid, sebacic acid,
Examples thereof include dimer acid, phthalic acid, phthalic acid alkyl ester, trimellitic acid, pyromellitic acid, maleic acid, fumaric acid, and itaconic acid. Moreover, the thing obtained by ring-opening polymerization of cyclic ester, such as lactone and caprolactone, is also mentioned. The polyether ester is the same as the above polyester except that a polyether polyol is used as a part of the polyhydric alcohol used in the polyester.

The cyclodextrin used in the present invention is 6
It is a cyclic oligosaccharide composed of at least one glucose group, and the molecule has a cage structure having a cavity inside, and various guest substances can be included in the cavity.
Examples of the cyclodextrin include α-cyclodextrin having 6 glucose groups, β-cyclodextrin having 7 glucose groups, γ-cyclodextrin having 8 glucose groups, and δ-cyclodextrin having 9 glucose groups. , Ε-cyclodextrin having 10 glucose groups, ζ-cyclodextrin having 11 glucose groups,
Examples include η-cyclodextrin having 12 glucose groups, θ-cyclodextrin having 13 glucose groups, and crude cyclodextrin before purification. Further, modified cyclodextrins obtained by chemically modifying these cyclodextrins such as methylated products and esterified products with carboxylic acids and sulfonic acids are also included.

The amount of cyclodextrin used in the present invention added to the polyol is preferably 0.1 to 5.0% by weight. If it is less than 0.1% by weight, there is no effect, and if it exceeds 5.0% by weight, the cost becomes high, which is not preferable. The cyclodextrin in the present invention can be added to the polyol by a usual addition method.

Examples of the polyisocyanate used in the present invention include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate and the like, and aromatic diisocyanates consisting of these isomers, 1,6- Aliphatic diisocyanates such as hexamethylene diisocyanate and 1,12-dodecane diisocyanate, cycloaliphatic diisocyanates such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate can be used.

The polyol composition obtained by the present invention contains other substances, if necessary, such as an antioxidant, an ultraviolet absorber, a heat resistance improver, a colorant, an inorganic and organic filler, a plasticizer, a lubricant, and a charge. An inhibitor, a reinforcing material, etc. can be added.

[0012]

According to the present invention, the control of the catalyst in the polyol becomes easy, and the prepolymer obtained by the reaction of the polyol composition and the organic polyisocyanate has excellent long-term stability.

[0013]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" and "%" indicate "parts by weight" and "% by weight", respectively.

Example 1 20 g of potassium hydroxide (Kishida Chemical, purity 85%) and glycerin (Kishida Chemical) at 120 ° C. until 3000 g of propylene oxide (Kishida Chemical) reacted.
Propylene oxide was passed through 1100 g of the mixture to synthesize a crude propylene oxide polyether polyol over 17 hours. This crude polyol is
It contained about 2% unreacted propylene oxide and about 0.5% residual potassium hydroxide. This is 110-120 ℃
After passing nitrogen gas for 4 hours while maintaining the above condition, 0.8% of hydrochloric acid (manufactured by Kishida Chemical Co., Ltd., purity: 35%) was added. After this,
With stirring, the mixture was heated to 100 ° C. and filtered. The obtained polyol has a hydroxyl value of 500 and potassium hydroxide of 0.0
It contained 5%.

Application Example 1 312.4 g of the prepared polyol and 9.0 g of β-cyclodextrin (manufactured by Tokyo Kasei) were weighed (3 times the amount of 1 mol of potassium hydroxide in the polyol) in a 500 ml separable flask. Then, while refluxing with nitrogen, 4 at 60 ° C
Stir for hours. After adjusting the liquid temperature to 40 ° C., Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd., polymethylene polyphenylene polyisocyanate, NCO content 3
35% of 1.1%) was added. The NCO content was measured 1 hour and 2 hours after the reaction was started, with the time when the addition of Millionate MR200 was taken as the reaction start time.
The reaction rate (%) to the content was measured. After 1 hour; it was reduced to 15% of the original. After 2 hours; it had decreased to 9% of the original.

Application Example 2 β-Cyclodextrin was acetylated to synthesize acetylated β-cyclodextrin. 312.4 g of the polyol prepared in Example 1 and 15.7 g of acetylated β-cyclodextrin (3 times the amount of 1 mol of potassium hydroxide in the polyol) were used under the same conditions as in Example 1 to obtain Millionate MR200. Experiment was conducted by reacting with. After 1 hour; it was reduced to 11% of the original. After 2 hours; it was reduced to 6% of the original.

Application Example 3 The same as Example 1 except that 312.4 g of the polyol prepared in Example 1 and 3.0 g of β-cyclodextrin (3 times the amount of 1 mol of potassium hydroxide in the polyol) were used. The experiment was conducted by reacting with Millionate MR200 under the conditions. After 1 hour; it was reduced to 13% of the original. After 2 hours; it was reduced to 8% of the original.

Application Example 4 312.4 g of the polyol prepared in Example 1 and 5.2.4 g of the acetylated β-cyclodextrin prepared in Example 3 were used.
2 g (1 mol of potassium hydroxide contained in the polyol
In contrast, the experiment was conducted by reacting with Millionate MR200 under the same conditions as in Example 1, using 3 times the amount). After 1 hour; it was reduced to 10% of the original. After 2 hours; it was reduced to 5% of the original.

Application Example 5 In a 500 ml separable flask, Niprolan 4002
(Polyester polyol manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl value 107) 236 g and β-cyclodextrin 2.
4 g was weighed and stirred at 80 ° C. for 4 hours while refluxing with nitrogen. Millionate MT (manufactured by Nippon Polyurethane Industry, 4,4'-diphenylmethane diisocyanate, N
114 g of CO content (33.6%) was added to synthesize an NCO group-terminated prepolymer. The reaction temperature was set to 80 ° C. The time when the reaction was started was the time when the mylionate MT was added, and the change with time of the NCO amount was measured in the same manner as in Example 1 to determine the reaction rate. In addition, the same experiment was conducted using Niprolan 4002 to which β-cyclodextrin was not added, and the reaction rate was obtained. After 2 hours, the reaction to which cyclodextrin had been added had the reaction proceeded to 72%. On the other hand, in the case where the cyclodextrin was not added, the reaction proceeded by 84%. Further, when the NCO group-terminated prepolymer after the reaction was heated at 120 ° C. for 2 days and the NCO content was measured, it was 100% with cyclodextrin added, but not added. Was 93%.

Comparative Example 1 312.4 g of the polyol prepared in Example 1 was added to 500 m
The sample was weighed in a 1-separable flask and reacted with Millionate MR200 under the same conditions as in Example 1 to carry out an experiment.
The NCO content after 1 hour had decreased to 8% at the beginning and to 3% after 2 hours. From Comparative Example 1, the reaction in which the potassium hydroxide in the polyol was neutralized with 37% hydrochloric acid, the reaction was extremely fast. On the other hand, from the results of Examples 1 to 5, there is no significant difference in the NCO reduction rate depending on the amount of β-cyclodextrin or acetylated β-cyclodextrin added. Therefore, it can be seen that the reaction is easier to control than the neutralization method.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area // (C08L 71/02 5:16)

Claims (1)

[Claims] 1. A polyol composition for polyurethane, characterized in that 0.1 to 5.0% by weight of cyclodextrin is added to the polyol.