JPH0514753B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a stabilizer for organic substances that undergo changes due to heat, light, oxidation, etc. [Prior Art] Organic substances, especially synthetic resins such as polyolefin resins, have excellent physical, chemical, and electrical properties, and are therefore processed into various molded products and used in a wide range of fields. However, when a polyolefin resin is used alone, its properties are significantly deteriorated by the effects of heat, oxygen, light, etc. during processing and use, and its value is lost. In order to prevent such a phenomenon, various phenol-based, sulfur-based, or phosphorus-based antioxidants have conventionally been added singly or in combination. For example, as a phenolic antioxidant,
2,6-di-t-butyl-4-methylphenol, n-octadecyl-β-(3,5-di-t-
butyl-4-hydroxyphenol) propionate, tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate], 1,3,5-trimethyl-2,4,
6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenol)butane, etc. Examples of sulfur-based antioxidants used in combination with phosphate-based antioxidants include dilaurylthiodipropionate, dimyristylthiodipropionate, pentaerythritol-tetrakis (β-dodecylthiopropionate), etc. Examples of the agent include triphenyl phosphite, diphenyl(iso)decyl phosphite, phenol(iso)decyl phosphite, tri(iso)decyl phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, di(iso)decyl phosphite, ) Decylpentaerythritol diphosphite and the like are exemplified. [Problems to be Solved by the Invention] However, even when these antioxidants are used alone or in combination, they have not yet reached a sufficiently satisfactory level of stabilizing effect on the base material against heat and oxidation. As a result of various studies to solve this problem, the inventors of the present invention have found that a specific organic cyclic phosphorus compound exhibits an excellent stabilizing effect against heat and oxidation without impairing various properties inherent to the base material. The present invention has been completed based on the discovery that this effect is particularly noticeable when used in combination with a phenolic antioxidant and/or a sulfur antioxidant. [Means for solving the problem] The feature of the present invention is the general formula () (In the formula, X and X' are each a hydrogen atom, a halogen atom, an acyl group, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, m and n are each an integer of 1 to 4, and R ₁ to _{R 3} is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, respectively) and a phenolic antioxidant and/or a sulfur antioxidant. A stabilizer composition. By adding and mixing the organic cyclic phosphorus compound represented by the general formula () with a phenolic antioxidant and/or a sulfur antioxidant during the production of the organic substance or during each molding process, the organic substance It maintains an excellent stabilizing effect against deterioration due to heat and oxidation, not only during manufacturing and processing steps but also during long-term storage and use. The compound represented by the general formula () is obtained by subjecting the compound represented by the general formula () and the compound represented by the general formula () to a heating reaction in an inert solvent. (In the formula, X, X', m, n, and R ₁ to _{R 3} are as described above). A general embodiment of this reaction will be outlined below. A mixture of the compound of general formula () and an inert solvent is kept at room temperature to 100°C (usually 50° to 80°C), and once dissolved, the compound of general formula () is mixed with the compound of general formula () by an equimolar amount to 0.8 mol. ratio equivalent (preferably 0.85
~0.5 molar ratio) is gradually added. After the addition is complete, heat the mixture at 70° to 150°C for 0.5 to 5 hours (usually at 100° to 130°C).
℃ for 1.5 to 3 hours). Precipitate the compound of general formula () by cooling or adding a solvent that does not dissolve the compound of general formula () very much and mix it with the insoluble solvent used, or by concentrating, and filter.
Wash and dry. The inert solvent is preferably one that dissolves the raw materials and reaction products when hot and has a low solubility of the reaction product when cold, such as ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and the like. Specific examples of compounds of general formula () include 2
-(9',10'-dihydro-9'-phosphor-9'-oxide-10'-oxaphenanthrene-9'-yl)-
1,4-dihydroxybenzene (-A); Hereinafter, using the compound (-A) above as the original form, the substitution positions are indicated as follows, and only the substitution positions and substituents are shown; 5-methyl (meaning that the 5-position of hydroquinone has a methyl group and no other substituents, the same applies hereinafter), 5-ethyl, 5-t-butyl, (1'-methyl), (1'-t
-butyl), (1'-cyclohexyl), (1',3'-
dimethyl), (1′-chlor), (1′,3′-dichlor)
,
(1'-methyl)-5-methyl, (1'-t-butyl)-
5-methyl, (1'-cyclohexyl)-5-methyl, (1'-methyl)-5-t-butyl, (1'-t-
butyl)-5-t-butyl, (1'-cyclohexyl)-5-t-butyl, (1'-chloro)-5-methyl, (1'-chloro)-5-t-butyl, (1', 3′−
dimethyl)-5-methyl, (1',3'-dimethyl)-5
-t-butyl etc. [Function] The amount of the compound represented by the general formula () of the present invention added to the base material to be stabilized is selected depending on the type of base material, purpose of use, etc., but is 0.001 to 10% by weight, usually 0.01%.
It is about 5% by weight. Furthermore, the amount of the phenol-based and/or sulfur-based antioxidant used in combination is 0.1 to 5 times the amount of the compound represented by the general formula () of the present invention, and the total amount thereof is based on the amount of the base material to be stabilized. It is about 10% by weight or less. Furthermore, phosphorus antioxidants and other additives such as light stabilizers, metal deactivators, metal soaps, nucleating agents, pigments, various fillers, etc. may be added. Examples of base materials to be stabilized include industrial chemicals, agricultural chemicals, synthetic and semi-synthetic resins, elastomers, synthetic and natural rubbers, paints, adhesives, lubricating oils, surfactants, and other organic substances that deteriorate due to heat and oxidation. Ru. Synthetic resins include polyolefin, polystyrene, ABS resin, AS resin, polyacetal, polycarbonate, polyester carbonate, polyacrylate, polyphenylene ether, modified polyphenylene ether, polysulfone, polyester, epoxy resin, phenol/aldehyde polycondensate. Examples include various resins such as, various synthetic rubbers, etc. [Example] Next, an example showing the effect of the stabilizer of the present invention will be described. Examples 1-1 to 1-6 (Comparative Examples 1-1 to 1-6) A predetermined amount of various stabilizers was added to polypropylene (no stabilizer added), dry-blended, and then melt-kneaded at 200°C with a heating kneader. It was made into pellets. Each pellet obtained was press-molded (temperature 200℃, pressure
A 180 x 180 x 10 mm flat plate was prepared using 200 kg/cm ² gauge), a 50 x 50 x 1 mm test piece was cut out from this plate, and a heat deterioration test was conducted at 150°C with the gear open. The time required for the material to change color and become brittle and crumble was measured. The stabilizers used are shown below. Compound represented by general formula (): formula (-A)
and a compound represented by formula (-B) The compound of formula (-A) was obtained as follows. 9,10-dihydro- to 1000g of ethyl cellosolve
9-Phosphor-10-oxaphenanthrene-9-
Add 540 g (2.5 mol) of oxide (HCA) and raise the temperature to 70°C with stirring. After the HCA is completely dissolved, fine powder p-benzoquinone (p −BQ) 243g (2.25
mol) was added portionwise over 2 hours. After the addition was completed, the temperature was maintained at 125° to 130°C for 2 hours, then cooled to 20°C, the precipitate was filtered, and the filtered mass was dissolved in ethyl cellosolve.
It was washed with 180 ml and then with 180 ml of methanol, and dried at 90° C. to obtain 540 g of white crystalline powder. yield
74.1% (vs. p-BQ). Melting point 250℃. The melting point of this product obtained by recrystallization and purification from ethyl cellosolve is
At 250.5°C, the elemental analysis values were as follows. C H P Actual value (%) 66.83 3.96 9.39 Theoretical value (%) 66.67 4.01 9.57 (as C ₁₈ H ₁₃ O ₄ P) The compound of formula (-B) is A similar procedure was performed using 369 g of 2-t-butyl-1,4-benzoquinone instead. The purified product was a white crystalline powder with a melting point of 295° to 300°C, and its elemental analysis values were as follows. C H P Actual value (%) 69.83 5.61 8.09 Calculated value (%) 69.47 5.53 8.16 (as C ₂₂ H ₂₁ O ₄ P) Concomitant stabilizer; Compounds represented by formula () to formula (): S(CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ ( ) (abbreviated as DLTP) The results are shown in Table 1. PHR in the table is resin
This is the part by weight added per 100 parts by weight (the same applies hereinafter).

[Table] [Effects of the Invention] As described above, organic cyclic phosphorus compounds represented by the general formula ( When an antioxidant and/or a sulfur-based antioxidant is used in combination, the stabilizing effect is significantly enhanced.

Claims (1)

[Claims] 1 General formula () (In the formula, X and X' each represent a hydrogen atom, a halogen atom, an acyl group, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, m
and n each represent an integer of 1 to 4, and R ₁ to
A stabilizer for organic substances consisting of an organic cyclic phosphorus compound represented by (R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, respectively) and a phenolic antioxidant and/or a sulfur antioxidant. Composition.