JPH0533231B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, R represents a hydrogen atom or a _C1 - _C3 alkyl group.) The present invention relates to a piperidine derivative represented by the following formula, a method for producing the same, and a stabilizer for synthetic polymers containing the same as an active ingredient. It is well known that synthetic polymers such as polyethylene, polypropylene, polyvinyl chloride, polyurethane, and ABS resins are degraded by light and their physical properties are significantly reduced, accompanied by phenomena such as softening, embrittlement, and discoloration. In order to prevent such deterioration due to light, various light stabilizers such as 2-hydroxy-
4-methoxybenzophenone, 2-hydroxy-
4-n-octoxybenzophenone, 2-(2-
Hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-
t-pentylphenyl) benzotriazole, ethyl 2-cyano-3,3-diphenyl acrylate, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate,
[2,2'-thiobis(4-t-octylphenolate)]-n-butylamine nickel (), bis(3,5-di-t-butyl-4-hydroxybenzylphosphoric acid) monoethyl ester of
Ni salt, bis(2,2,6,6)-tetramethyl-
Although it is known to use 4-piperidyl) sebacate, etc., these light stabilizers are still not fully satisfactory in terms of light resistance. As a result of various studies aimed at solving these problems, the present inventors found that the piperidine derivative represented by the above general formula () has an extremely excellent effect on preventing photo-induced deterioration of synthetic polymers. , led to the present invention. The piperidine derivative of the present invention represented by the above general formula () is a new substance synthesized for the first time by the present inventors, and is represented by the general formula () (In the formula, R has the same meaning as above.) A triacetonamine derivative or a salt thereof represented by the formula () It can be produced by reacting sorbitol shown in Here, examples of salts of triacetonamine derivatives include salts with mineral acids such as hydrochloric acid, phosphoric acid, and sulfuric acid, carboxylic acids such as acetic acid and oxalic acid, and sulfonic acids such as para-toluenesulfonic acid. In addition, as the C ₁ to C ₃ alkyl group, methyl group,
Examples include ethyl group, n-propyl group, and isopropyl group. This reaction takes place in the presence of an acidic catalyst or dehydrating agent.
It is carried out in a solvent or without a solvent. When using a solvent, examples of the solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, alicyclic hydrocarbons such as cyclohexane, N,N-dimethylformamide, and dimethyl sulfoxide. , water-soluble polar solvents such as dioxane and sulfolane, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butanol, n-amyl alcohol, isoamyl alcohol, 2-ethylhexyl alcohol, and cyclohexanol, ethylene glycol monomethyl ether , ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and other glycol ethers, which may be used alone or in combination of two or more. Examples of acidic catalysts include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, hydrobromic acid, para-toluenesulfonic acid, zinc chloride, boron trifluoride, cation exchange resins, polymer complexes of aluminum chloride, selenium oxide, and ammonium chloride. Calcium chloride is exemplified as a dehydrating agent. The reaction between the triacetonamine derivative or its salt and sorbitol is carried out under conditions such that approximately two of the six hydroxyl groups in one molecule of sorbitol remain. Specifically, the reaction is carried out using 1.8 to 2.2 moles of the triacetonamine derivative or its salt per mole of sorbitol. Further, the acidic catalyst or dehydrating agent is 0.01 to 4 mol, preferably 0.1 mol per mol of sorbitol.
~3 mol is used. The reaction temperature is 10-300°C, preferably 60-200°C. After completion of the reaction, the target product can be isolated from the reaction mixture by, for example, making the reaction mixture alkaline, removing the solvent from the organic layer, and recrystallizing it with an appropriate solvent if necessary. The piperidine derivative of the present invention thus obtained is 1,3:2,4-bis-O-(2,2,6,
6-tetramethyl-4-piperidylidene) sorbitol, 1,3,:2,4-bis-O-(1,2,
2,6,6-pentamethyl-4-piperidylidene) sorbitol, 1,3:2,4-bis-O-
(2,2,6,6-tetramethyl-1-propyl-4-piperidylidene) sorbitol etc. are exemplified, but when using the method of the present invention, depending on the reaction conditions etc., it may be applied by the present inventors. Special request 1988-
Although the compound described in No. 163734 may be produced simultaneously and obtained as a mixture with the compound of the present invention, there is no particular problem in using such a mixture as it is when used as a stabilizer or the like. When the piperidine derivative of the present invention is used as a stabilizer for synthetic polymers, the amount of the compound is
It is usually 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight per 100 parts by weight, and the blending method is a known device for mixing and blending stabilizers, pigments, fillers, etc. into synthetic polymers. And the operating method can be applied almost as is. When using the stabilizer for synthetic polymers of the present invention, other additives such as antioxidants, light stabilizers, metal deactivators, metal soaps, nucleating agents, lubricants, and antistatic agents are required. additives, flame retardants, pigments, fillers, etc. may be used in combination. In particular, thermal and oxidative stability can be improved by using a phenolic antioxidant in combination. Examples of these phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl 3-(3,5
-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butyl) phenol), 4,4'-thiobis(3-methyl-6-t
-butylphenol), 2-t-butyl-6-(3
-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenyl acrylate, 1,
1,3-tris(2-methyl-4-hydroxy-
5-t-butylphenyl)butane, 1,3,5-
Trimethyl-2,4,6-tris(3-alkyl-5-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-alkyl-5
-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3-(3-alkyl-5-t-butyl-4-hydroxyphenyl)propionyloxyethyl)isocyanurate, ethylene glycol bis (3,3-bis(4-hydroxy-3-t-butylphenyl)butanate), pentaerythritol tetrakis (3-(3-alkyl-5-t-butyl-4-hydroxyphenyl)propionate), and the like. Further, by using a phosphite antioxidant in combination, the hue can be improved. These phosphite antioxidants include:
For example, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-t-butyl-4
-methylphenyl)phosphite, bis(2,4
-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis(2,4-di-t
-butylphenyl)-4,4'-biphenylene diphosphonite. Also, dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), 3,
9-bis(2-dodecylthioethyl)-2,4,
Sulfur-based antioxidants such as 8,10-tetraoxaspiro[5,5]undecane can also be used in combination. Furthermore, the light resistance can be further improved by adding a light stabilizer other than the hindered piperidine compound. Examples of these light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,
Benzophenone compounds such as 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-(2-
Hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-
Hydroxy-3,5-di-t-pentylphenyl)benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole , 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,
5-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-t
-octylphenyl)benzotriazole, 2-
Benzotriazole compounds such as (2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl)benzotriazole, phenyl salicylate, pt-butylphenyl salicylate,
2,4-di-t-butylphenyl 3',5'-di-
Benzoate compounds such as t-butyl-4'-hydroxybenzoate, hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate, Ni salt of dibutyl-dithiocarbamic acid, [2,2'-
Thiobis(4-t-octylphenolate)]-n
-butylamine Ni complex, bis(3,5-di-t
-butyl-4-hydroxybenzyl phosphoric acid) monoethyl ester, etc.
cyanoacrylate compounds such as ethyl 2-cyano-3,3-diphenyl acrylate and N-2-ethylphenyl-N'-2-ethoxy-5-t-butylphenyl oxalic acid diamide, N-2- Examples include oxalic acid diamides such as ethyl phenyl-N'-2-ethoxyphenyl oxalic acid diamide. Synthetic polymers stabilized by the piperidine derivatives of the present invention include low density polyethylene, medium high density polyethylene, linear low density polyethylene,
Polyα- such as polypropylene and polybutene-1
Olefins, polyα-olefin copolymers such as propylene-ethylene random or block copolymers, ethylene-butene-1 random copolymers, copolymers of polyα-olefins and vinyl monomers such as maleic anhydride-modified polypropylene, and mixtures of these, chlorinated polyethylene,
EVA resin, polyvinyl chloride, methacrylic resin,
Polystyrene, high-impact polystyrene, ABS resin, AES resin, MBS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, unsaturated polyester resin, as well as isoprene rubber, butadiene rubber,
Examples include rubbers such as acrylonitrile-butadiene copolymer rubber and styrene-butadiene copolymer rubber, and blends of these resins. EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Example 1 100 g (0.52 mol) of triacetonamine hydrochloride, 45.5 g (0.25 mol) of sorbitol, and 300 g of toluene were placed in a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and para-toluenesulfonic acid was added while stirring. Prepare 100.8g of hydrate. Increase temperature to 110
Incubate at ℃ for 1 hour. After the reaction is complete, an aqueous sodium hydroxide solution is added to the reaction solution to solubilize the product in toluene. The toluene layer in which the product was dissolved was separated, washed with water, dried, and then the toluene was distilled off to give 1,3:2,4-bis-O-(2,2,
71 g of 6.6-tetramethyl-4-piperidylidene) sorbitol (yield 62.3% vs. sorbitol) was obtained. The yellow crystals were dissolved in toluene and treated with activated carbon to obtain pale yellow crystals. Melting point 167-173°C Parent ion peak 456 was confirmed by FD-MS. 1H-NMR (DMSO, D ₂ O, TSP) δ 1.16 24H s δ 1.53 8H s δ 3.66 5H d δ 4.00 3H s Example 2 In a flask similar to Example 1, 80.7 g (0.52 mol) of triacetonamine and sorbitol were added. 45.5 g (0.25 mol) and 300 g of toluene are charged, and while stirring, 100.8 g of para-toluenesulfonic acid hydrate is charged. The temperature was increased to 110°C for 1 hour. After the reaction is completed, the same post-treatment as in Example 1 is carried out to obtain 1,3:2,4-bis-O-(2,2,
6.6, tetramethyl-4-piperidylidene) sorbitol (68 g (60% vs. sorbitol)) was obtained. The physical properties of this product were the same as those of the product obtained in Example 1. Example 3 In a flask similar to Example 1, 1, 2, 2, 6,
102.4 g (0.6 mol) of 6-pentamethyl-4-piperidone, 54.7 g (0.3 mol) of sorbitol, and 300 ml of xylene are charged, and while stirring, 116.0 g of paratoluenesulfonic acid hydrate is charged. Raise the temperature to 120
Incubate at ℃ for 1 hour. After the reaction is completed, the same post-treatment and purification as in Example 1 yields pale yellow oily 1,3:2,4-
Bis-O-(1,2,2,6,6-pentamethyl-4-piperidylidene) sorbitol 110.4g (76
% vs. sorbitol) was obtained. M ⁺ 1 (485) was confirmed by FD-MS. 1H-NMR (DMSO, D ₂ O, TSP) δ 1.11 24H s δ 1.52 8H s δ 2.22 6H s δ 3.63 5H d δ 4.03 3H s Elemental analysis C ₂₆ H ₄₈ N ₂ O ₆ Calculated value in parentheses C 64.00% (64.43%) H 9.72% (9.98%) N 5.00% (5.78%) Example 4 After mixing the following composition with a mixer for 5 minutes,
The compound obtained by melt-kneading with a mixing roll at 180°C was molded into a sheet with a thickness of 1 mm using a hot press at 210°C to prepare a test piece of 150 x 30 x 1 mm. This test piece was attached to a sunshine weather meter (light source: carbon arc, black panel temperature:
The weather resistance was evaluated by irradiating the film with light at 83±3°C (spray cycle: 120 minutes, spray time: 18 minutes), bending it into a shrimp shape every 60 hours, and measuring the time until it broke. The results are shown in Table-1. <Formulation> Unstabilized polypropylene 100 parts by weight Calcium stearate 0.1 2,6-di-t-butyl-4-methyl phenol 0.05 Test compound 0.2 In the table, UVA-1 to I-9 and I-1
-2 represents the following compounds. UVA-1 2-hydroxy-4-methoxy benzophenone UVA-2 2-hydroxy-4-n-octoxybenzophenone UVA-3 2-(2-hydroxy-5-methylphenyl)benzotriazole UVA-4 2- (2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole UVA-5 2-(2-hydroxy-3,5-di-t-pentylphenyl)benzotriazole UVA-6 Ethyl 2-cyano-3,3'-diphenyl acrylate UVA-7 Ni salt of bis(3,5-di-t-butyl-4-hydroxybenzylphosphoric acid) monoethyl ester UVA-8 Bis(2,2,6 ,6-tetramethyl-4-piperidyl) sebacate UVA-9 Bis-O-(2,2,6,6-tetramethyl-4-piperidylidene)pentaerythritol-1 1,3:2,4-bis- O- (Example 1 compound) (2,2,6,6-tetramethyl-4-piperidinylidene)sorbitol-2 1,3:2,4-bis-O- (Example 3 compound) (1,2 ,2,6,6-pentamethyl-4-piperidylidene) sorbitol

【table】

[Table] Example 5 25% urethane dope (25 parts polyurethane resin, 3.75 parts dimethylformamide and 71.25 parts
After adding 1% of the test compounds shown in Table 2 to the above polyurethane resin (Tetrahydrofuran), it was coated on a polyester film to a thickness of 1.2 mm and dried in a dryer at 45°C for 1 hour.
The sheet thus obtained was punched out using a No. 3 dumbbell, irradiated with light for 60 hours and 120 hours using a fade meter (light source: ultraviolet carbon arc, black panel temperature: 63±3°C), and then subjected to a tensile test (pulling speed: 200 mm/min). , measurement temperature: 25℃),
The breaking strength retention rate was determined. The results are shown in Table-2.

[Table] Example 6 The following composition was melt-kneaded using a mixing roll at 150°C, and then a sheet with a thickness of 0.5 mm was prepared using a hot press at 160°C. Use this sheet as a sunshine weather meter (light source: carbon arc, black panel temperature:
It was irradiated for 1200 hours at 63±3°C, spray cycle: 120 minutes, spray time: 18 minutes, and the degree of discoloration was observed. The results are shown in Table-3. <Formulation> Polyvinyl chloride 100 parts by weight Dioctyl phthalate 38 Epoxidized soybean oil 2 Barium stearate 1 Zinc stearate 0.3 Test compound 0.2

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R represents a hydrogen atom or a _C1 - _C3 alkyl group.) A piperidine derivative represented by the following formula. 2 General formula (In the formula, R represents a hydrogen atom or a C ₁ to C ₃ alkyl group.) The triacetonamine derivative or its salt represented by the following formula and sorbitol are mixed in a proportion of the triacetonamine derivative or its salt per 1 mole of sorbitol.
General formula characterized by the reaction using 1.8 to 2.2 moles (In the formula, R has the same meaning as above.) A method for producing a piperidine derivative represented by the following. 3 General formula (In the formula, R represents a hydrogen atom or a _C1 - _C3 alkyl group.) A stabilizer for synthetic polymers containing a piperidine derivative represented by the following as an active ingredient.