JPH0447676B2 - - 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 synthetic resin stabilizer containing the same as an active ingredient. It is well known that synthetic resins 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-dipentylphenyl)benzotriazole , ethyl-
2-cyano-3,3-diphenyl acrylate,
2,4-di-t-butylphenyl-3,5-dit
-butyl-4-hydroxybenzoate, [2,
2'-thiobis(4-t-octylphenolate)]-
n-butylamine, nickel(), bis(3,
Ni salt of 5-di-t-butyl-4-hydroxybenzylphosphoric acid) monoethyl ester,
Although it is known to use bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like, 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 of preventing light-induced deterioration of synthetic resins, This 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 guccicol 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. In the reaction of such a triacetonamine derivative or its salt with sorbitol, the triacetonamine derivative or its salt reacts with sorbitol 1
Usually 2 to 5 moles per mole, preferably 2.5 to 4 moles
molar used. Further, the acidic catalyst or dehydrating agent is used in an amount of 0.01 to 6 mol, preferably 0.1 to 4 mol, per mol of sorbitol. The reaction temperature is 10~
The temperature is 300°C, preferably 60-200°C. Reaction completed,
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 performing recrystallization treatment with an appropriate solvent if necessary. The piperidine derivative of the present invention thus obtained is 1,3:2,4:5,6-tris-O-
(2,2,6,6-tetramethyl-4-piperidinylidene)sorbitol, 1,3:2,4:5,
6-tris-O-(1,2,2,6,6-pentamethyl-4-piperidinylidene) sorbitol,
1,3:2,4:5,6:-Tris-O-(2,
2,6,6-tetramethyl-1-propyl-4-
Examples include piperidinylidene) sorbitol. When the piperidine derivative of the present invention is used as a stabilizer for synthetic resins, the amount blended into the synthetic resin is usually 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the synthetic resin. As a method, almost all known apparatuses and operating methods for mixing and blending stabilizers, pigments, fillers, etc. into synthetic resins can be applied as they are. When using the stabilizer for synthetic resins of the present invention, other additives such as antioxidants, light stabilizers, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, 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-β-(3,5
-di-t-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)
Butane, 1,3,5-trimethyl 2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,
5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 1,3,5-tris[β-
(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 1,3,5-tris(2,6-di-methyl-3-hydroxy-4-t-butylbenzyl) ) isocyanurate, pentaterithritol-tetrakis [β-(3,5-di-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, distearylpentaethythritol 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-
Examples include t-butylphenyl)-4,4'-biphenylene phosphonite. Also, dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis (β-laurylthiopropionate), pentaerythritol-tetrakis (β-hexylthiopropionate), etc. A sulfur-based antioxidant can also be used in combination. Examples of synthetic resins stabilized by the synthetic resin stabilizer of the present invention include low density polyethylene, high density polyethylene, linear low density polyethylene, chlorinated polyethylene, EVA resin, polypropylene,
Polyvinyl chloride, methacrylic resin, polystyrene, high-impact polystyrene, ABS resin, AES resin, MBS resin, polyethylene terephthalate,
Examples include polybutylene terephthalate, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, and unsaturated polyester resin. 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, 20.94 g of sorbitol in a four-necked flask equipped with a thermometer, stirrer, and Dean Stark trap.
(0.12 mol), 300 g of toluene, and 100.8 g of para-toluenesulfonic acid hydrate were charged, the temperature was raised while stirring, and the reaction was carried out at 110 to 120°C for 3 hours. During this time, water is removed from the reaction system using a Dean-Stark trap. After the reaction is complete, an aqueous sodium hydroxide solution is added to the reaction solution to solubilize the product in toluene. After separation, the toluene layer in which the product was dissolved is washed with water, dried, and then the toluene is distilled off to obtain a yellowish brown glassy 1,3:2,4:5,6-tris-O-
51.89 g of (2,2,6,6-tetramethyl-4-piperidinylidene)sorbitol are obtained. (Yield 73% vs. sorbitol) Hexane and water were added to this yellowish brown glassy substance and recrystallized to obtain 25.92 g of white crystals. (Melting point 43-46℃) FD-Mass spectrometry Confirmed parent ion peak 593 ¹ H-NMR (CDCl ₃ , D ₂ O) δ 1.22 (36H, s) δ 1.55 (12H, m) δ 4.05 (8H, m) ₁₃ C−NMR δ31.106 (at off-resonance, q), 31.261 (q),
31.839(q), 32.058(q), 32.220(q), 32.315
(q), 32.279 (q), 32.681 (q), 32.900 (q),
44.756 (t), 45.342 (t), 45.968 (t), 46.388
(t), 46.614 (t), 46.921 (t), 51.342 (s),
65.309(t), 67.386(t), 74.666(d), 76.656
(d), 77.717(d), 79.238(d), 110.031(s)
,
110.273 (s), 110.477 (s) Example 2 In a flask similar to that used in Example 1, 94.1 g (0.6 mol) of triacetonamine and 36.4 g of sorbitol were added.
(0.2 mol), 500 g of xylene and 149.5 g of para-toluenesulfonic acid hydrate, 135 ~
React at 140°C for 4 hours. After the reaction is completed, post-treatment and purification are carried out in the same manner as in Example 1 to obtain a yellow-brown glassy 1,3:2,4:
5,6-Tris-O-(2,2,6,6-tetramethyl-4-piperidinylidene)sorbitol
73.2g was obtained. (Yield: 62% vs. sorbitol) In addition, by recrystallizing this product from hexane and water, 61.7 g of white crystals (yield: 52% vs. sorbitol) were obtained. This crystal was confirmed to be the same compound as obtained in Example 1 by melting point, elemental analysis, and ¹ H-NMR. Example 3 In a flask similar to that used in Example 1, 1, 2,
2,6,6-pentamethyl-4-piperidone
102.4 g (0.6 mol), 36.4 g (0.2 mol) of sorbitol, 500 g of xylene and 123.6 g of para-toluenesulfonic acid hydrate were charged and reacted in the same manner as in Example 2, followed by post-treatment to give a pale yellow viscous substance. 87.8 g of 1,3:2,4:5,6-Tris-O as liquid
-(1,2,2,6,6-pentamethyl-4-piperidinylidene)sorbitol was obtained. (69% yield vs. sorbitol) FD-Mass spectrometry Parent ion peak 635 was confirmed. ¹ H-NMR (CDCl ₃ , 60MHz) δ 1.15 (36H, s) δ 1.54 (12H, m) δ 2.24 (9H, s) δ 4.04 (8H, m) Example 4 Mix the following formulation with a mixer for 5 minutes After that,
The compound obtained by melting and kneading with a mixing roll at 180°C was formed 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 used with a sunshine weather meter (light source: carbon arc, black panel temperature:
Weather resistance was evaluated by irradiating 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-methylphenol 0.05 〃 Test compound 0.2 〃 In the table, UVA-1 to -8 and -1
-2 represents the following compounds. UVA-1 2-hydroxy-4-methoxybenzophenone 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-dipentylphenyl)benzotriazole UVA-6 Ethyl-2-cyano-3,3 -Diphenyl acrylate UVA-7 bis(3,5-di-t-butyl-4
-Hydroxybenzylphosphoric acid)
Ni salt of monoethyl ester UVA-8 Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate-1 1,3:2,4:5,6-tris-O-
(2,2,6,6-tetramethyl-4-piperidinylidene)sorbitol-2 1,3:2,4:5,6-tris-O-
(1,2,2,6,6-pentamethyl-4-piperidinylidene)sorbitol

[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 with 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/mm). , and the measurement temperature was 25°C to determine the retention of breaking strength. 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 hot-pressed at 160°C to form a sheet with a thickness of 0.5 mm. Use this sheet as a sunshine weather meter (light source: carbon arc, black panel temperature:
It was irradiated for 1200 hours at 68±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 Ba-stearate 1 Zn-stearate 0.3 Test compound 0.2

【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 _C1 - _C3 alkyl group.) A general formula characterized by reacting a triacetonamine derivative or a salt thereof with sorbitol. (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 resins containing a piperidine derivative represented by the following as an active ingredient.