JPS59190960A - 3-alkyl or alkylenethiopropionic acid amide based compound and antioxidant and slip agent for organic base material containing the same as main component - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R is CnH2n+1 or CnH2n-1; n is 3-22). EXAMPLE:3-Octylthiopropionic acid amide. USE:An antioxidant and slip agent for organic base materials, particularly useful as the antioxidant effective for use at high temperatures, and having great effect on the inhibition of deterioration accelerating action of a metal in the organic base materials in the use in contact with a metal and the organic base materials containing metal ions. PREPARATION:A 3-alkyl or alkylenethiopropionic acid chloride is reacted with ammonia to give a 3-alkyl or alkylenethiopropionic acid amide compound expressed by the formula. The reaction is carried out by stirring the reaction mixture while kept under heated conditions for several hours.

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 novel 3-
The present invention relates to an antioxidant and a slip agent for organic substrates such as plastics containing alkyl or alkylenethiopropionic acid amide and the compound as an active ingredient.

R-8-CH2-CH, -CO-NHz [wherein R is CI
(or CH group n 2n+1 n 2n
-1n is an integer from 3 to 22] CnH2n+, examples of groups are propyl, isopropyl, n
-butyl, isobutyl, t-butyl, hexyl, octyl, decyl, undecyl, dodecyl (commonly known as lauryl),
Tridecyl, hexadecyl, octadecy/L/ (commonly known as stearyl), eicosyl and tocosyl groups, and CH
Examples are octenyl, n 2n-1 do-anglenyl, oleyl, erucyl, behenyl, cyclopentyl, cyclohexanyl, Schifftetraoctyl, Schiff-dodecyl groups, and the like. That is, an alkyl, cycloalkyl, or alkylene group is a higher alkyl or alkylene group having 3 to 22 carbon atoms, most preferably 8 to 18 carbon atoms.

Suitable examples of the novel 3-alkyl or alkylenethiopropionic acid amide of the present invention include 6-octylthiopropionic acid amide, 3-laurylthiopropionic acid amide, 3-stearylthiopropionic acid amide, 3-octylthiopropionic acid amide, and 3-octylthiopropionic acid amide. Examples include nylthiopropionic acid amide, 3-dodecenylthiopropionic acid amide, and 3-oleylthiopropionic acid amide, and the chemical structural formulas of these are as follows.

c, HI3-8-CH2-CH2-Co-NH.

cttl (z-8-CH snow-CH2-Co-NH.

C11H37-S -CH2-CH2-C0-NH2C
, Hls-8-CH, -CH, -Go-NH.

Cl2H23-S -CH2-CH2-Co-NH2
Cl, Hs, -8-CH, -CH, -CO-NH.

The novel 3-alkyl or alkylene lentiopropionic acid amide compounds of the present invention are produced by a process that involves the reaction of a 6-alkyl or alkylene lentiopropionic acid peride 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 tetraphytes and ammonia can be quantitatively obtained by stirring for several hours while keeping the reaction vessel heated, and then by adding alcohol and cooling, 6-alkyl or alkylene can be obtained. Thiopropionic acid amide precipitates.

The compounds of the present invention are effective as antioxidants when incorporated in small amounts in organic substrates, particularly when used at high temperatures, and then used in contact with metals. In cases where the metal has a deterioration accelerating effect in an organic base material containing metal ions, the effect of suppressing the effect is equal to or greater than that of conventional metal deactivators, and the organic base material is further made of an organic base material. When contained in a film-like molded product, it is highly effective as a slip agent and is also effective in preventing cracks in the molded product.

The compound of the present invention is contained in an organic base material for the purpose of achieving these effects, and the amount thereof is 0.01 to 10 parts by weight, preferably α05 to 5 parts by weight, and has other antioxidant effects and metal deactivation effects. Effect: Can be used in combination with additives that have slip effects, etc.

Further additives (including auxiliaries and fillers) include crosslinking agents and crosslinking promoters, phenolic, aminic and other antioxidants, conductive materials (e.g. carbon black), fillers, flow Examples of such additives include 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.

The organic base material containing the antioxidant of the present invention includes polyolefins, polystyrene, and ABS.

Refers to thermoplastic resins such as As, PVC, polymethyl methacrylate, polyacrylate, polycarbonate, thermosetting resins, synthetic rubbers, oils, lubricating oils, etc., especially high-density polyethylene, medium-density polyethylene, low-density polyethylene, Polypropylene, ethylene-alpha olefin copolymers, ethylene-vinyl ester copolymers, ethylene-alkyl acrylate copolymers, etc. are particularly suitable for applications that come into contact with metals, particularly as primary insulation materials for electric cables and semiconductive materials. , Printed wiring boards that come into contact with other metals, plastic/mold molded products, laminates of metal plates and plastics, laminates of metal and plastic foam, organic substrates (with metal products embedded in them) The oxidation stabilizer of the present invention can also be used for electrical parts, automobile parts, other mechanical parts, and molded products containing metal fibers, metal powders, or particles as structural reinforcements, heat resistance improvers, etc. in organic base materials. It is also effective when forming a film-like product using the above-mentioned polyolefin as Ti equipment material.
When the organic compound of the present invention is contained, in addition to acting as an oxidation stabilizer and deteriorating upon contact with metal, a small amount of the compound of the present invention constantly oozes out onto the film surface, giving the film appropriate lubricity and making it easier to stack. It imparts slipperiness to the film and has the effect of making bag-shaped products easier to open.

Hereinafter, the present invention will be further illustrated by examples.

Example 1 A 500-year-old four-day Kolben equipped with a condenser, thermometer, stirring barrel, and a gas absorption trap from the top of the condenser was charged for 3 days.
-Stearylthiopropionic acid chloride 39.2 f
(0,1mot), NH4OH28% 1'5.
49 (0.22 mot) and heated at 90 to 95°C for 3 hours, and then added 2 Dml of isopropyl alcohol at 75°C or below and cooled, 6-styarylthiopionic acid amide precipitates. The product was separated and washed with 20-g of isopropyl alcohol to obtain the desired product with a melting point of 1070-108.5°C at 35.1 f and a yield of 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-stearylthiopetetrapionic acid amide was confirmed.

[Elemental analysis data] (C*xHts S ON )
Example 2 In the same manner as in Example 1, only the raw material was mixed with 3-oleylthiopropionic acid chloride (39,0?, 0,1 mol
) was implemented instead. The melting point of the precipitated 3-oleylthiopropionic acid amide after purification is 105.0 to 106
．． At 5°C, the product is 35. Of, the yield was 94%. The results of elemental analysis also showed good agreement with the theoretical values.

[Elemental analysis data] (C21H41SON) 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] (C11HstSON) Example 4 The same method as in Example 1 was carried out except that the raw material was changed to 3-dodecenylthiopropionic acid amide. Melting point 97-99℃
3-dodecenylthiopropionic acid amide was obtained.

[Results of elemental analysis] (C15lh*SON) Example 5 The same method as in Example 1 was carried out except that the raw material was changed to 6-octylthiopropionic acid amide. The melting point of the obtained 3-octylthiopropionic acid amide was 76.5-77.
The temperature was 5°C. The results of elemental analysis of this compound are in good agreement with C, Hl, and S C2H4C0NH, as shown below.

[Results of elemental analysis]

Example 6 The same method as in Example 1 was carried out except that the raw material was changed to 3-octenylthiopropionic acid chloride.

One point of octenylthiopropionic acid amide having a temperature of 72.5°C to 7565°C was obtained.

[Results of elemental analysis]

Example 7 Unstabilized polyethylene (NUc902 manufactured by Nippon Unicar Co., Ltd.
5) 0.1 part by weight of the compound obtained in Example 3 was added to 100 parts by weight, and the mixture was melted and kneaded in a high-shear twin-screw extruder, and passed through a pelletizer to obtain pellets.

This pellet is pressure-molded at 160°C using a compression molding machine to obtain a sheet with a thickness of 1 inch.
A 0-speed disk was punched out as a test piece, placed on a well-polished copper plate, and placed in an air circulation constant temperature oven maintained at 150°C to observe discoloration of the test piece over time. did. 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. In addition, the known Kinae inactivating agent N,
When using N/-diphenyl oxamide, the same effect as when adding 0.5 parts by weight, which is about 5 times as much, is observed, but in this case, the effect as an oxidation stabilizer or slip agent is not expected. I can't do it.

Example 8 Example 1 to 100 parts by weight of unstabilized polypropylene (Profax 6501 manufactured by Vercules Powder)
5 parts by weight of the compound 0 obtained above and 0.5 parts by weight of copper stearate or copper powder were kneaded for 10 minutes in an internal kneader kept at 170°C. Differential thermal analysis was conducted using kneaded product 5■ 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, which 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 Irg was added to the sample under the same crosstalk conditions as on the day of the example.
anox-1010 (oxidation stabilizer, manufactured by Ciba-Geigi)
An additional 0.5 part by weight was added. Differential thermal analysis was performed in the same manner as in the previous example, and the exothermic peak temperature was 249°C.

This shows that when used in combination with other antioxidants, the oxidative deterioration inhibiting effect can be significantly improved even under severe conditions in the presence of copper ions.

Example 10 Low density polyethylene (NUC-902 manufactured by Nippon Unicar Co., Ltd.
5) 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 mix 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-oleylthiopropionic acid amide (Example 2)
The coefficient of dynamic friction was 0.15 for the film containing 0.12.3-laurylthiopropionic acid amide (Example 3), and 0.15 for the film containing 0.12. It was 1. This shows that the compound of the present invention provides the film with the necessary appropriate slipperiness.

Claims (1)

[Claims] 1) The chemical structural formula is represented by R-S-CH-CH2-Co-NHz [in the formula, R is CnH2n+ or CnH2n-1, and n is an integer from 3 to 22] 3-alkyl or alkylenethiopropionic acid amide type compounds. 2) The chemical structural formula is R-8-CHz-CHz-Co-NHz [R in the formula is C
nH2n+1 or CnH2n-1, where n is an integer from 3 to 22] An organic-based antioxidant containing a 6-alkyl or alkylenethiopropionic acid amide compound represented by the following as an active ingredient. 3) The chemical structural formula is R-S -CH2-CH2-CO-1'JHz [in the formula, R is CnH2n+ or CnH2n-1 and n is 3
An integer between 22 and 22. ] An organic-based slip agent containing a 3-alkyl or alkylentiopropionic acid amide compound represented by the following as an active ingredient.