JPH06184534A - Stabilized organic material composition - Google Patents

Abstract

PURPOSE:To impart a stability against heat deterioration and thermal oxidation deterioration to an organic material by incorporating specific compounds in the material. CONSTITUTION:This composition is prepared by mixing a monosulfoxide compound of formula O=S(CH2CH2COOR)2 (wherein R is a 1-18C alkyl group) and a phenolic antioxidant with an organic material, particularly one which is susceptible to deterioration by heat and oxygen. The composition containing these compounds exhibits a high stability against heat deterioration and thermal oxidation deterioration.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic material composition imparted with stability against thermal deterioration and thermal oxidative deterioration. More specifically, the present invention relates to an organic material composition having improved processing stability and long-term heat resistance by using a specific monosulfoxide compound together with a phenolic antioxidant.

[0002]

2. Description of the Related Art Organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubbers, mineral oils, lubricating oils, adhesives and paints are subject to the action of heat and oxygen during production, processing and use. It is known that the physical properties are deteriorated and the commercial value is remarkably impaired due to deterioration and accompanying phenomena such as molecular cutting and molecular crosslinking. As means for imparting stability against such deterioration, various phenol-based, phosphorus-based, sulfur-based, amine-based and other stabilizers have been used singly or in combination of two or more. However, the use of conventional stabilizers has not been sufficiently satisfactory in stability, and further improvements have been desired.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an organic material composition having excellent stability against thermal deterioration and thermal oxidative deterioration.

The inventors of the present invention have conducted extensive studies to develop a stabilizer capable of imparting an excellent stabilizing effect against heat deterioration and thermo-oxidative deterioration to organic materials. As a result, they have found that the combined use of a specific monosulfoxide compound with a phenolic antioxidant can impart excellent stability to organic materials, and have completed the present invention.

[0005]

[Means for Solving the Problems]

That is, the present invention provides an organic material with the following formula (I):

[0007]

Embedded image O = S (CH ₂ CH ₂ COOR) ₂ (I)

(In the formula, R represents alkyl having 1 to 18 carbon atoms)

The present invention provides an organic material composition comprising a monosulfoxide compound represented by and a phenolic antioxidant in a stabilizing effective amount.

The monosulfoxide compound represented by the above formula (I) can be produced, for example, by oxidizing the corresponding sulfide compound with an organic peracid in an organic solvent. Halogenated hydrocarbons such as methylene chloride and chlorobenzene are suitable as the organic solvent, and m-chloroperbenzoic acid is suitable as the organic peracid. A specific example of the method for producing this compound is shown in the synthetic example described below.

In the above formula (I), the alkyl represented by R may be a straight-chain alkyl, or may be branched or cyclic when it has 3 or more carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, cyclohexyl, isooctyl, tert-octyl, nonyl, decyl, lauryl, myristyl, stearyl and the like. Among them, alkyl having a relatively large number of carbon atoms,
For example, those having 6 to 18 carbon atoms are preferable.

The phenolic antioxidant used in the present invention is a compound having a phenol skeleton and having a substituent, preferably an alkyl, on at least one of the ortho positions of the phenolic hydroxyl group, and preferably both. Any material may be used as long as it imparts an antioxidant property to the material. At least one of the ortho positions of the phenolic hydroxyl group is an alkyl having a quaternary carbon bonded to a benzene ring, such as tert-butyl, tert-pentyl, tert.
-Octyl and the like are preferred. Specific examples of such phenolic antioxidants include the following.

2,6-di-tert-butyl-4-methylphenol, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,
2'-methylenebis (6-tert-butyl-4-methylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl]-
4,6-di-tert-pentylphenyl acrylate,
4,4'-butylidene bis (6-tert-butyl-3-methylphenol), 3,9-bis [2- {3- (3-te
rt-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,
4,8,10-Tetraoxaspiro [5.5] undecane, 2- (3,5-di-tert-butyl-4-hydroxyanilino) -4,6-bis (n-octylthio) -1,
3,5-triazine, 2,2'-ethylidene bis (4,
6-di-tert-butylphenol), 2,2'-ethylidenebis (4-sec-butyl-6-tert-butylphenol),

1,1,3-tris (5-tert-butyl-
4-hydroxy-2-methylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) phenyl] terephthalate, tetrakis [methylene-3 −
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,2'-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate], 1,
3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris [2- {3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionyloxy} ethyl] isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris (3,5) -Di-tert
-Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene.

The organic material to be stabilized in the present invention may have a property of being deteriorated by heat or oxygen. Specifically, for example, the following may be mentioned, and each of them may be a single substance or a mixture of two or more types, but is not necessarily limited thereto.

(1) Polyethylene, for example, low density polyethylene (LD-PE), high density polyethylene (HD-P)
E), linear low density polyethylene (LLD-PE); (2) polypropylene; (3) methylpentene polymer; (4) EEA (ethylene / ethyl acrylate copolymer) resin; (5) ethylene / vinyl acetate copolymer resin (6) Polystyrenes such as polystyrene, poly (p
-Methylstyrene), poly (α-methylstyrene); (7) AS (acrylonitrile / styrene copolymerization) resin; (8) ABS (acrylonitrile / butadiene / styrene copolymerization) resin; (9) AAS (special acrylic rubber / (Acrylonitrile / styrene copolymerization) resin; (10) ACS (acrylonitrile / chlorinated polyethylene /
Styrene copolymer) resin;

(11) Chlorinated polyethylene, polychloroprene, chlorinated rubber; (12) Polyvinyl chloride, polyvinylidene chloride; (13) Methacrylic resin; (14) Ethylene / vinyl alcohol copolymer resin; (15) Fluorine resin (16) Polyacetal; (17) Grafted polyphenylene ether resin and polyphenylene sulfite resin; (18) Polyurethane; (19) Polyamide; (20) Polyethylene terephthalate, Polybutylene terephthalate; (21) Polycarbonate; (22) Polyacrylate (23) Polysulfone, polyetheretherketone, polyethersulfone; (24) Aromatic polyester resin; (25) Epoxy resin; (26) Diallyl phthalate prepolymer; (27) Silicone resin; (28) Unsaturated polyester resin (29) Acrylic modified benzoguanamine resin; (30) Benzo Anamin / melamine resins; (31) urea resins;

(32) polybutadiene; (33) 1,2-polybutadiene; (34) polyisoprene; (35) styrene / butadiene copolymer; (36) butadiene / acrylonitrile copolymer; (37) ethylene / propylene copolymer Polymer; (38) Silicone rubber; (39) Epichlorohydrin rubber; (40) Acrylic rubber; (41) Natural rubber;

(42) Chlorine rubber paint; (43) Polyester resin paint; (44) Urethane resin paint; (45) Epoxy resin paint; (46) Acrylic resin paint; (47) Vinyl resin paint; (48) Amino Alkyl resin paint; (49) Alkyd resin paint; (50) Nitrocellulose resin paint; (51) Oil paint; (52) Wax; (53) Lubricating oil.

When the monosulfoxide compound of the formula (I) and the phenolic antioxidant are used in combination with such an organic material, the combined ratio of the two can be arbitrarily set, but preferably, The monosulfoxide compound of the formula (I) is used in an amount of 0.5 to 10 times by weight that of the phenolic antioxidant. Even if the amount of the monosulfoxide compound is less than 0.5 times by weight, some effect is exhibited, but it is not always sufficient, and it is possible to use more than 10 times by weight. It is difficult to obtain the effect that is worth the cost, which is economically disadvantageous.

As the monosulfoxide compound, one kind in which R in the formula (I) is a specific alkyl can be used, or of course, two or more kinds in which R is different can be used in combination. . Also, only one type of phenolic antioxidant can be used,
It is also possible to use two or more types in combination.

When the monosulfoxide compound of the formula (I) and the phenolic antioxidant are compounded in the organic material, a stabilizing effective amount of each is compounded, but usually, each is added to 100 parts by weight of the organic material. A range of 0.01 to 5 parts by weight is suitable. In use, the monosulfoxide compound and the phenolic antioxidant may be mixed in advance and then added to the organic material, or they may be separately blended.

The organic material prepared by blending the monosulfoxide compound and the phenolic antioxidant according to the present invention may further contain other additives such as sulfur compounds other than the compound represented by the formula (I), if necessary. Antioxidant, phosphorus antioxidant, UV absorber, hindered amine light stabilizer,
It may also contain a lubricant, a plasticizer, a flame retardant, a nucleating agent, a metal deactivator, an antistatic agent, a pigment, an inorganic filler and the like. When these additives are used, they can be compounded at the same time as the monosulfoxide compound of the formula (I) and / or the phenolic antioxidant, or at a stage different from them. it can.

In blending the monosulfoxide compound of formula (I) and the phenolic antioxidant, or other optional additives, with the organic material,
Any known method and apparatus for obtaining a homogeneous mixture can be used. For example, when the organic material is a solid polymer, a monosulfoxide compound and a phenolic antioxidant or further optional additives,
Can be blended directly with the solid polymer,
Further, the monosulfoxide compound and the phenolic antioxidant or further optional additives may be added to the solid polymer in the form of a masterbatch. When the organic material is a synthetic polymer, it should be added to the polymer solution during or immediately after the polymerization in the form of a solution or dispersion of a monosulfoxide compound and a phenolic antioxidant or any other additive. You can also On the other hand, when the organic material is a liquid such as oil, it is possible to directly add and dissolve the monosulfoxide compound and the phenolic antioxidant or any other additive, or the monosulfoxide. It is also possible to add the compound and the phenolic antioxidant or further optional additives in a state of being dissolved or suspended in a liquid medium.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The% and parts in the examples are on a weight basis unless otherwise specified.

Synthesis example

30 ml of a methylene chloride solution in which 2.9 g of dioctadecyl 3,3'-thiodipropionate was dissolved.
To the above, 0.75 g of m-chloroperbenzoic acid was added and stirred at room temperature for 25 hours. After washing with water, diethyl ether was added to the organic solvent layer, and the precipitated crystals were collected by filtration to obtain 1.3 g of dioctadecyl 3,3'-sulfinyl dipropionate.

Yield: 44% Appearance: White crystals Melting point: 84.0-85.5 ° C. Mass spec (FD-MS): m / z 698

The following compounds were used in the following examples.

AO-1: 2,6-di-tert-butyl-4-methylphenol AO-2: tetrakis [methylene-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate] methane AO-3: 3,9-bis [2- {3- (3-tert-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4
8,10-Tetraoxaspiro [5.5] undecane SY-1: didodecyl 3,3′-thiodipropionate TMS1: didodecyl 3,3′-sulfinyl dipropionate TMS2: dioctadecyl 3,3′-sulfinyl dipro Peonate

Example 1: Stabilization of polypropylene against thermal degradation

[Composition] Unstabilized polypropylene 100 parts Calcium stearate 0.05 parts Phenolic antioxidant (AO-1) 0.05 parts Test stabilizer 0.1 parts

The above mixture was melt-kneaded at 230 ° C. by a 30 mmφ single screw extruder and pelletized. Using these pellets, melt flow with a melt indexer
The rate (MFR) was measured and the thermal stability was evaluated.
Here, according to JIS K 7210, 270 ° C
The fluidity (g / 10 minutes) after retention for 10 minutes was measured with M
It was set to FR. Since polypropylene causes the molecular chain to be broken by heat to increase the fluidity, the smaller MFR after high temperature retention in the melt indexer, the better the thermal stability (processing stability). The test results are shown in Table 1.

[0034]

[Table 1]

Example 2: Stabilization of polypropylene against thermal oxidative degradation

[Composition] Unstabilized polypropylene 100 parts Calcium stearate 0.05 parts Stabilizers listed in Table 2

The above mixture was melt-kneaded at 230 ° C. by a 30 mmφ single-screw extruder and pelletized. The pellets were molded by an injection molding machine at 230 ° C. to obtain 1 mm thick test pieces. The test piece was placed in a gear oven and heated by circulating air at 160 ° C., and the time until the test piece became brittle (brittle life) was measured. The longer the brittle life,
This means that the stability against thermal oxidative deterioration is excellent. The test results are shown in Table 2.

[0038]

[Table 2]

[0039]

According to the present invention, the organic material composition in which the specific sulfoxide compound is blended with the phenolic antioxidant exhibits excellent stability against heat deterioration and heat oxidation deterioration. Therefore, a high-quality product can be obtained by blending such a sulfoxide compound and a phenolic antioxidant with various organic materials including thermoplastic resins such as polyolefin.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Tetsuo Yamaguchi 3-98 Kasugade, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd.

Claims (1)

[Claims] 1. An organic material containing a monosulfur represented by the following formula: O = S (CH ₂ CH ₂ COOR) ₂ (I) (wherein R represents alkyl having 1 to 18 carbon atoms). An organic material composition comprising a foxide compound and a phenolic antioxidant in a stabilizing effective amount.