JPS62131014A - Lactone-modified amide diol - Google Patents

Abstract

PURPOSE:To obtain a lactone-modified amide diol excellent in heat resistance, flexibility, water resistance and dispersibility and useful as soft segments, by addition-polymerizing a lactone with the amino groups of a specified diamine polyamide by ring opening. CONSTITUTION:A lactone-modified amide diol obtained by addition-polymerizing, by ring opening, 5-97pts.wt. lactone (c) with the amino groups 95-3pts.wt. diamine polyamide obtained by reacting at least one polyamide-forming compound (a) selected from among a 6-12C aminocarboxylic acid, a 6-12C lactam and a nylon salt of a 4-12C dicarboxylic acid with a 4-12C diamine with a 2-12C diamine (b). Said addition polymerization by ring opening is performed at 100-230 deg.C, for the rate of reaction is low when it is below 100 deg.C while the depolymerization of the lactone which has been addition-polymerized by ring opening occurs to cause an increase in the amount of low-MW by-products when it is above 230 deg.C.

Description

[Detailed Description of the Invention] (Field of Industrial Application) The present invention provides a soft segment with excellent heat resistance, flexibility, water resistance, and dispersibility that is useful as a soft segment used in the synthesis of paints, various elastomers, resin modification, etc. This invention relates to a novel lactone-modified amide diol containing an amide group, an ester group, and a hydroxyl group.

(Prior Art) Polyurethane, polyester, polyamide elastomers, etc. are required to have properties such as heat resistance, water resistance, solvent resistance, weather resistance, and flexibility depending on the application.

The oligomer resin as a soft segment used in the synthesis of these resins is an adipate polyester such as ethylene glycol adipate, 1,4-butylene glycol adipate, 1,6-hexanediol adipate, etc., with an average molecular weight of 500 to 5,000. Various soft segments are widely used, such as polycaprolactone and polyethers such as polyethylene glycol, polyb-O-pyrene glycol, and polydetramethylene glycol, and polybutadiene polyol.

(Problems to be Solved by the Invention) However, polyester polyols such as adipate polyols and polycaprolactone have a drawback of poor water resistance and solvent resistance due to their ester bonds.

For example, polyurethane using ethylene glycol adipate polynisdel, which is an adipate-based polynisdel, has excellent elastic recovery properties, but has poor water resistance, and the product becomes unusable within one to two years.

Furthermore, although polyether polyols have excellent low-temperature properties because they have ether bonds, they have the drawback of being easily degraded by oxidation and having extremely poor weather resistance and heat resistance.

Polybutadiene polyol Although isotropic reflex polyol has excellent water resistance etc., it has a drawback of poor compatibility with other resins.

In addition, as a recent trend, polyurethane with heat resistance,
Polyester elastomers, nylon elastomers, etc. are in demand, and in order to improve heat resistance, it is necessary to use the soft segment 1 component, which has excellent heat resistance, flexibility, and high reactivity, as a rough 1 segment of the polymer. It is necessary to use

However, at present, there is no polymer or oligomer that can serve as sonotosegment 1- that fully satisfies the above performance, and it is difficult to improve the heat resistance of the polymer.

Therefore, the present inventors conducted intensive studies to obtain polymers or oligomers that can be used as soft segments that have excellent heat resistance and flexibility. The lactone-modified polyamide diol obtained by synthesizing diamine polyamide and reacting it with lactones is not only heat resistant, flexible, and has a highly reactive hydroxyl group, but also can be used with polyurethane, polyamide, polyester or The present invention was completed based on the discovery that the dispersibility of these elastomers is important.

(Structure of the Invention) That is, the present invention provides: ``(a) an aminocarboxylic acid having 6 to 12 carbon atoms, a lactam having 6 to 12 carbon atoms, or a dicarboxylic acid having 4 to 12 carbon atoms; A diamide polyamide obtained by reacting one or more polyamide-forming compounds selected from nylon salts consisting of diamines with ([1) diamines having 2 to 12 carbon atoms]. (c) Lactone-modified amide diol J obtained by ring-opening monopolymerization of 5 to 97 lactones.

Examples of aminocarboxylic acids having 6 to 12 carbon atoms in the present invention include 6-aminocaproic acid, 7-aminocaprylic acid, 8-aminocapric acid, W-aminocaproic acid, W-aminoperboxylic acid, 11-aminoundecanoic acid, 12-aminocaproic acid, Among them, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid are particularly preferably used.

Examples of the lactam having 6 to 12 carbon atoms include caprolactam, enantlactam, capryllactam, and lauryllactam, with caprolactam and lauryllactam being particularly preferably used.

On the other hand, dicarboxylic acids having 4 to 12 carbon atoms and dicarboxylic acids having 4 to 12 carbon atoms
Examples of the nylon salt consisting of 12 diamines include adipic acid-hexamethylene diamine salt, Q bacic acid-hexamethylene diamine salt, isophthalic acid-hexamethylene diamine salt, terephthalic acid-trimedylhexamethylene diamine salt, etc. It will be done.

In the present invention, diamines having 2 to 12 carbon atoms include ethylenediamine, diaminopropane, diaminobutane,
Examples include hexamethylene diamine, phenylene diamine, tolylene diamine, xylylene diamine, diamine diphenyl ether, and particularly preferred are ethylene diamine and hexamethylene diamine.

As the lactones in the present invention, 4-membered ring bu[1-biolactone] and 70-ring caprolactones can generally be used, but particularly preferred are ε-caprolactones.

ε-caprolactones are produced industrially by oxidizing cyclohexanone with peracetic acid by the Bayer-Villiger reaction.

The method for producing the modified amide diol of the present invention includes:
A polyamide-forming compound and a diamine are synthesized to form a diamine polyarimide, and a lactone is subjected to ring-opening addition polymerization to the diamine polyamide.

The condensation reaction to obtain the diamine polyamide in the present invention may be carried out by a conventional method. 1. That is, the condensation reaction is carried out at a reaction temperature of 100 to 280° C. in the presence of a catalyst.

Catalysts used include tetramethyl titanate, atriisopropyruditane-1, tetrabutyl titanate,
Tetraalkyl titanates such as tetra-2-edylhexyl titanate, tetradodecyl titanate, and tetrahexadodecyl titanate; titanium catalysts such as potassium titanium nitrate; tin catalysts such as dibutyltin oxide, dibutyltin dilaurate, and heptabutyltin oxide; Preferably used are silconium tetraalkoxide catalysts such as rhabtoxide and zirconium isobroboxide, hafnium tetraalkoxide catalysts such as hafnium tetraethoxide, and lead catalysts such as lead acetate.

The ring-opening addition polymerization reaction of lactones to the amino groups of the diamine polyamide in the present invention is carried out at 100 to 230°C, preferably at 120 to 180°C.

If it is lower than 100°C, the reaction rate will be slow and 2
This is because if the temperature is higher than 30° C., depolymerization of the lactones which have been cycloadded between /V may occur, leading to an increase in low molecular weight by-products.

Although the reaction is carried out at normal pressure F, the pressure may be reduced at the beginning of the reaction in order to completely remove the condensation water generated in the step of obtaining the diamine polyamide and the water contained in the lactones.

If the water content is 0.1% or more (based on the total amount of diamine polyamide lactone A1),
Using this water as an initiator, the lactones undergo ring-opening addition polymerization, and there is a possibility that polylactones that are not bonded to the diamine polyamide may be produced.

For this reaction, it is preferable to use a catalyst, such as tetrabutyl titanate, tetraethyl titanate,
Titanium compounds such as tetraethyl titanate, organic tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin dilaurate, and tin halide compounds such as stannous chloride, stannous bromide, and stannous iodide can be used. can.

The catalyst used ω is 0.01 to 11000 relative to the starting material.
ppm, preferably 0.2 to 500 ppm.

The ring-opening addition polymerization reaction of lactones may be carried out without a solvent, or in a solvent containing no active hydrogen such as -luene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or the like.

However, solvents having ester bonds are not preferred.

This is because, during the reaction, a transesterification reaction may occur with the ester group of the polylactone, resulting in the production of polylactone that is not bonded to the diamine polyamide.

When using stannous chloride as a catalyst, it hardly promotes the Nisder exchange reaction, so it is possible to use a lactone-modified polyamide diol with a narrow molecular force distribution, and it is also possible to use an ester solvent.

However, when using a titanium-based catalyst, it is particularly desirable to avoid Nisder-based solvents because they promote the transesterification reaction.

The proportion of lactones in the lactone-modified amide diol of the present invention is 5 to 9 per 100 parts by weight of the modified amide diol.
The single hanging part, preferably 20 to 801 parts.

The reason for this is that if there is too much, the desired heat resistance cannot be obtained, and on the other hand, if there is too little, sufficient flexibility cannot be obtained.

(Effects of the Invention) The lactone-modified amide diol of the present invention will be explained below with reference to examples, but the present invention is not limited to these.

In the example, part means a heavy part.

Example 1 430 parts of 12-aminododecanoic acid was placed in a 3N separable flask equipped with a nitrogen inlet tube, a thermometer, a dehydrator, and a stirring device.
116 parts of hexamethylene diamine, 0.06 parts of tetrabutyl titanate, 150-200 parts under nitrogen atmosphere
The solidification reaction was carried out at ℃ for about 5 hours.

As a result, a diamine polyamide with an amine value of 190 (01+Itg/g) was obtained.

Next, 1490 parts of ε-caprolactone was charged into the flask, and addition polymerization was carried out at 160°C. When the unreacted ε-caprolactone amounted to 0.5i 1%, the reaction was stopped, and water was added.
) 1,920 parts of lactone-modified amide diol having an average molecular weight of 2,078 was obtained. The ring-opening addition polymerization of ε-caprolactone was carried out for about 5 hours.

The obtained lactone-modified amide diol has an appearance (Gardner) 1 hydroxyl value (NiollIItg/bi) 54.0 melting point (
'C) 130-134 Remaining caprolactone 11 (%) 0.5 In the infrared absorption spectrum, the following absorption bands were observed, and the material was found to be a lactone-modified amide diol based on the assignment of each absorption band.

3550 α-1 → 0-H stretching vibration of primary hydroxyl group 2925 n → stretching vibration of CH2 1730
II → Characteristic absorption band of ester carbonyl compound 1655 , , → Characteristic absorption band of secondary acid carbonyl compound The molecular structure is as follows.

By using the obtained lactone-modified amide diol as a soft segment for polyurethane, polyester elastomer, nylon elastomer, paint, etc., it is possible to obtain a polymer with excellent heat resistance, and to obtain a polymer with excellent heat resistance. It is expected that the field of application will further expand.

Claims (1)

[Scope of Claims] (a) Nylon consisting of an aminocarboxylic acid having 6 to 12 carbon atoms, a lactam having 6 to 12 carbon atoms, or a dicarboxylic acid having 4 to 12 carbon atoms, and a diamine having 4 to 12 carbon atoms Diamine polyamide obtained by reacting one or more polyamide-forming compounds selected from salts with (b) a diamine having 2 to 12 carbon atoms, 95 to 3 parts by weight of amino groups, and (c) 5 to 97 parts by weight of lactones. Lactone-modified amide diol obtained by ring-opening addition polymerization (parts by weight)