JP3111714B2 - Stabilized organic material composition - Google Patents

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 having stability against thermal degradation and thermal oxidation degradation. 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 in combination 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 subjected to the action of heat and oxygen during production, processing and use. It is known that physical properties are reduced and the commercial value is significantly impaired due to deterioration, accompanied by phenomena such as molecular cleavage and molecular crosslinking. As a means for imparting stability against such deterioration, various phenol-based, phosphorus-based, sulfur-based, and amine-based stabilizers have heretofore been used alone or in combination. However, the use of conventional stabilizers has not yet been able to provide sufficient stability, and further improvements have been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic material composition provided with better stability against thermal degradation and thermal oxidative degradation.

[0004] The present inventors have intensively studied to develop a stabilizer capable of imparting an excellent stabilizing effect against thermal degradation and thermal oxidation degradation to an organic material. As a result, they have found that excellent stability can be imparted to organic materials by using a specific monosulfoxide compound in combination with a phenolic antioxidant, and have completed the present invention.

[0005]

[Means for Solving the Problems]

That is, according to the present invention, an organic material is represented by the following formula (I)

[0007]

## STR2 ## O = S (CH ₂ CH ₂ COOR) ₂ (I)

(Wherein R represents alkyl having 1 to 18 carbons)

It is intended to provide an organic material composition containing a stabilizing effective amount of each of the monosulfoxide compound and the phenolic antioxidant represented by the formula (1).

The monosulfoxide compound represented by the formula (I) can be produced, for example, by oxidizing a 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. Specific examples of the method for producing this compound will be described in Synthesis Examples below.

In the formula (I), the alkyl represented by R may be linear or branched when it has 3 or more carbon atoms, or may be cyclic. 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 a substituent, preferably an alkyl, in at least one, and preferably both, of the ortho positions of the phenolic hydroxyl group. Any material may be used as long as it imparts antioxidant performance to the material. The ortho-position of the phenolic hydroxyl group may be an alkyl at least one of which is bonded to a benzene ring with a quaternary carbon, such as tert-butyl, tert-pentyl,
-Octyl and the like are preferred. Specific examples of such a phenolic antioxidant include the following.

2,6-di-tert-butyl-4-methylphenol, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
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'-butylidenebis (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'-ethylidenebis (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) propionyloxydiethyl] 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.

In the present invention, the organic material to be stabilized can have a property of being deteriorated by heat or oxygen. Specifically, for example, the following may be mentioned, and these may be each alone or a mixture of two or more, but are 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 copolymer) resin; (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin; (9) AAS (special acrylic rubber / Acrylonitrile / styrene copolymer) 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) fluororesin (16) polyacetal; (17) grafted polyphenylene ether resin and polyphenylene sulphite 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) diallylphthalate prepolymer; (27) silicone resin; (28) unsaturated polyester resin (29) acryl-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 (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 (49) Alkyd resin paint; (50) Nitrocellulose resin paint; (51) Oil paint; (52) Wax; (53) Lubricating oil.

When such an organic material is used in combination with the monosulfoxide compound of the formula (I) and the phenolic antioxidant, the proportion of both can be arbitrarily selected, but preferably, The monosulfoxide compound of the formula (I) is used in an amount of 0.5 to 10 times by weight of the phenolic antioxidant. Even if the amount of the monosulfoxide compound is less than 0.5 times by weight, a certain 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 desired effect, and it is economically disadvantageous.

As the monosulfoxide compound, one compound in which R in the formula (I) is a specific alkyl can be used alone, or two or more compounds having different Rs can be used in combination. . Also, only one type of phenolic antioxidant can be used,
Two or more kinds can be used in combination.

When compounding the monosulfoxide compound of the formula (I) and the phenolic antioxidant with the organic material, they are each added in a stabilizing effective amount, but usually each is added to 100 parts by weight of the organic material. A range of from 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 each may be separately compounded.

The organic material containing the monosulfoxide compound and the phenolic antioxidant according to the present invention may further contain, if necessary, other additives such as a sulfur-based compound other than the compound represented by the formula (I). Antioxidants, phosphorus antioxidants, ultraviolet absorbers, hindered amine light stabilizers,
It may 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 may be added together with the monosulfoxide compound of the formula (I) and / or the phenolic antioxidant, or may be added at a different stage from those. it can.

When the monosulfoxide compound of the formula (I) and the phenolic antioxidant or other optional additives are blended in 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,
It can be blended directly into the solid polymer,
Further, a monosulfoxide compound and a phenolic antioxidant or further optional additives can be blended with the solid polymer in the form of a masterbatch. If the organic material is a synthetic polymer, besides, add it 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. Can also. On the other hand, when the organic material is a liquid such as oil, a monosulfoxide compound and a phenolic antioxidant or any other additive can be directly added and dissolved, or the monosulfoxide can be dissolved. The compound and the phenolic antioxidant or further optional additives may be added in a state of being dissolved or suspended in a liquid medium.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The percentages and parts in the examples are by weight unless otherwise specified.

Synthesis example

30 ml of a methylene chloride solution containing 2.9 g of dioctadecyl 3,3'-thiodipropionate
To this was added 0.75 g of m-chloroperbenzoic acid, and the mixture was 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'-sulfinyldipropionate.

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

In the following examples, the following compounds were used.

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 Pionate

Example 1: Stabilization of polypropylene against thermal degradation

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

The above composition was melt-kneaded at 230 ° C. with a 30 mmφ single screw extruder and pelletized. Using these pellets, melt flow
The latet (MFR) was measured, and the thermal stability was evaluated.
Here, 270 ° C by a method according to JIS K 7210
The fluidity (g / 10 minutes) after 10 minutes residence was measured with M
FR. Polypropylene causes molecular chains to be cut by heat and increases fluidity. Therefore, the smaller the MFR after staying at a high temperature in the melt indexer, the better the thermal stability (processing stability). Table 1 shows the test results.

[0034]

[Table 1]

Example 2: Stabilization of polypropylene against thermo-oxidative degradation

[Compound] Unstabilized polypropylene 100 parts Calcium stearate 0.05 part Test stabilizer listed in Table 2

The above composition was melt-kneaded at 230 ° C. with a 30 mmφ single screw extruder to form pellets. The pellet was molded at 230 ° C. by an injection molding machine to obtain a 1 mm thick test piece. The test piece was placed in a gear oven, circulated and heated at 160 ° C., and the time required for the test piece to become brittle (brittle life) was measured. The longer the embrittlement life,
It means that stability against thermal oxidation deterioration is excellent. Table 2 shows the test results.

[0038]

[Table 2]

[0039]

According to the present invention, an organic material composition containing a specific sulfoxide compound together with a phenolic antioxidant exhibits excellent stability against thermal degradation and thermal oxidation degradation. Therefore, a high-quality product can be obtained by blending such a sulfoxide compound and a phenolic antioxidant with various organic materials such as a thermoplastic resin such as a polyolefin.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tetsuo Yamaguchi 3-1-198 Kasuganaka, Konohana-ku, Osaka City Inside Sumitomo Chemical Co., Ltd. (56) References JP-A-59-74182 (JP, A) Kaihei 7-292355 (JP, A) "Fourth Edition Experimental Chemistry Lecture 23 Organic Synthesis -V-Oxidation Reaction-", Maruzen Co., Ltd., published in 1991, p. 276 (58) Fields investigated (Int. Cl. ⁷ , DB name) C09K 15/12 C08K 5/41 C08L 101/00 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A monosulfoxide compound represented by the following formula: O = S (CH2CH2COOR) 2 (I) wherein R represents an alkyl having 1 to 18 carbon atoms. And a phenolic antioxidant each containing an effective stabilizing amount. (2) Monosulfoxide compounds and pheno
Content of organic antioxidants to 100 parts by weight of organic materials
Wherein each is 0.1 to 5 parts by weight.
The composition of claim 1.