JPS62167320A - Production of lactone-modified diol - Google Patents

Abstract

PURPOSE:To obtain the titled novel diol, having improved hydrolytic resistance and suitable as a raw material for elastomers, adhesives, coating materials etc., by reacting decanediol with a lactone having a specific number of carbon atoms. CONSTITUTION:(B) 2-20mol 4-8C lactone, e.g. epsilon-caprolactone, etc., is added to (A) 1mol 1,10-decanediol and a catalyst, e.g. stannous chloride, etc., in an amount of preferably 0.1-1,000ppm based on the starting raw material is added to carry out reaction. Thereby the aimed diol, expressed by the formula (Y is ring-opened residue of 4-8C lactone; n and m are number of added mol) and having 500-50,000 molecular weight is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel lactone-modified diol.

More specifically, the present invention relates to a novel lactone polymer having excellent hydrolysis resistance, which is characterized by ring-opening polymerization of lactones using 1,10-decanediol as an initiator.

(Prior Art) Lactone polymers are very useful as raw materials for elastomers, adhesives, polyurethane polymers such as synthetic leather, and paints.

It is also used as a modifier for imparting toughness, processability, etc. to polyester resins, polycarbonate resins, polyvinyl chloride resins, acrylic nitrile-styrene resins, etc., and raw materials for urethane acrylic resins.

However, the conventionally known ethylene glycol, diethylene glycol, neopentyl glycol, 1.4
In the case of a polyurethane polymer obtained by reacting a lactone polymer obtained by ring-opening polymerization of lactones using an initiator such as butanediol with a diisocyanate compound, hydrolysis resistance based on the ester group of the lactone It has the disadvantage of low performance.

In order to overcome this drawback, hydrolysis inhibitors such as carbodiimide are added and used.

(Problem to be solved by the invention) However, carbodiimide is toxic and irritates the skin, so it is not recommended to use it in applications where it comes into direct contact with the human body.Additionally, if the amount added is too large, powdery particles may appear on the surface of the product. The disadvantage is that (blooming) is more likely to occur.

The present inventors conducted intensive studies to improve these drawbacks, and found that when urethane-formed using a lactone-modified diol having a linear and long-chain alkyl group, the urethane resin itself has water resistance. Therefore, the present invention was achieved based on the discovery that there is no need to add additives such as those described above, and other properties are not impaired.

(Structure of the Invention) That is, the present invention provides “1, 10 represented by the following formula (I)
Adding 2 to 4 to 8 lactones to decanediol
Lactone-modified diol HO(C8,,)10OH-- obtained by adding 20 mol and reacting with the formula (II)
---(I) (However, Y is a residue obtained by ring-opening polymerization of lactones having 4 to 8 carbon atoms, n and m are the number of moles added, n+m-
2 to 20). sJ, Article 1 also provides a detailed description of the invention.

1,10-decanediol represented by formula (1) of the present invention is a known substance and is widely used in industry, such as as one of the polyol components of urethane.

The reaction molar ratio of the compound represented by formula (I) and lactones is 2 to 20 lactones per mole of compound (1).
Moles are appropriate.

If the amount is less than 2 moles, the flexibility of the lactone chains in the produced lactone adduct will not be imparted sufficiently.

On the other hand, if it exceeds 20 moles, the molecular weight becomes too large and the viscosity increases during urethane formation, making it difficult to handle.

Furthermore, since the proportion of substance (I) in one molecule decreases, the desired weather resistance cannot be imparted.

Since the compound (1) used in the present invention is a crystalline solid, when it is used for an addition reaction with a lactone, it is dissolved in a liquid lactone and a predetermined catalyst is added to cause the reaction.

Examples of the lactones used in the present invention include γ-butyrolactone, ε-caprolactone, and δ-valerolactone. Among them, ε-caprolactone is preferred from various points of view.

1.10 To carry out ring-opening polymerization of lactones using decanediol as an initiator, the reaction mixture is heated to 50°C to 230°C, preferably 130°C to 220°C, in a nitrogen atmosphere at normal pressure.

The reason why the atmosphere is nitrogen gas is to prevent the product from being significantly colored.

If the temperature is below 50'C, the reaction rate is extremely slow, and if it exceeds 230C, oxycaproic acid is produced by thermal decomposition, resulting in a high acid value, which is not preferable.

Compound (I) used in the present invention is not inferior in reactivity to alkylene glycols, which are common initiators for the ring-opening reaction of lactones.

Note that a catalyst is preferably present in order to promote the reaction during ring opening and polymerization.

Examples of catalysts include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, organic tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin laurate, stannous chloride, stannous bromide, and stannous iodide. 1 halogenated material such as tin
Tin etc. are used.

The amount of catalyst added is 0.05 to 10,001 based on the starting material.
) El-1 is preferably 0.1 to toopp-.

The reaction is completed in about 6 hours, and the amount of unreacted lactone is confirmed by gas chromatograph or the like to be 1% or less.

The obtained reaction product is a white wax-like solid substance at room temperature, and when it is to be converted into urethane, it is heated and melted before use.

(Effects of the Invention) Since the lactone-modified diol obtained by the method of the present invention has a long chain and contains a straight alkyl group, this alkyl enhances the waterproof effect, and when converted into a urethane, it has extremely high water resistance.

In addition, the structure is a linear polymer with hydroxyl groups at both ends,
The molecular weight can be set within a wide range by adjusting the amount of lactone depending on the purpose and use.

For example, when used as a diol component in polyurethane polymers, polyesters, urethane acrylic resins, etc., the
1000G is appropriate, but when used as a modifying agent for polyester resins, polycarbonate resins, polyvinyl chloride, acrylonitrile-styrene resins, etc., it is preferable that the molecular weight is higher to some extent, and the number average molecular weight is at least 1000 or more, Preferably 5000 to so, oo.

It is.

Next, the contents of the present invention will be specifically explained with reference to examples. The water wi group values shown in the examples are values measured by the phthalic anhydride-pyridine method based on JISK-1557, and the acid value is the value obtained by neutralization selection using acetone solvent.

The melting point is a value measured using a micro melting point meter manufactured by Yanagimoto Seisakusho. Note that all parts in the examples indicate parts by weight.

Example-1 174 parts of 1.10 decanediol, 1826 parts of ε-caprolactone, and 0.002 parts of tetrabutyl titanate were charged into a four-cylinder flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, and the mixture was heated at 170°C for 6 hours. Hydroxyl value (KOHjl)
! j/9) 56.3, acid value (KOGq/g) 1.2
5. A lactone-modified diol which was solid at room temperature and had a melting point of 53°C was obtained. The molecular weight of this product was 1,990. Example-2゜1.10 decanediol 17 in the same apparatus as Example-1
4 parts of ε-caprolactone, 826 parts of ε-caprolactone, and 0.002 parts of tetrabutyl titanate.
In response, a waxy lactone-modified diol which was solid at room temperature and had a hydroxyl value (KOHIIg/bi) of 90.2, an acid value of 1.05, and a melting point of 42 to 46°C was obtained.

Claims (1)

[Claims] A lactone-modified compound represented by formula (II) obtained by adding 2 to 20 moles of a lactone having 4 to 8 carbon atoms to 1,10 decanediol represented by formula (I) below and reacting the mixture. Diol HO (CH_2)_1_0OH---(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼------(II) (However, Y is a ring-opening polymerization of lactones having 4 to 8 carbon atoms. residues, n and m are the number of moles added, n+m=2 to 20)