JPH0562890B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polycaprolactone compound having a carboxyl group at the end thereof, and more specifically, a polycaprolactone compound having a carboxyl group at the end thereof, which provides polyamide elastomers, polyamide resins, and epoxy resins with excellent heat resistance and improved flexibility. This invention relates to polycaprolactone compounds. [Prior art] Polyamide elastomers have recently attracted attention as new materials in the elastomer field, and among polyamide elastomers, aliphatic polyesteramide elastomers that use polycaprolactone as the polyester component are particularly lightweight, have low-temperature properties,
As a material with excellent chemical resistance, oil resistance, sound deadening properties, moldability, heat resistance, and water resistance, it is used for automobile hoses, tubes, wiper rubber, sports shoe soles, etc., as well as food and medical products. Demand is expected in fields that require strict quality in terms of hygiene, such as equipment. [Problems to be Solved by the Invention] However, during the synthesis of aliphatic polyesteramide elastomers using polycaprolactone, polycaprolactone depolymerizes during synthesis under high temperature and high vacuum conditions, causing manufacturing problems such as blocking vacuum lines. It has major problems. On the other hand, epoxy resins can also be used as adhesives, FRP, flooring materials, etc.
Epoxy resins are used for various purposes such as powder coatings, but since epoxy resins are generally hard and brittle, there is a need for epoxy resins to be made more flexible. [Means for Solving the Problems] Therefore, the present inventors have made efforts to obtain a polycaprolactone compound that is resistant to depolymerization under high temperature and high vacuum conditions and can impart flexibility to epoxy resins and polyamide resins. As a result of investigation, it was discovered that a polycaprolactone compound having a carboxyl group at the terminal represented by the following general formula is a polycaprolactone compound suitable for the above-mentioned purpose, and the present invention was completed. That is, the present invention is based on the general formula

【table】 ‖
〓O−(OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ C) _o4 −OH〓 _n4

(However, R is an aromatic hydrocarbon group having 1 to 2 aromatic rings, an alicyclic hydrocarbon group having 4 to 37 carbon atoms, or a radical having 1 to 30 carbon atoms) It is an active aliphatic group and does not contain a hydroxyl group, an amino group, or an acid anhydride group in the molecule. n ₁ , n ₂ , n ₃ and n ₄ are 0 or an integer from 1 to 50; The sum is 1 to 50. m ₁ , m ₂ , m ₃ and m ₄ are 0 or 1, and the sum is an integer of 1 to 4. be. Monocarboxylic acids or polycarboxylic acids used in the present invention include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, mystylic acid, palmitic acid, stearic acid, crotonic acid, Oleic acid, linoleic acid, linolenic acid, methylcyclohexenecarboxylic acid, benzoic acid, toluic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nadic acid, Hettic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 3-methyltetrahydrophthalic acid, 3-methylhexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, methylterephthalic acid, naphthalene dicarboxylic acid, tetrachlorophthalic acid, tetra Bromphthalic acid, 1,3-dimethyl-1,2,3-cyclohexanetricarboxylic acid, 1-carboxy-4-methylcyclohexylsuccinic acid, trimellitic acid, trimesic acid, methylcyclohexenetetracarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid Examples include carboxylic acids. Preferably acetic acid, propionic acid, lauric acid,
Mention may be made of stearic acid, benzoic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid. Epsilon-caprolactone, a necessary component for producing the compounds of the present invention, is produced industrially by oxidizing cyclohexanone with peracetic acid by the Bayer-Villiger reaction. In addition to ε-caprolactone, other lactones such as 4-membered ring propiolactone can also be used in combination with ε-caprolactone as long as they do not impair the characteristics of the present invention. Regarding the synthesis of a polycaprolactone compound having a carboxyl group at the end, the amount of ε-caprolactone added to the carboxylic acid is determined depending on the molecular weight of the target product, but is 25 to 10,000 parts per 100 parts by weight of the carboxylic acid. is preferred. ε- to the carboxyl group of the carboxylic acid of the present invention
The ring-opening addition reaction of caprolactone is generally 80 to 240
℃, especially 120 to 200℃ is preferred. It is preferable to use a catalyst for this reaction, and examples of the catalyst include aluminum chloride, sulfuric acid, P-trienesulfonic acid, benzenesulfonic acid, tetrabutyl titanate, tetrapropyl titanate, soot octylate, dibutyltin oxide, dibutyltin dilaurate, and monochloride. tin, stannic chloride,
Stannous bromide, stannous iodide, etc. can be used. The amount used is preferably 0.0001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total amount of carboxylic acid and ε-caprolactone. The reaction may be carried out without a solvent, or with benzene,
The reaction may be carried out in a solvent that does not contain active hydrogen, such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or the like. Further, a polycaprolactone compound having a carboxyl group at the terminal can also be obtained by an esterification reaction between a carboxylic acid and ω-oxycaproic acid. [Effect of the invention] The polycaprolactone having a carboxyl group at the terminal of the present invention obtained as described above was heated at 250°C and 6 mm
It is useful as a raw material for aliphatic polyesteramide elastomers using polycaprolactone because it hardly undergoes depolymerization under Hg high temperature and high vacuum conditions. On the other hand, carboxyl group-terminated polycaprolactone compounds set to a predetermined average molecular weight are used as flexibility imparting agents for epoxy resins and as flexibility curing agents for epoxy powder coatings. By replacing the compound with dimer acid, it is expected that a flexible polyamide resin can be obtained. The present invention will be explained below using examples, but the present invention is not limited thereto. In addition, the number of parts in the examples represents parts by weight. [Example 1] Adipic acid was placed in a 15-necked flask equipped with a nitrogen inlet tube, thermometer, cooling tube, dropping funnel, and stirring device.
36.5 parts of toluene, 250 parts of toluene, and 15 parts of P-toluenesulfonic acid were added, and while stirring under nitrogen atmosphere, about
The temperature was raised to 100℃. While keeping the can temperature at 100-120℃, 463.5 parts of ε-caprolactone was added dropwise over about 4 hours, and after the dropwise addition was allowed to react at 120-125℃ for about 2 hours, 0.93wt each of unreacted ε-caprolactone adipic acid was added. A toluene solution of a polycaprolactone compound containing % and 0.11wt% was obtained. Next, 500 parts of toluene was added to this reaction solution to reduce the viscosity, and the temperature was maintained at approximately 70°C.
After neutralizing by adding 32 parts of a 10% aqueous sodium hydroxide solution, the mixture was washed twice with 500 parts of ion-exchanged water. Subsequently, toluene was removed using a rotary evaporator to obtain 490 parts of polycaprolactone dicarboxylic acid having an acid value of 58.40 (mg KOH/g, average molecular weight determined from the acid value: 1921). The obtained polycaprolactone dicarboxylic acid had the following properties. Acid value (mg KOH/g) 58.40 Hydroxyl value (mg KOH/g) 2.1 Unreacted adipic acid content (wt%) 1.40 Unreacted ε-caprolactone content (wt%) 0.17 GPC analysis results Figure 1 IR analysis results 2 Figure The characteristics of the main absorption wave number in the IR absorption spectrum diagram are as follows.・ 2925cm ^-1 → −CH ₂ − Asymmetric stretching vibration ・ 2850cm ⁻¹ → −CH ₂ − Symmetrical stretching vibration ・ 1735cm ⁻¹ → C=O stretching vibration of ester −COO− ・ 1710cm ⁻¹ → C of acid −COOH− =O stretching vibration・1460cm ^-1 →−CH ₂ −Scissors bending vibration・1160cm ⁻¹ →−C−O− of ester −COO−
Stretching vibration of C-structure NMR analysis results Figure 3 The signals in the NMR spectrum diagram are as follows.

[Table] Proton signals of
The formula of the obtained polycaprolactone dicarboxylic acid is as shown below. Table 1 shows the results of depolymerization of the polycaprolactone dicarboxylic acid with an average molecular weight of 1921 obtained as described above and the polycaprolactone diol with an average molecular weight of about 2000 having a normal terminal hydroxyl group at 250°C and 6 mmHg. Indicated.

[Table] Depolymerization conditions 250℃, 6mmHg, addition of tetrabutyl titanate at 0.1 part for 4 hoursNote-1 Amount Depolymerization rate = Distillate (monomer + dimer) / Charge amount x
100 Note-2 Manufactured by Daicel Chemical Industries, Ltd. OH value = 56.2 (Average molecular weight determined from OH value 1996) From Table 1, polycaprolactone with a carboxyl group at the end has a higher molecular weight than normal polycaprolactone with a hydroxyl group at the end It is recognized that it is difficult to depolymerize.

[Brief explanation of the drawing]

Figure 1 is a GPC chromatogram of the polycaprolactone having a carboxyl group at the end obtained in Example 1, and Figure 2 is an infrared absorption spectrum diagram of the same.
FIG. 3 is an NMR spectrum diagram of the same.

Claims (1)

[Claims] 1 General formula [Table] ‖
〓CO−(OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ C) _o4 −OH〓 _n4

(However, R is an aromatic hydrocarbon group having 1 to 2 aromatic rings, an alicyclic hydrocarbon group having 4 to 37 carbon atoms, or a radical having 1 to 30 carbon atoms) It is an active aliphatic group and does not contain a hydroxyl group, an amino group, or an acid anhydride group in the molecule. n ₁ , n ₂ , n ₃ and n ₄ are 0 or an integer from 1 to 50; The sum is 1 to 50. m ₁ , m ₂ , m ₃ and m ₄ are 0 or 1, and the sum is an integer of 1 to 4.) Polycaprolactone having a carboxyl group at the terminal.