JPH0368857B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel 3-alkyl or alkylenethiopropionic acid amide compound, and an organic-based antioxidant and slip agent containing the compound as an active ingredient. More specifically, the present invention relates to a novel 3-alkyl or alkylenethiopropionic acid amide represented by the chemical structural formula below, and an antioxidant and slip agent for organic substrates such as plastics containing the compound as an active ingredient. R-S-CH ₂ -CH ₂ -CO-NH ₂ [In the formula, R is CnH _2o+1 or CnH _2o-1 group, and n
is an integer from 3 to 22] Examples of CnH _2o+1 groups are propyl, isopropyl, n
-butyl, isobutyl, t-butyl, hexyl,
Octyl, decyl, undecyl, dodecyl (commonly known as lauryl), tridecyl, hexadecyl, octadecyl (commonly known as stearyl), eicosyl and docosyl groups, examples of CnH _2o-1 are octenyl,
These include dodecenyl, oleyl, erucyl, behenyl, cyclobentyl, cyclohexanyl, cyclooctyl, and cyclododecyl groups. That is, alkyl groups, cycloalkyl groups, and achilene groups have 3 to 22 carbon atoms, most preferably 8 to 18 carbon atoms.
It is a higher alkyl group or alkylene group having . Suitable examples of the novel 3-alkyl or alkylentiopropionic acid amide of the present invention include:
3-octylthiopropionic acid amide, 3-laurylthiopropionic acid amide, 3-stearylthiopropionic acid amide, 3-octenylthiopropionic acid amide, 3-dodecenylthiopropionic acid amide, 3-oleylthiopropionic acid amide These chemical structural formulas are as follows. C ₈ H ₁₇ −S−CH ₂ −CH ₂ −CO−NH ₂ C ₁₂ H ₂₅ −S−CH ₂ −CH ₂ −CO−NH ₂ C ₁₃ H ₃₇ −S−CH ₂ −CH ₂ −CO−NH ₂ C ₈ H ₁₅ −S−CH ₂ −CH ₂ −CO−NH ₂ C ₁₂ H ₂₃ −S−CH ₂ −CH ₂ −CO−NH ₂ C ₁₈ H ₃₅ −S−CH ₂ −CH ₂ −CO− _NH2 The novel 3-alkyl or alkylentiopropionic acid amide compounds of the present invention are produced by a process involving the reaction of 3-alkyl or alkylentiopropionic acid chloride with ammonia. Although the reaction can be carried out in a solvent, the use of a solvent is not particularly necessary. The reaction between these acid chlorides and ammonia can be quantitatively obtained by stirring for several hours while maintaining the reaction vessel in a heated state, and then by adding alcohol and cooling. Alkyl or alkylenethiopropionic acid amide precipitates out. The compound of the present invention is effective as an antioxidant when contained in a small amount in an organic base material, especially when used at high temperatures, and then used in contact with metals. and when the metal has a deterioration accelerating effect in organic substrates containing metal ions, the effect of suppressing the effect is equivalent to or greater than that of conventional metal preservatives and activation agents, and in addition, in organic substrates containing metal ions. When contained in a film-like molded article made of , it is highly effective as a slip agent, and is also effective in preventing cracks in the molded article. The compound of the present invention is contained in an organic base material for the purpose of achieving these effects, but the amount is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and has other antioxidant effects and metal deactivation effects. It does not preclude use in combination with additives that have a slip effect, etc. Further additives (including auxiliaries and fillers) include crosslinking agents and crosslinking promoters, phenolic, amine and other antioxidants, conductive materials (e.g. carbon black), fillers, flow oxidizing agents, flame retardants, foaming agents, ultraviolet stabilizers, dyeing and coloring agents, voltage stabilizers, tree inhibitors, metal deactivators, coupling agents, lubricants such as fatty acid soaps, and the like. Organic substrates containing antioxidants of the present invention include polyolefins, polystyrene, ABS,
Thermoplastic resins such as AS, PVC, polymethyl methacrylate, polyacrylate, polycarbonate,
and thermosetting resins, synthetic rubbers, oils, lubricating oils, etc., especially high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, ethylene-α olefin copolymer, ethylene-vinyl ester copolymer, Ethylene-alkyl acrylate copolymers, etc. are used for applications that come into contact with metals,
Particularly suitable as a primary insulation material and semiconducting material for electric wire cables, and for areas that come into contact with other metals, such as printed wiring boards, plastic plated molded products, metal plate and plastic laminates, metal and plastic. Foam laminates, electrical parts, automobile parts, and other mechanical parts with metal products embedded in organic base materials, as well as metal fibers, metal powders, or metal products as structural reinforcements, heat resistance improvers, etc. in organic base materials. The oxidation stabilizer of the present invention is also effective for molded articles containing particles. Even when forming a film-like product using the above-mentioned polyolefin as an organic base material, if the organic compound of the present invention is included, in addition to being an oxidation stabilizer and deteriorating when metal comes into contact with it,
A small amount of the compound of the present invention constantly oozes out on the film surface, giving the film appropriate lubricity, imparting lubricity to stacked films, and making it easier to open bag-shaped products. Hereinafter, the present invention will be further illustrated by examples. Example 1 39.2 g (0.1 mol) of 3-stearylthiopropionic acid chloride and 13.4 g of NH ₄ OH 28% were placed in a 500 ml four-necked colben equipped with a condenser, a thermometer, a stirring rod, and a gas absorption trap attached to the top of the condenser.
(0.22 mol) and heated at 90-95℃ for 3 hours, and then heated with isopropyl alcohol at 75℃ or below.
When 120 ml of 3-stearylthiopropionic acid amide is added and cooled, it is separated at below 5°C and washed with 20 ml of isopropyl alcohol, yielding 35.1 g of the target product with a melting point of 107.0-108.5°C.
Obtained at 94.1%. The results of elemental analysis of this product were in good agreement with the theoretical values as shown in the table below, and the formation of 3-stearylthiopropionic acid amide was confirmed. [Elemental analysis data] (C ₂₁ H ₄₃ SON)

[Table] Example 2 In the same manner as in Example 1, only the raw materials were mixed with 3-oleylthiopropionic acid chloride (39.0g,
0.1mol). The melting point of the precipitated 3-oleylthiopropionic acid amide after purification is
At 105.0-106.5°C, the product was 35.0 g, yield 94%. The results of elemental analysis also showed good agreement with the theoretical values. [Elemental analysis data] (C ₂₁ H ₄₁ SON)

[Table] Example 3 The same method as in Example 1 was carried out except that the raw material was changed to 3-laurylthiopropionic acid chloride.
The obtained compound was 3-laurylthiopropionic acid amide with a melting point of 98 to 98.5°C, and the results of elemental analysis were in good agreement with the theoretical values. [Elemental analysis] (C ₁₅ H ₃₁ SON)

[Table] Example 4 The same method as in Example 1 was carried out except that the raw material was changed to 3-dodecenylthiopropionic acid amide. 3-dodecenylthiopropionic acid amide with a melting point of 97-99°C was obtained. [Results of elemental analysis] (C ₁₅ H ₂₉ SON)

[Table] Example 5 The same method as in Example 1 was carried out except that the raw material was changed to 3-octylthiopropionic acid chloride. The melting point of the obtained 3-octylthiopropionic acid amide was 76.5-77.5°C. The results of elemental analysis of this compound are as shown below.
Good agreement with C ₈ H ₁₇ SC ₂ H ₄ CONH ₂ . [Results of elemental analysis]

[Table] Example 6 The same method as in Example 1 was carried out except that the raw material was changed to 3-octenylthiopropionic acid chloride.
Octenylthiopropionic acid amide with a melting point of 72.5°C to 75.5°C was obtained. [Results of elemental analysis]

[Table] Example 7 Unstabilized polyethylene (manufactured by Nippon Unicar Co., Ltd.)
NUC9025) 100 parts by weight of the compound obtained in Example 3
Add 0.1 part by weight and melt in a high shear twin screw extruder.
The mixture was kneaded and passed through a pelletizer to obtain pellets.
This pellet is pressure-molded at 130°C using a compression molding machine to obtain a sheet with a thickness of 1 mm. . A disk with a diameter of 30 mm was punched out from this sheet as a test piece, placed on a well-polished copper plate, and placed in an air circulation thermostat kept at 150°C. observed. After 24 hours, spots appear locally, and after 48 hours, spots appear all over the area. However, at this point, no difference was observed in the mechanical properties of the films, demonstrating that this measurement method is extremely sensitive. Also known metal deactivator N,
When using N'-diphenyl oxamide, the same effect as when adding 0.5 parts by weight, about 5 times as much, is observed, but in this case, as an oxidation stabilizer,
Otherwise, the effect as a slip agent cannot be expected. Example 8 100 parts by weight of unstabilized polypropylene (Profax 6501 manufactured by Hercules Powder), 0.5 parts by weight of the compound obtained in Example 1 and 0.5 parts by weight of copper stearate or copper powder were mixed in an internal kneader kept at 170°C. in
Kneaded for 10 minutes. Differential thermal analysis was conducted using 5 mg of the kneaded material as a sample, and the exothermic peak temperature was 245°C.
In the case of the comparative sample to which the compound of Example 1 was not added, the exothermic peak was at 226°C and appeared on the lower temperature side of 19°C. This shows that the compound of Example 1 suppresses the oxidative deterioration reaction caused by copper ions until it reaches a high temperature. Example 9 Under the same kneading conditions as Example 8, Irganox-1010 (oxidation stabilizer, manufactured by Ciba-Geigi) was added to the sample.
An additional 0.5 part by weight was added. Differential thermal analysis was performed in the same way as in the previous example, and the exothermic peak temperature was 249°C. This shows a considerable improvement in the deterioration suppressing effect. Example 10 Low-density polyethylene (NUC- manufactured by Nippon Unicar Co., Ltd.)
9025) Add 0.1 part by weight of the compound obtained in Example 2 or the compound obtained in Example 3 to 100 parts by weight, and knead and blend under the conditions of Example 8. A blown film was produced using this kneaded material, and after being left at 23° C. and 50% relative humidity for 24 hours, the dynamic coefficient of friction (according to ASTM D 1894) was measured. 3
- 0.12 for the film added with oleylthiopropionic acid amide (Example 2), 0.15 for the film added with 3-laurylthiopropionic acid amide (Example 3), and a comparative film sample to which these compounds were not added. In this case, the dynamic friction coefficient was 1. This shows that the compound of the present invention provides the film with the appropriate slipperiness required.

Claims (1)

[Claims] 1. The chemical structural formula is R-S-CH ₂ -CH ₂ -CO-NH ₂ [R in the formula is CnH _2o+1 or CnH _2o-1 , and n
is an integer from 3 to 22] A 3-alkyl or alkylenethiopropionic acid amide compound represented by: 2 The chemical structural formula is R-S-CH ₂ -CH ₂ -CO-NH ₂ [R in the formula is CnH _2o+1 or CnH _2o-1, and n
is an integer from 3 to 22.] An organic-based antioxidant containing a 3-alkyl or alkylenethiopropionic acid amide compound represented by the following as an active ingredient. 3 The chemical structural formula is R-S-CH ₂ -CH ₂ -CO-NH ₂ [R in the formula is CnH _2o+1 or CnH _2o-1, and n
is an integer from 3 to 22. ] An organic-based slip agent containing a 3-alkyl or alkylentiopropionic acid amide compound represented by the following as an active ingredient.