JPS6054391A - Piperidine derivative, its preparation and synthetic resin stabilizer containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is H or C1-9 alkyl). EXAMPLE:1,3:2,4:5,6-Tris-O-(2,2,6,6-tetramethyl-4-piperidinylidene)-so rbitol. USE:Stabilizer of various synthetic resins such as PE. PP, PVC, ABS resin, polyethylene terephthalate, polyamide, polyurethane, etc. PREPARATION:The objective compound can be produced by reacting the triacetoneamine derivative of formula II or its salt with sorbitol of formula III preferably in the presence of an acidic catalyst (e.g. p-toluene-sulfonic acid) or a dehydration agent (e.g. calcium chloride), optionally in a solvent such as toluene, preferably at 60-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a piperidine derivative represented by the general formula (1) (in the formula, 几 represents a hydrogen atom or a C3 to C3 alkyl group), a method for producing the same, and a piperidine derivative using the same as an active ingredient. This invention relates to stabilizers for synthetic resins.

It is well known that synthetic resins such as polyethylene, polypropylene, polyvinyl chloride, deli 1/tan, Al18 resin, etc. 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
-1-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-8,5-dipentylphenyl)benzotriazole, Ejiru 2-
Cyano-8,8-diphenylacrylate, 2 @ 4
-n*-butylphenyl-8,5-di-t-butyl-4
-Hydroxybenzoate, (2,2'-thiobis(4
-1-octylphenolad)]-]n-butylamine nickel ('I), bis(8,5-di-t-butyl-4-
It is known to use Ni salt of hydroxybenzylphosphoric acid) monoethyl ester, bis(2°2.6.6-tetramethyl-4-piperidyl) sebacate, etc., but these light stabilizers have poor light resistance. I am still not completely satisfied with my sexuality.

As a result of various studies aimed at solving these problems, the present inventors found that the piperidine derivative represented by the general formula (1) has an extremely excellent effect on preventing photo-induced deterioration of synthetic resins. , led to the present invention.

The piperidine derivative of the present invention represented by the above general formula (1) is a new substance synthesized for the first time by the present inventors, and has the general formula 1) % formula % (wherein, pore has the same meaning as above). It can be produced by reacting the triacetol miso derivative or its salt represented by the formula with sorbitol represented by the symbol 2.

Here, examples of salts of triacetone 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.

Further, examples of the C1 to C3 alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

This reaction is carried out in the presence of an acidic catalyst or a dehydrating agent, 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, Water-soluble polar solvents such as dimethyl sulfoxide, dioxane, sulfolane, methanol, ethanol, propatool, isopropyl alcohol, butanol, tert--, n-amyl alcohol, isoamyl alcohol, 2-ethylhexyl alcohol Examples include alcohols such as cyclohexanol, and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether, and these may be used alone or in combination of two or more types. .

Examples of acidic catalysts include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, hydrobromic acid, para-toluenesulfonic acid, salivary lead chloride, boron trifluoride, cation exchange resins, polymer complexes of aluminum chloride, selenium oxide, and ammonium chloride. An example of the dehydrating agent is calcium chloride.

In the reaction of the triacetonamine derivative or its salt with sorbitol, the triacetonamine derivative or its salt is usually used in an amount of 2 to 5 per mole of sorbitol.
Moles, preferably 2.5 to 4 moles <17. In addition, the acidic catalyst or dehydrating agent is t per mole of sorbitol.
) 0.01 to 6 mol, preferably 0.1 to 4 mol.

The reaction temperature is 10-800°C, preferably 60-211°C.
It is 0°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 with an appropriate solvent if necessary.

The piperidine derivative of the present invention thus obtained is 1
．． 8:2.4:5.6-Dorissu0-(2゜2.6.6
-tetramethyl-4-piperidinylidene)sorbitol, 11B:214:516-)lis-〇-(1,2,2
, 6,6-penkyutyl-4-piperidine derivative) Sorbitol, 1.8:2.4:5.6-Dolisu0-(2,
Examples include 2,e,6-tetramethyl-l-propyl-4-piperidinylidene) sorbitol.

When the piperidine derivative of the present invention is used as a stabilizer for synthetic resins, the amount added to the synthetic resin is usually 0.01 to 5 parts by weight, preferably 0.0 parts by weight, per 100 parts by weight of the synthetic resin.
The amount is 5 to 2 parts by weight, and most of the known mounting and operating methods for mixing and blending stabilizers, pigments, fillers, etc. into synthetic resins can be applied as is.

When using the stabilizer for synthetic resins of the present invention, other additives such as antioxidants, light stabilizers, metal deactivators, metal soap bases, nucleating agents, lubricants, antistatic 1E agents, A repellent, a pigment, a filler, etc. may be used in combination.

In particular, thermal and oxidative stability can be improved by using a phenolic antioxidant 11-agent in combination. Examples of phenolic antioxidants include 2.
6-di-t-butyl-4-methylphenol, n-octa-decyl-β-(8,5-di-t-butyl-4-hydroxyphenyl)propionate, t,t,a-tris(2-methyl- 4-hydroxy-5-butylphenyl)butane, 1,8.5-)dimethyl-2,4,6-1
- Lis(8,6-di-monobutyl-4-hydroxybenzyl)benzene, 1 m 8 * R) Lis(8,5-
Di-butyl-4-hydroxybenzyl)isocyanurate, (9) 1,R,5-)lis[β-(8,5-di-butyl-4-hydroxyphenyl)propionyloxyethyl]
isocyanate, ] t 8 e5-tris (2,6
-di-methyl-8-hydroxy-4-t-butylbenzyl) isocyanurate, pentaerythritol-tetrakis [β-(8,5-di-t-butyl-4-hydroxyphenylene) propionate], etc. can be given.

In fact, by using a phosphite-1-based antioxidant in combination, the hue can be changed.

Examples of these phosphite-based antioxidants include tris(nonylphenyl)phosphite, distearylpentaerythritol diphosphite, and tris(2,4
-di-t-butylphenyl) phosphite, tris(2
-1-Butyl-4-methylphenyl (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2.

4-di-t-butylphenyl) = 4.4'-bi(10
) Examples include phenylene diphosphonite.

In addition, dilauryl thiodipropionate, simiristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (β-lauryl thiopropionate), pentaerythritol tetrakis (β-hexylthiopropionate) A sulfur-based antioxidant such as pionate) can also be used in combination.

Examples of the 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, E
VM resin, polypropylene, polyvinyl chloride, methacrylic resin, polystyrene, high-impact polystyrene, ABS
resin, AE8 resin, u, ns resin, polyethylene terephthalate, polybutylene terephthalate, polyamide,
Examples include polyamide, polycarbonate, polyacetal, polyurethane, and unsaturated polyester resin.

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

Example 1 100 g of triacetonamine hydrochloride in a four-hole flask equipped with a thermometer, stirrer and Dean-Stark trap.
f (0,52 moa 1/), sorbitol 20.949
(0.12 moJl/), 300 g of toluene, and 100.8 F of para-toluenesulfonic acid hydrate are charged, and the temperature is raised while stirring at intervals, and the reaction is 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, add sodium hydroxide aqueous solution to the reaction solution,
Solubilize the product in toluene. The toluene layer in which the product was dissolved is separated, washed with water, dried, and then the toluene is distilled off to obtain a yellowish brown glassy 1.8:2.4:5
,6-Dolisu0-(2,2,6,6-chitramethyl
t-4-hyhelidinylidene) sorbitol 51.89f
is obtained. (Yield 78% vs. sorbitol) Hexane and water were added to this yellowish brown glass and recrystallized to obtain white crystals 25.92F. (
Melting point 4B~46°C) FD-Mass spectrometry confirmed parent ion peak 598'H-NMR (CDO/, , D20) δ 1.2
2 (86H, s) δ 1.55 (12H, m) δ 4.05 (s H* m) 180-NMR δ81.106 (at off-resonance, q), 81.26
1(q), 81.889(q), 82.058(9),
82.220(q), 82.815(q), 82.87
9 ((1), 82.681(q), 82.900(9)
, 44.758(t), 45.842(t), 45.9
68(t), 46.888(t), 46.614(1)
, 46.92] (t), 51.042 (s), 65
．． 809(t), 67.886(t), 74.666(
1B) (d), 76.656(d), '77, '71TCd>
, 79.288(d), 1111.081(8), 11
0.278 (R), 110.477 (8) Example 2 In a flask similar to that used in Example 1, 94.1 f (0.6 mol) of triacetonamine and 86.1 f (0.6 mol) of sorbitol were added.
41 (0.2 mol), 500y of xylene and 149.5f of para-toluenesulfonic acid hydrate,
React at 5-140°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 yellow-brown glassy 1,3:2, 4:5, 6.
-1-Lis-〇-(2,2,6゜6-tetramethyl-4
-biperidinylidene) sorbitol'18.21 was obtained. (Yield 62% vs. sorbitol) Furthermore, by recrystallizing this product from hexane and water, white crystal 61.7F (yield 52% vs. sorbitol) was obtained.

This crystal was confirmed to be the same compound as obtained in Example 1 by melting point, elemental analysis, and 'H-NMR (14).

Example 3 In a flask similar to that used in Example 1, 1°2.2,6.
6-bentamethyl-4-piperidone IQ2.4F (0,
6 mol), sorbitol 86.4 f (0.2 mol)
, 500 g of xylene and 128.61 g of para-toluene sulfonic acid hydrate were charged, and the reaction was carried out in the same manner as in Example 2. After treatment, a pale yellow viscous liquid of 87.8 y was prepared.
1,8:2.4:5.6-) squirrel-〇-(1,2,2
e6*6-bentamethyl-4-piperidinylidene) sorbitol was obtained.

(69% yield vs. sorbitol) F, r) - mass spectrometry Parent ion peak 685 was confirmed.

'H-NMTL (ODO(1?3, 60 MIT
z ) δ 1.15 (8611, s) δ 1.54 (12'TI, rn) δ 2.241i (91T, s) δ 4.04
(8T(,m) Example 4 After mixing the following formulation with a mixer for 5 minutes, the mixture was heated to 180°C.
The compound obtained by melting and kneading with a t-kissing roll is
A 11 nIO) sheet was formed using a hot press at 210'C to prepare a 150 x 80 x I octopus test piece.

This test piece was irradiated with light in a sunshine weather meter (light source: carbon arc, black panel temperature: 88°C, 8°C, 1 spray cycle: 120 minutes, soufflé hour: 18 minutes) and bent into a shrimp shape every 60 hours. The weather resistance was evaluated by measuring the time it took to break.

The results are shown in Table-1.

<Formulation> Unstabilized polypropylene tO(ltj1m Calcium stearate 0.1// 2.6-di-butyl-4-methylphenol 0.
05'// Test compound 0.2 tt In the table, UVA-1 to 8 and t-1 to 2 indicate the following compounds.

UVA-12-hydroxy-4-methoxybenzophenone UVA-22-hydroxy-4-n-octoxybenzophenone UVA-82 (2-hydroxy-5-methylphenyl)benzotriazole UVA-42 (2-hydroxy -8- to -butyl-5-
methylphenyl) -5-chlorobenzotriazole UVA-52 (2-hydroxy-8,5-dipentylphenyl)benzotriazole UVA-6 ethyl-2-cyano-B, B'-diphenylacrylate UVA-7 his( Ni salt of 8,5-sheet t-h-4-hydroxybenzylphos(17) holic acid) monoethyl ester UVA-s his(2,2,6,6-te)ramethyl-4
-piperidyl) sebacate 1-1 1,8:2,4:5.6-)-lis-〇-(2
, 2,6,6-titramethyl-4-piperidinylidene) sorbitol 1-2 1.8:2.4 5.6-dolisu 0-(1,
2,2,6,6-bentamethyl-4-piperidinylidene)sorbitol (18) Table-1 Example 6 2596 urethane dope (25 parts of polyurethane resin,
The test compounds shown in Table 2 were added to 8.75 parts of dimethylformamide and 71.25 parts of tetrahydrofuran at 1% based on the polyurethane resin, and then coated on a polyester film to a thickness of 1.2 ffFJ.
It was dried for 1 hour in a drying mold at 5°C. The sheet thus obtained was punched out using a No. 3 dumbbell, and a fade meter (light source: ultraviolet carbon arc, black panel temperature 268±
After light irradiation for 60 hours and 120 hours at 8℃), tensile test (tensile speed: 200s + w/mg, measurement temperature: 2
5°C) to determine the retention of breaking strength.

The results are shown in Table-2.

Table 2 Example 6 The following composition was melt-kneaded using a 1fiO°C mixing roll, and then a sheet with a thickness of 0.51N was created using a hot press at 160°C.

This sheet was placed in a sunshine weather meter (light source: carbon arc, black panel temperature = 68±8°C, spray cycle = 120 minutes, spray time = 18 minutes) for 12 minutes.
After irradiation for 00 hours, the degree of discoloration was observed.

The results are shown in Table-8.

<Composition> Polyvinyl chloride 100 parts by weight Dioctyl phthalate 8B’/ Epoxidized soybean oil 2 // Ba-stairley) 1 // Zn-stearate 0.8 1/ Test compound 0,2 (21) Table-8 / (22 completed)

Claims (1)

[Claims] (1) A piperidine derivative represented by the general formula (in the formula, ■ represents a hydrogen atom or an alkyl group of Cl-03). (1) (In the formula, 几 represents a hydrogen atom or an alkyl group of 01-C3. A method for producing a piperidine derivative represented by (In the formula, the pores represent hydrogen atoms or 01 to C1 alkyl groups.) A stabilizer for synthetic resins containing a piperidine derivative represented by the following as an active ingredient: