JPS62143926A - Lactone-modified diol - Google Patents

Abstract

PURPOSE:To obtain the titled novel compound of high weatherability, requiring no additive, by incorporating hydroxy ethyl-tetramethyl-hydroxypiperidine with specified amount of specific lactone followed by reaction. CONSTITUTION:The objective compound of formula II (Y is mole number of 4-8C lactone; n+m=2-15) can be obtained by incorporating (A) 1-(2'- hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy-piperidine of formula I with (B) 2-15 moles of a 4-8C lactone (pref. epsilon-caprolactone) followed by reaction at 130-220 deg.C, pref. in a nitrogen atmosphere under ambient pressure.

Description

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

More specifically, 1-(2'-hydroxyethyl)-2
, 2,6,6,tetramethyl-4-hydroxybiperidine as an initiator to carry out ring-opening polymerization of lactones, and relates to a novel lactone polymer having excellent weather resistance.

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, acrylonitrile-styrene resins, etc., and raw materials for urethane acrylic resins.

(Prior art) However, conventionally known ethylene glycol, diethylene glycol, neopentyl glycol, 1.4
Polyurethane polymers obtained by reacting diisocyanate compounds with lactone polymers obtained by ring-opening polymerization of lactones using an initiator such as butanediol have the disadvantage of insufficient weather resistance. be.

Therefore, in general, ultraviolet absorbers, antioxidants, etc. are added for the purpose of imparting weather resistance.

(Problem to be solved by the invention) However, these are additives, and when added in large amounts,
There is a drawback that powder blowing phenomenon (blooming) tends to occur on the surface of the product.

The inventors of the present invention conducted intensive studies to improve these drawbacks, and found that when urethane is formed using a lactone-modified diol having a hindered amine structure in the molecule, the urethane resin itself has weather resistance, and the above-mentioned The present invention was achieved based on the discovery that there is no need to add such additives and other properties are not impaired.

(Structure of the Invention) That is, the present invention provides 1-(2'-
hydroxyethyl)-2,2,6,6゜tetramethyl-
A novel lactone-modified diol represented by formula (II) obtained by adding 2 to 15 moles of a lactone having 4 to 8 carbon atoms to 1 mole of 4-hydroxypiperidine and reacting the mixture.

(I) (X-) (However, Y is the number of moles of a lactone having 4 to 8 carbon atoms, and n+m=2 to 15.) Next, the present invention will be explained in detail.

First, 1-(2'-hydroxyethyl)-2゜2.6,6. represented by formula (I) having a hindered amine structure. Butramethyl-4-hydroxypiperidine is a known substance, and can be synthesized by the following method, for example, as disclosed in JP-A-57-21368.

Dissolve 1-(2″-hydroxyethyl)-2,2,6゜6,tetramethyl-4-hydroxypiperidine in water,
Ethylene oxide is blown in and dissolved at 25-30°C.

Thereafter, the reactor was heated and stirred under reflux for 1 hour, and then 6
After cooling to 0° C. and blowing in ethylene oxide, the mixture was further stirred under reflux for 2 hours.

Next, after cooling to room temperature, the precipitated crystals are separated by filtration, dried, and recrystallized from toluene to obtain natural crystals with a melting point of 180 to 182° C. in a yield of 15% or more.

The reaction molar ratio of the compound represented by formula (I) and lactones is 2 to 15 lactones per mole of compound (I).
Moles are appropriate.

If the amount is less than 2 moles, the lactone chains in the produced lactone adduct will not have sufficient flexibility.

On the other hand, if it exceeds 15 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 (I) 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 specified catalyst is added thereto for 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.

To carry out ring-opening polymerization of lactones using 1-(2'-hydroxyethyl)-2,2,6゜6,tetramethyl-4-hydroxypiperidine as an initiator, the reaction time is 50°C to 230°C in a nitrogen atmosphere at normal pressure. °C, preferably 130 °C to 2
Heat to 20°C.

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

If the reaction rate is below 50°C, the reaction rate is extremely slow, and if it exceeds 230°C, ogicicabronic acid is produced by thermal decomposition, which increases the acid value, which is not preferable.

The compound ([) used in the present invention is not inferior in reactivity to alkylene glycol, which is a general initiator for the ring-opening reaction of lactone.

In addition, it is preferable to have a catalyst present in order to promote the reaction during intercyclic depolymerization.

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 11000 relative to the starting material.
pp, preferably 0.1 to 100 pl) Ilr.

The reaction completes in about 6 hours, and the process is carried out by confirming that the unreacted lactone is less than 1% using a gas chromatograph.

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) The lactone-modified diol having a hindered amine structure of the present invention does not cause blooming because the weathering component is bonded within the molecule, unlike diols that add additives that affect weather resistance. It also does not impair other properties.

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, polynisdel, urethane acrylic resins, etc., the
1oooo is appropriate, but when used as a modification modifier for polyester resins, polycarbonate resins, polyvinyl chloride, acrylonitrile monostyrene resins, etc., it is preferable that the molecular ti1 is higher to some extent, and the number average molecular weight is at least 1000 or more. , preferably 5000
to 50,000.

Next, the contents of the present invention will be specifically explained with reference to examples. The 8m value of water shown in the examples is a value measured by the anhydrous hydrofluoric acid-pyridine method based on JISK-1557,
The acid value is the value obtained by neutralization 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゜1-(2=-hydroxyethyl)-2,2,6,6,tetramethyl-4-hydroxypiperidine [Sankyo Co., Ltd. (product name C10-2625) 1
201 parts, ε-caprolactone 1799 parts, [1-(2
"-Hydroxyethyl)-2,2,6,6,tetramethyl-4-hydroxypiperidine and ε-caprolactone molar ratio 1:15] 0.002 part of tetrabutyl titanate was charged and reacted at 110°C for 6 hours to remove hydroxyl groups. Value (K O
Hrng/bi) 56.3, acid value (KOGIftg/g)
A lactone-modified diol having a melting point of 43° C. and a solid at room temperature was obtained. The molecular weight of this product was 1,990. Example-2, 1-(2'-hydroxyethyl)-2,2,6,6,tetramethyl-4-hydroxypiperidine [Sankyo Co., Ltd. (product name C10-2625)] in the same apparatus as in Example-1.
2201 parts ε-caprolactone 1049 parts, [1-(
2'- and droxyethyl)-2,2,6,6,tetramethyl-4-hydroxypiperidine and ε-caprolactone molar ratio 1:9], tetrabutyl titanate 0.003
of hydroxyl value (K
OHIItg/! ? >90.2, acid value 1.05,
The melting point is 42-46°C. 1 q of waxy lactone-modified diol that is solid at iδ temperature.

Claims (1)

[Scope of Claims] 1-(2'-hydroxyethyl)-2,2,6,6,tetramethyl-4-hydroxypiperidine represented by the following formula (I) is combined with 2 lactones having 4 to 8 carbon atoms. ~15
Lactone-modified diol shown by formula (II) obtained by adding moles and reacting ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, Y The number of moles of lactones having 4 to 8 carbon atoms, n+m=2 to 15)