JPH06104823B2 - Organic cyclic phosphorus compound stabilizer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizer for organic substances which is changed by heat, light, oxidation and the like.

[0002]

2. Description of the Related Art Organic materials, particularly synthetic resins such as polyolefin resins, have excellent physical, chemical and electrical properties, and are processed into various molded products and used in a wide variety of fields. However, the polyolefin resin alone loses its value due to the remarkable deterioration of its characteristics due to the effects of heat, oxygen, light, etc. during processing and use.

In order to prevent such a phenomenon, various phenol-based, sulfur-based or phosphorus-based antioxidants have been conventionally added individually or in combination.

For example, phenol-based antioxidants include 2,6-di-t-butyl-4-methylphenol,
n-octadecyl-β- (3,5-di-t-butyl-4
-Hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,3,5-trimethyl-2,4,6-tris (3,3. 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-
Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and the like, and sulfur-based antioxidants used in combination therewith include dilaurylthiodipropionate and dimyristylthiodipropionate. , Pentaerythritol-tetrakis (β-dodecylthiopropionate), and the like, as the phosphorus-based antioxidant, triphenylphosphite, diphenyl (iso) decylphosphite, phenyl (iso) decylphosphite, tri (isodecylphosphite). ) Decyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (iso) decyl pentaerythritol diphosphite, etc. are each exemplified.

[0005]

However, these antioxidants have not yet reached a sufficiently satisfactory level in the effect of stabilizing the base material against heat and oxidation even when used alone or in combination.

The present inventor has conducted various studies in order to solve such a problem, and as a result, a specific organic cyclic phosphorus compound has an excellent stabilizing effect against heat and oxidation without deteriorating various characteristics inherent to the substrate. The present invention has been completed by discovering that

[0007]

The features of the present invention are represented by the general formula (I)

[0008]

[Chemical 2] (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 is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group). It is a stabilizer for organic substances composed of an organic cyclic phosphorus compound.

By adding and mixing the organic cyclic phosphorus compound represented by the above general formula (I) during the production of the organic substance or during each step of molding and processing, it goes without saying that the production and processing steps of the organic substance are carried out for a long period of time. It retains an excellent stabilizing effect against deterioration due to heat and oxidation during storage and use.

The compound represented by the general formula (I) has the general formula
It is obtained by heating the compound represented by (II) and the compound represented by the general formula (III) in an inert solvent by heating.

[0011]

[Chemical 3] (Where X, X ', m, n and R are as described above).

An outline of an example of a general embodiment of this reaction will be described below.

A mixture of the compound of the general formula (II) and an inert solvent is kept at room temperature to 100 ° C. (usually 50 ° to 80 ° C.), and when dissolved, the compound of the general formula (III) is converted to the compound of the general formula (II). Equimolar to 0.8 molar ratio equivalent amount (preferably 0.85 to
0.95 molar ratio) is gradually added. After the addition is complete, the mixture is heated at 70 ° -150 ° C for 0.5-5 hours (usually 100 °-
The reaction is carried out at 130 ° C. for 1.5 to 3 hours. The compound of the general formula (I) is precipitated by cooling or by adding a solvent which does not dissolve the compound of the general formula (I) so much and is mixed with the insoluble solvent used, or by concentrating, and then filtering, washing and drying.
As an inert solvent, it dissolves raw materials and reaction products when heated,
Those having a low solubility of the reaction product when cold are preferable, and examples thereof include ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, and xylene.

Specific examples of the compound represented by formula (I) include 2- (9 ', 10'-dihydro-9'-phospha-
9'-oxide-10'-oxaphenanthrene-9 '
-Yl) -1,4-dihydroxybenzene (B) as a prototype, its substitution position is shown as follows, and only the substitution position and the substituent are shown:

[0015]

[Chemical 4]

5-methyl (having a methyl group at the 5-position of hydroquinone and having no other substituents, the same applies hereinafter), 5-ethyl, 5-t-butyl, (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 and the like.

[0017]

The amount of the stabilizer of the present invention added to the substrate to be stabilized is selected depending on the type of substrate, purpose of use, etc.
It is about 10 to 10% by weight, usually about 0.01 to 5% by weight.

Further, phosphorus-based antioxidants and other additives such as light stabilizers, metal deactivators, metal soaps, nucleating agents, pigments and various fillers may be added.

As the material to be stabilized, industrial chemicals, agricultural chemicals, synthetic and semi-synthetic resins, elastomers, synthetic and natural rubber,
Listed are paints, adhesives, lubricating oils, surfactants, and other organic substances that deteriorate due to heat and oxidation.

As the synthetic resin, polyolefin, polystyrene, ABS resin, AS resin, polyacetal, polycarbonate, polyester carbonate, polyacrylate, polyphenylene ether, modified polyphenylene ether, polysulfone, polyester, epoxy resin, phenol / aldehyde polycondensate, etc. Various resins, various synthetic rubbers, etc. are exemplified.

[0021]

EXAMPLES Next, examples showing the effect of the stabilizer of the present invention will be described.

Example 1 (Comparative Examples 1-1 to 1-4) Predetermined amounts of various stabilizers were added to polypropylene (no stabilizer added) and dry blended, and then 200 ° C. with a heating kneader.
It was melt-kneaded and pelletized. Each pellet thus obtained is press-molded (temperature: 200 ° C., pressure: 200 kg / cm ² gauge) to form a flat plate of 180 × 180 × 10 mm, and a test piece of 50 × 50 × 1 mm is cut out from the flat plate, and 1
A heat deterioration test was performed with a gear open at 50 ° C., and an embrittlement time (a time until the test piece was discolored and embrittled to become tattered) was measured.

The stabilizers used are shown below.

Stabilizers of the invention: compounds of formula (IA)

[0025]

[Chemical 5] The compound of formula (IA) was obtained as follows.

Ethyl cellocerb 1,000 g 9,10
-540 g (2.5 mol) of dihydro-9-phospha-10-oxaphenanthrene-9-oxide (HCA) was added and the temperature was raised to 70 ° C with stirring, and HCA was completely dissolved and then reacted. Fine powder 2-t-butyl-p-benzoquinone (369 g) while maintaining the temperature of the mixture at 70 to 90 ° C.
(2.25 mol) was added portionwise over 2 hours. After the addition is complete, hold at 125 ° -130 ° C for 2 hours and then at 20 ° C.
The precipitate was filtered, and the filter cake was washed with ethyl cellosolve 1
Wash with 80 ml, then 180 ml of methanol, 90
After drying under reduced pressure at ℃, 636 g of white crystalline powder was obtained. The product was recrystallized from ethyl cellosolve and purified, and the melting point was 295 to 300 ° C., and its elemental analysis values were as follows.

[0027] (As C ₂₂ H ₂₁ O ₄ P) Comparative stabilizer; compound represented by formula (II) to formula (IV):

[0028]

[Chemical 6]

[0029]

[Chemical 7] S (CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ (IV) (abbreviated as DLTP) The results are shown in Table 1. PHR in the table is the addition weight part per 100 weight parts of resin (the same applies hereinafter).

[0030]

[Table 1]

Example 2 (Comparative Examples 2-1 to 2-3) 100 g of methylhexahydrophthalic anhydride, 1 g of benzylmethylamine and 3 g of HCA-HQTB were added at 120.degree.
The mixture was stirred and homogenized with a homogenizing solution to obtain an epoxy resin (Ciba-Geigy; Araldite GY-250 ^(R) ) 1
The resin liquid obtained by uniformly mixing with 00g has a thickness of 4 m.
m, width 15 mm, length 150 mm (4 x 15 x 15 m
It was poured into a mold from which the cured resin of m) was obtained and heated at 130 ° C. for 30 minutes. Then, the cured resin was taken out from the mold and colored with the naked eye and evaluated for transparency. Further, the cured resin was left at 100 ° C. for 1,000 hours, and the same evaluation was performed. For comparison, stabilizer-free and HCA-HQTB
When triphenyl phosphite (abbreviated as TPP) or BHT was used instead of, the same operation was performed and evaluated. The evaluation ranks are as follows.

◎ Colorless and transparent 〇 Transparent but slightly colored Δ Transparent but slightly colored × Strongly colored The results are shown in Table 2.

[0033]

Example 3 (Comparative Examples 3-1 to 3-2 ) 7,400 g of styrene monomer, 2,600 g of acrylonitrile, 100 g of lauroyl peroxide and a stabilizer were added to a stainless steel reactor charged with 20 liters of distilled water. Suspension polymerization was carried out at 70 ° C. in a nitrogen atmosphere using 0.1 g of tricalcium phosphate and 0.5 g of sodium dodecylbenzenesulfonate as a dispersant. After completion of the polymerization reaction, 35% hydrochloric acid water was added to neutralize, the weight beads were washed with water, dehydrated and dried at 70 ° C. This was pelletized by an extruder and injection molding machine (temperature 280 ° C, residence time 15
Min.) Was molded into a 2 × 40 × 120 mm test piece, and the color tone and transparency were measured and evaluated according to the following criteria.

Color tone evaluation stage: 1 water white 10 dark yellow 2 white 13 dark yellow 4 very light yellow 20 brown 6 light yellow 20 or more dark brown 8 yellow color transparency evaluation; thickness according to ASTM D-1003 2.
Create a 0 mm sample and haze the transparency
Expressed as

As comparative examples, tests were carried out in the case where no stabilizer was added and when BHT was used in combination with tris (nonylphenyl) phosphite (abbreviated as TNP) as a stabilizer. The results are shown in Table 3.

[0037]

Example 4 (Comparative Examples 4-1 to 4-3) 100 parts of the following natural rubber-based glue base (weight basis, the same applies hereinafter) and polyisocyanate A (manufactured by Asahi Kasei; Duranate AD-50 ^(R)) ) 5 parts and 1.0 part of the stabilizer were mixed to obtain an adhesive composition.

Natural rubber type glue base; (1) Natural rubber (RSS) 300 parts (2) Magnesium carbonate 75 parts (3) White gloss CC (product of Shiraishi Calcium Co.) 75 parts (4) Zinc white 25 parts (5) ) Stearic acid 5 parts (6) Sulfur 15 parts (7) Noxcellar N 5 parts Total 500 parts Kneading with a 3 inch roll while adding the above materials (2) to (7) in the order of numbers to the natural rubber. 400 parts of the resulting kneaded product is dissolved and mixed in 1,600 parts of toluene to obtain 2,000 parts of a natural rubber-based glue base having a nonvolatile content of 20%.

Approximately 260 parts of this adhesive composition was applied to a cotton cloth.
A coating amount of g / m ² was applied, and the coating was dried at room temperature for about 15 minutes and then heated at 140 ° C. for 30 minutes in a hot air circulation dryer to visually determine the degree of coloring of the adhesive composition. As comparative examples, no stabilizer was added, 2,5-di-t-butylhydroquinone (abbreviated as NS-7) was used as a stabilizer, and TNP and BHT were used in combination. The results are shown in Table 4.

Evaluation of degree of coloring: ◎ High degree of whiteness ○ Slightly colored △ Slightly colored × Strongly colored

[0042]

Example 5 (Comparative Examples 5-1 to 5-3) 0.01% stabilizer to aniline (hue, Hazen number 20)
Soxhlet flask (100 ml
Volume of 50 ml in an oil bath maintained at 185 ° C.
After heating for 0 minutes, the hue (Gardner number) was measured. As a comparative example, the same test was performed for the case where TPP or 2,4-dimethyl-6-t-butylphenol (abbreviated as DMBP) was added as a stabilizer at the same concentration and the case where no addition was made. The results are shown in Table 5.

[0044]

[0045]

As described above, the stabilizer of the present invention has a remarkable stabilizing effect on an organic substance which is easily colored or deteriorated by heat or oxidation.

Claims (1)

[Claims] 1. The general formula I: (In the formula, X and X'are each a hydrogen atom, a halogen atom,
Represents an acyl group, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and m and n are each 1 to
4 represents an integer of 4 and R represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group).