JPH056567B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a soft segment oligomer or polymer that has heat resistance, flexibility, and water resistance and is useful as a soft segment oligomer or polymer used in the synthesis of paints and various elastomers, resin modification, etc. This invention relates to an excellent novel lactone-modified oxycarboxylic acid having an amide group, a carboxyl group, and a hydroxyl group.

[Prior Art] Ring-opening addition polymerization of lactones is generally carried out using an active hydrogen-containing initiator, such as a hydroxyl group in alcohols or an amino group in amines.

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 oligomers or polymers as soft segments used in the synthesis of these resins are
Adipate-based polyesters such as ethylene glycol adipate, 1,4-butylene glycol adipate, and 1,6-hexanediol adipate having an average molecular weight of ~5000, polycaprolactone,
Also widely used are polyethers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and polybutadiene polyols.

[Problems to be Solved by the Invention] However, polyester polyols such as adipate polyols and polycaprolactone have the drawback of poor water resistance and solvent resistance due to their ester bonds. For example, polyurethane made from ethylene glycol adipate polyester, which is an adipate polyester, has excellent elastic recovery properties, but has poor water resistance, and its products are
It will become unusable in ~2 years. Furthermore, polyether polyols have excellent low-temperature properties because they have ether bonds, but they have the drawback of being susceptible to oxidative deterioration and having extremely poor weather resistance and heat resistance.

Although olefin polyols such as polybutadiene polyols have excellent water resistance, they have the disadvantage of poor compatibility with other resins.

In addition, as a recent trend, heat-resistant polyurethane, polyester elastomer, nylon elastomer, etc. are required, and in order to improve heat resistance, it is natural that the soft segment of the polymer has excellent heat resistance, towability, and reactivity. It is necessary to use highly oligomers or polymers.

However, at present, there are no oligomers or polymers having soft segments that can sufficiently satisfy the above performance, and it is difficult to improve the heat resistance of elastomers as described above.

Therefore, the present inventors conducted intensive studies to obtain oligomers or polymers that can be used as soft segments that have excellent heat resistance and towability. The present invention was completed by discovering that a lactone-modified oxycarboxylic acid having an amide group obtained by ring-opening addition polymerization is an oligomer or polymer that becomes a soft segment having heat resistance and towability.

[Structure of the Invention] That is, the present invention has the following structural formula: <<However, in formulas () and (), R is hydrogen or an aminocarboxylic acid residue, when R is hydrogen, n is an integer of 1 to 11, and when R is an aminocarboxylic acid residue, n is 1, R ^a and R ^b are hydrogen, methyl group or ethyl group, and can be changed into other groups at the same time. m is an integer from 4 to 8, x is 0<x<
A lactone-modified oxycarboxylic acid with a numerical value of 100.

The aminocarboxylic acid, which is one of the starting materials used in the present invention, has one or more carboxyl groups and one or more primary or secondary amino groups in the molecule, and has the following general formula: ≪However, R is hydrogen or an aminocarboxylic acid residue, when R is hydrogen, n is an integer of 1 to 11, and when R is an aminocarboxylic acid residue, n is 1≫ or the following structural formula It is expressed as

The compound represented by the structural formula () has a primary amino group, and the compound represented by the structural formula () has a secondary amino group, which is proline.

For example, compounds represented by the structural formula () include glutamine, glutamic acid, glutathione, aminocaprylic acid, aminocapric acid, aminoenanthic acid, aminopergonic acid, aminoundecanoic acid, glycylglycine, alanine, aminobutyric acid, aminocaproic acid, arginine, Asparagine, aspartic acid, titrulline, tryptophan, threonine, glycine, cystine, histidine, oxyproline, isoleucine, leucine, lysine, methionine, ornithine, phenylalanine, phenylglycine, serine, aminododecanoic acid, tyrosine, valine, etc. I can do it.

Particularly preferred are aminocaproic acid, aminoundecanoic acid, aminododecanoic acid, and the like. The above structural formula () is obtained when an aminocarboxylic acid having a primary amino group is used as a starting material, and the structural formula () is obtained when an aminocarboxylic acid having a secondary amino group is obtained as a starting material. It is a carboxylic acid.

In addition, the other starting material, lactones, has the following structural formula: ≪R ^a and R ^b are hydrogen, methyl or ethyl groups, and can be changed to other groups at the same time. m is an integer from 4 to 8≫.

Specifically, 4-membered ring propiolactones, 7
Although ring-membered caprolactones can generally be used, ε-caprolactone is particularly preferred.

In the case of ε-caprolactone, R ^a in the above structural formula
and R ^b are both hydrogen and the value of m is 5.

ε-caprolactone is produced industrially by oxidizing cyclohexanone with peracetic acid by the Baeyer-Villiger reaction.

The proportion of lactone units in the lactone-modified oxycarboxylic acid represented by the structural formula () or () of the present invention is 99 to 1 part by weight, preferably lactone-modified oxycarboxylic acid represented by the structural formula () or (). Average molecular weight of acid is 500
~5000.

That is, x in the structural formula () or () has a value of 0<x<100.

For example, when aminocaproic acid and ε-caprolactone are used as starting materials, the proportion of ε-caprolactone in the synthesized modified oxycarboxylic acid is 73.8 to 97.4 parts by weight.

This is because if the proportion of lactones is too small, the resin synthesized using it will not have sufficient flexibility, and if it is too large, heat resistance cannot be expected.

The water content of the aminocarboxylic acid used in the synthesis is preferably 0.1 parts by weight or less based on the aminocarboxylic acid. If the amount exceeds 0.1 part by weight, the lactones undergo ring-opening addition polymerization using water in the aminocarboxylic acid as an initiator, and the formation of polycaprolactone that is not bonded to the aminocarboxylic acid cannot be ignored.

The reaction temperature for ring-opening addition polymerization of lactones to primary or secondary amino groups of aminocarboxylic acids is:
It is carried out at 100-240°C, preferably 120-180°C.
If the temperature is lower than 100℃, the reaction rate will be low;
If the temperature is higher than ℃, the self-condensation rate of aminocarboxylic acid will increase, producing polyaminocarboxylic acid, and lactones will boil and escape from the reaction system, causing the raw material ratio to change from the original molecular design. This is because there is.

Further, the reaction is carried out under normal pressure, but in order to suppress self-condensation of the aminocarboxylic acid, a pressure of 0.5 Kg/cm ³ G or more may be applied with an inert gas such as N ₂ or CO ₂ as appropriate.

Although this reaction proceeds satisfactorily even without a catalyst, various metal catalysts may be added. As a catalyst, titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetraethyl titanate, etc.
Organotin compounds such as tin octylate, dibutyltin oxide, and dibutyltin dilaurate. Furthermore, tin halide compounds such as stannous chloride, stannous bromide, and stannous iodide can be used. The amount used is 1000~ for the total starting materials.
0.01 ppm, preferably 500-0.2 ppm.

The reaction may be carried out without a solvent, or with toluene,
The reaction may be carried out in a solvent having no active hydrogen such as xylene, methyl ethyl ketone, methyl isobutyl ketone, etc. However, a solvent having an ester bond is not preferred.

This is because a transesterification reaction with the ester group of polycaprolactone may occur during the reaction, resulting in the production of polycaprolactone that is not bonded to the aminocarboxylic acid.

[Effect of the invention] The lactone-modified oxycarboxylic acid having an amide bond obtained as described above can be used as an oligomer or polymer having a soft segment in various resins such as polyester, polyamide, and polyurethane that require heat resistance. It is also used as a raw material, and because it has an amide bond in its molecule, it has high compatibility with polyamides and the like, and as an external plasticizer that maintains heat resistance.

The lactone-modified oxycarboxylic acid of the present invention will be explained below with reference to examples, but the present invention is not limited to these.

In the examples, parts mean parts by weight.

Example 1 6-aminocaproic acid 131 was placed in a four-necked flask equipped with a nitrogen inlet tube, thermometer, cooling tube, and stirring device.
1, 456 parts of ε-caprolactone, and 0.0587 parts of tetrabutyl titanate, and heated at 150℃ under nitrogen atmosphere.
By reacting for about 3 hours, the amount of unreacted ε-caprolactone was reduced to 0.2 parts or less.

The obtained lactone-modified oxycarboxylic acid has the following properties: Appearance (Gardner) Acid value of 1 or less (mgKOH/g) 95.3 OH value (〃) 95.3 Viscosity (cp/60°C) 550 Melting point (°C) 47-49 It had The acid value and OH value indicate that the obtained lactone-modified oxycarboxylic acid has the same amount of hydroxyl groups as carboxyl groups.
In the infrared absorption spectrum, the following absorption bands were observed.

3550cm ^-1 : OH stretching vibration of primary hydroxyl group 2933cm ^-1 : stretching vibration of -CH ₂ - 1727cm ^-1 : Characteristic absorption band of ester carbonyl compound 1655cm ^-1 : Characteristic absorption band of amide carbonyl compound Each of the above absorption bands From the assignment and analysis results, it was found that this substance is a lactone-modified oxycarboxylic acid represented by the following structural formula, which is a specific structural formula of general formula ().

Claims (1)

[Claims] 1. The following structural formula Or the structural formula below <<However, in formulas () and (), R is hydrogen or an aminocarboxylic acid residue, when R is hydrogen, n is an integer of 1 to 11, and when R is an aminocarboxylic acid residue, n is 1, R ^a and R ^b are hydrogen, methyl group or ethyl group, and can be changed into other groups at the same time. m is an integer from 4 to 8, x is 0<x<
A lactone-modified oxycarboxylic acid represented by a numerical value of 100.