JPS59221343A - Stabilizer for synthetic resin - Google Patents

Abstract

PURPOSE:To provide a stabilizer capable of imparting extremely excellent heat and oxidation stability to synthetic resins, by mixing a specific phenolic compound with a specific sulfur compound. CONSTITUTION:The objective stabilizer is prepared by mixing (A) a phenolic compound of formula I (R1 is H, 1-4C alkyl or 1-5C acyl; n is 1-3) with (B) a sulfur compound of formula II or III (R2 is 4-20C alkyl; R3 is 3-18C alkyl; R4 and R5 are H or 1-6C alkyl). The weight ratio of (A):(B) is 1:0.5-15, preferably 1:2-6. The compound of formula I is e.g. 2,2,2-tris[3-(3-methyl-5-t-butyl-4- hydroxyphenyl)propionyloxymethyl]ethanol, etc., the compound of formula II is tetrakis(3-dodecylthiopropionyloxymethyl)-methane, and the compound of formula III is 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5] undecane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilizer for synthetic resins that provides excellent stability to synthetic resins.

Polyolefins such as polyethylene and polypropylene,
Styrenic synthetic resins such as polystyrene, high-impact polystyrene, and AB8, engineering plastics such as polyacetal and polyamide, and various synthetic resins such as polyurethane are widely used in various fields. When a resin is used alone, it deteriorates during processing due to the action of heat, light, and oxygen, and its mechanical properties deteriorate with phenomena such as softening, embrittlement, surface cracks, or discoloration. It is well known that there are problems with its stability, such as a significant decrease in physical properties.

In order to solve these problems, it is well known that various phenol-based, phosphorus-based, sulfur-based, and other antioxidants are added and used during the manufacturing and processing processes of synthetic resins. For example, 2,6-di-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,41-butylenebis(8-methyl-6-t-butylphenol), n-
Octadecyl 8-(8,5-di-t-butyl-4-hydroxyphenyl) flobionate, 1,1,8-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, Tetrakis[8- Using phenolic antioxidants such as (8,5-di-butyl-4-hydroxyphenyl)propionyloxymethylcomethane alone, these phenolic antioxidants and Tris(
Nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, and other phosphorus-based antioxidants may be used together, or the above phenolic antioxidants may be used with dilauryl thiodipropionate, simiristyl thiodipropionate, or A method of using a sulfur-based antioxidant such as stearyl thiodipropionate in combination is known.

However, these methods are still unsatisfactory in terms of thermal and oxidative stability, thermal discoloration resistance, evaporation resistance, and the like.

As a result of various studies to solve these problems, the present inventors found that a mixture consisting of a specific phenolic compound and a specific sulfur compound in a specific ratio is effective as an antioxidant for synthetic resins. It has been discovered that the present invention provides extremely excellent thermal and oxidative stability that could not be predicted using similar combination techniques.

That is, the present invention is represented by the general formula (Il (wherein R1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 8). The phenolic compound (1) and the general formula (■-1
) and (II-2) (Rg -8-CH2CHaC-0-CH2 large C(n-
1) (In the formula, R2 represents an alkyl group having 4 to 20 carbon atoms.) (In the formula, Rs represents an alkyl group having 8 to 18 carbon atoms, and R 4 and R5 each independently represent a hydrogen atom or a C 1 alkyl group. -6 alkyl group.) At least one sulfur-based compound (If) selected from the compounds represented by (I): tn>= t: 0
．． The present invention provides a stabilizer for synthetic resins containing a mixture as an active ingredient in a proportion of 5 to 15 (by weight).

The phenolic compound represented by the general formula (I) is a novel compound synthesized for the first time by the present inventors,
For example, 8-(8-methyl-5-t-butyl-4-hydroxyphenyl) represented by the general formula @) (wherein, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) Propionic acids and general formula (P1') (HOCH2Rust (3÷OHgOR+)4-n (
ffi (where n and R1 have the same meanings as above) at a molar ratio of 0.5 to 4.
:1 and can be produced by reacting in the presence of an acidic or basic catalyst.

In the phenolic compound represented by the general formula (I), n represents an integer of 1 to 8, but from the viewpoint of thermal and oxidative stability, n is preferably 2 to 8, particularly 8, and the substituent R1 is a hydrogen atom or C! such as a methyl group, an ethyl group, an acetyl group, etc. -2 alkyl groups and acyl groups are preferred. Such phenolic compounds include 2,2゜2-tris[8-(8-methyl-5-t-butyl-4-
hydroxyphenyl)propionyloxymethyl]ethanol, 2,2.2-tris[8-(8-methyl-5-
t-Butyl-4-hydroxyphenyl)propionyloxymethyl]ethyl acetate or 2,2,2-tris[8-(8-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl]-1-methyl Examples include dou-xyethane.

In the compound represented by the general formula (II-1), the substituent R2 is preferably an alkyl group having 6 to 18 carbon atoms, most preferably a dodecyl group, from the viewpoint of thermal and oxidative stability.

Representative examples of such compounds are shown in Table-1.

Table-1 1 (Rg -8-0HsCHs+0-U-Of12 large CAlso, in the compound represented by general formula (II-2), substituent R11 is an alkyl group having 12 to 18 carbon atoms, R6 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, respectively, from the viewpoints of thermal and oxidative stability.

Representative examples of such compounds are shown in Table-2.

Table-2 The stabilizer for synthetic resins of the present invention is a phenolic compound (1) represented by the above-mentioned general formula (I) and a general formula (It-1).
It consists of a mixture of at least one sulfur-based compound (II) selected from the compounds represented by
1:0.5-15, preferably 1:1-10, more preferably 1:2-6.

Here, if the sulfur-based compound (I[) is less than 0.5 times the weight of the phenolic metal compound (1), it is difficult to obtain the desired effect, and even if it exceeds 15 times the weight, it is not worth it. It is difficult to obtain the desired effect, and it is economically disadvantageous.

When using the stabilizer for synthetic resins of the present invention, the amount added to the synthetic resin is usually 0.0 parts by weight per 100 parts by weight of the synthetic resin.
1 to 6 N11 parts, preferably 0.05 to 1 part by weight. Moreover, upon use, the phenol compound (1) and the sulfur compound (Jl) may be separately blended into the synthetic resin without being mixed in advance.

The method of compounding into synthetic resin is to add stabilizers,
Known devices and operating methods for mixing and blending pigments, fillers, etc. can be applied almost as they are.

When using the stabilizer for synthetic resins of the present invention, other additives such as ultraviolet absorbers, light stabilizers, antioxidants, metal deactivators, metal soaps, nucleating agents, lubricants, and electrostatic charges are required. Inhibitors, flame retardants, pigments, fillers, etc. may be used in combination.

In particular, ultraviolet absorbers, hindered amine light stabilizers, etc., such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2(2-hydroxy-5-methylphenyl)benzotriazole, 2( 2-Hydroxy-B-t-butyl-5'-methylphenyl)-5-chloro-benzotriazole, 2(2-hydroxy-8s5-di-t-butylphenyl)-5-chloro-benzotriazole, 2(2
-Hydroxy-8,6-di-amylphenyl)benzotriazole, [2,2'-thiobis(4-t-octylphenolate)]-butylamine nickel salt, 2,2゜6.6-tetramethyl-4- Piperidinyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2-(8゜6-di-t-butyl-4
-Hydroxybenzyl)-2-n-butyl-wonic acid bis(1,2,2゜6.6-bentamethyl-4-piperidyl), 1-C2-(B-(8,5-di-t-butyl- 4
-hydroxyphenyl)propionyloxy)ethyl]
-4-[8-(8,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6〒
Tetramethylpiperidine, dimethyl succinate 1-(2
-hydroxyethyl)-4-hydroxy-2,2,6,
The light resistance can be improved by using a 6-titramethylpiperidine polycondensate or the like in combination.

Furthermore, the hue can be improved by adding a phosphite antioxidant. Examples of these phosphite-based antioxidants include distearyl pentaerythritol diphosphite, tris(2,4-
di-t-butylphenyl) phosphite, tris(2-
1-Butyl-4-methylphenyl) phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-t-butylphenyl)-4゜4'- Examples include biphenylene diphosphite.

Thus, by using the stabilizer for synthetic resins of the present invention, the stability of synthetic resins is greatly improved, but such synthetic resins include low density polyethylene, high density polyethylene, linear low density polyethylene, chlorinated polyethylene,
EVA resin, polypropylene, polyvinyl chloride, methacrylic resin, polystyrene, high-impact polystyrene, AB
8 resin, AE8 resin, ) (BS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, unsaturated polyester resin, etc.
It is particularly effective for polypropylene.

EXAMPLES Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Reference Example 1 Production of 2.2,2-trisC3-(8-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl]ethanol (compound I'-1) 8-(8-methyl-5 12.52f (0,050
mole) and pentaerythritol 2.72f (0,0
20 mol) and 0.0 mol of sodium methoxide.
After adding 185N (0,0025 mol), the temperature was raised.

After reacting at 140°C for 1 hour, the pressure was reduced and 25-20-
f. React for an additional 800 hours at 140-150°C. During this reaction, as the reaction progressed, 0.4051/(0,0075 mol) of sodium methoxide was added in 8 equal portions.

After the reaction was completed, the internal temperature was cooled to 80°C, the catalyst was neutralized with hydrochloric acid, and 20ON of toluene was added to separate the mixture. After washing the toluene layer with water, the toluene was distilled off under reduced pressure. The thus obtained crude product, 9.8 g (yield: 99%), had a purity of 78%, and was purified by silica gel chromatography to obtain 6.7 g of a colorless glassy substance with a purity of 96%.

Melting point: 40-50°C Elemental analysis C4yHesUx.

Actual value C; 71.6% fl; 8.1% theoretical value
C+71.4% H48, 4% mass spectrometry value (FD-mass) Molecular weight 790 Proton-NMK δ1.89 (27H8) δ2.18 (9H8) δ2.70 (12fi m) δ8.26 (2Hg) δ8 .95 (6H8) δ4.97 (4)1 br, s) δ6.79
(811S) δ6.92 (8'Ef s) Reference Example 2 2.2.2-Tris[8-(8-methyl-5-t-phthyl-4-hydroxyphenyl)propionyloxymethyl]ethyl acetate (compound l- Production of 2) Compound 1-1 obtained in Reference Example 1 was acylated by a conventional method to obtain a reddish-brown viscous body.

Elemental analysis 04sflaaOtt Actual value 0f70.2% Hi 7.8% Theoretical value
Ci+70.7% H; 8.2% mass spectrometry value (FD-mass) Molecular ion peak 882 Proton-NMR δ1.89 (27H8) δ2.17 (8111[11) δ2.19 (9Hfl) δ171 (12Hm) δ8 .92 (8HII) δ4.75 (an br, s) δ6.88 (8H8) δ6.97 (8HII) Reference Example 8 2.2.2-Tris[8-(8-methyl-5-t-butyl- Production of 4-hydroxyphenyl)propionyloxymethyl]=-1-methoxyethane (compound l-8) By carrying out the reaction under the same reaction conditions except for using pentaerythritol monomethyl ether in place of pentaerythritol in Reference Example 1, A reddish-brown viscous substance was obtained.

Elemental analysis 048H68010 Actual value (3+71.2% H+8.1% theoretical value
C171,6% H-8,55% mass spectrometry value (FD-mass) Molecular ion peak 804 Proton-NMR δ1.89 (27H11) δ2.18 (9H8) δ2.70 (12Hm) δ8.15 (8Hg), δ8.27 (2H8) δ8.94 (6H8) δ4.95 (8Hbr, s) δ 6.81 (8Hs) δ 6.9B (8Hs) Example 1 After mixing the following formulation for 5 minutes with a mixer, 180 °
The compound obtained by melt-kneading with a C mixing roll was formed into a 1-inch thick sheet using a hot press at 210°C.
A 40x40x1- test piece was prepared. The time until 80% of the area of the test piece became embrittled in a gear oven at 160°C was measured, and this time was taken as the thermal embrittlement induction period, and the thermal and oxidation stability was evaluated. The results are shown in Table-8.

Blend] Unstabilized polypropylene resin 100 parts by weight In Table 8, the symbols of the test compounds indicate the following compounds.

AO-1n-octadecyl 8-(8,5-di-t-butyl-4-hydroxyphenyl)propionate AO-2tetrakis[8-(8,5-dimo-phthyl-4-hydroquinphenyl)propionyloxymethyl Comethane A (J-81,8,5-trimethyl-2,4°6-tris(8,5-di-butyl-4-hydroxybenzyl)benzene AU-41,1,8-tris(2-methyl- 4-Hydroxy-5-t-butylphenyl)butane AO-5 dilaurylthiodipropionate AO-6 distearylthiodipropionate Table-8 (1) (21) Table-8 (2) Table-8 (8 ) Table 8 (4) Table 8 (5) Table 8 (6) Example 2 A suspension prepared by bead-decomposing the test compounds shown in Table 4 with an anionic surfactant on Graftom B8 latex was prepared. A predetermined amount was added as shown in -4.Salting out with magnesium sulfate aqueous solution according to the usual method, filtering, washing with water, and drying.The obtained AB8 resin powder was used as a test sample.Using this AB8 resin powder, the following Thermal and oxidative stability was evaluated using the following method.

The results are shown in Table-4.

1.AE8 after heat aging in 180℃ gear oven
The degree of discoloration of the resin was observed.

2. Using an oxygen absorption induction period measuring device, the oxygen absorption induction period (I, P,) was measured in an acidic atmosphere at 170°C.

8. Transfer MuB8 resin powder to a small extruder (screw D
=20 so8. L/D=25. Strand 14 D=8+
w8, L/D=IO) The extrusion was repeated under the following conditions, and the degree of discoloration of the AB8 pellets of the fourth time was evaluated by the color difference ΔYI from the additive-free AB8 pellets of the first time.

Extrusion conditions rotation speed: 40 rpm Ct C11 (3a D Temperature = 220℃ 240℃ 260℃ 280℃ 4, above 8
AB8 pellets obtained by extrusion four times were heated at 180°C.
A No. 1 test piece specified in JI8 K7111 was prepared by compression molding for ×lO minutes. Next, the Charpy impact value was measured using a Charpy impact tester in accordance with JI8 K7111.

In addition, in the table, AO-7 indicates the following compound.

AU-72,6-di-t-butyl-4-methylphenol Table 4 (1) Note) The amount added is the weight of the test compound (solid content) per 100]i parts of resin solid content. 4(2) Table-4(8) Table-4(4) Example 8 25% urethane dope (25 parts of polyurethane resin, 8
．． After adding the test compounds shown in Table 5 to 75 parts of dimethylbormamide and 71.25 parts of terahydrofuran in the weight parts shown in the table per 100 parts by weight of the above polyurethane resin, the mixture was applied onto a polyester film. 1.2 vm
It was coated thickly and dried in a dryer at 45°C for 1 hour. The sheet obtained in this way was punched out with a No. 8 dumbbell,
60 hours and 120 hours with a fade meter (light source: ultraviolet carbon arc, black panel temperature: 68 parts, 8°C)
After time light irradiation, tensile test (tensile speed: 200w/m
(in measurement temperature: 25° C.) to determine the breaking strength retention rate. The results are shown in Table-5.

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Claims (1)

[Scope of Claims] (1) General formula (I) (wherein R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 5 carbon atoms, and n is a hydrogen atom having 1 to 8 carbon atoms) The phenolic compound (I) represented by the general formula % (represents an integer) and the general formula % (
2) ) (In the formula, R2 represents an alkyl group having 4 to 20 carbon atoms.) (In the formula, Rs represents an alkyl group having 8 to 18 carbon atoms, R4
and decoration each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) At least one sulfur compound (n) selected from the compounds represented by (I):(I[
)=1: A stabilizer for synthetic resins containing a mixture as an active ingredient in a ratio of 0.5 to 15 (weight ratio). C) The phenolic compound (I) is 2.2-tris[8-(8-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl]ethanol, 2
, 2,2-tris[8-(8-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl]ethyl acetate t or 2,2,2-tris[8-(
The stabilizer for synthetic resins according to claim 1, which is 8-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl]-1-methoxyethane. (8) Sulfur-based compound Cx-1) is tetrakis(3
The stabilizer for synthetic resins according to claim 11, item 2, which is (-dodecylthioprobionyloxymethyl)methane. (4) Claim No. 2, wherein the sulfur-based compound (n-2) is 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane. 1. Stabilizer for synthetic resins according to item 2. (5) The stabilizer for synthetic resins according to claims 1 to 4, wherein the synthetic resin is a polyolefin resin. (6) The stabilizer for synthetic resins according to claim 5, wherein the polyolefin resin is polypropylene.