JPH0132223B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a bis(2-hydroxyethyl)aminotriazine compound having a 2,2,6,6-tetramethylpiperidyl group, which is useful as a light stabilizer for synthetic resins and an intermediate thereof. Triazine compounds having a 2,2,6,6-tetramethylpiperidyl group are useful compounds as light stabilizers for organic materials such as synthetic resins, and a large number of these compounds have been known. For example, Tokukai Akira
49-21389 describes that triazine compounds having a structure similar to the compound used in the present invention are useful as light stabilizers for organic materials. However, when these compounds are used as light stabilizers for synthetic resins, their effects are not sufficient, and they have the disadvantage that their effects are significantly reduced, especially after high-temperature processing, and further improvements are needed. It was hot. For this reason, various proposals have been made to increase the molecular weight of triazine compounds having a 2,2,6,6-tetramethylpiperidyl group. For example, JP-A-52-
No. 71786, JP-A-52-73886, JP-A-53-67749
No., JP-A-54-106483, JP-A-54-126249,
JP-A-55-98180, JP-A-55-102637, JP-A-55-104279, JP-A-56-4639, JP-A-56-
30974 and Japanese Patent Application Laid-open No. 56-75488,
A high molecular weight compound in which a triazine compound having a 2,2,6,6-tetramethylpiperidyl group is bonded with a polyamine, polyalcohol, or polyepoxy compound has been proposed. However, many of these high molecular weight compounds are difficult to manufacture and have poor compatibility with synthetic resins, causing bloom or bleed.
Moreover, the effect was not satisfactory. As a result of repeated studies on triazine compounds having a tetramethylpiperidyl group, the present inventors found that the compound represented by the following general formula () has particularly excellent effects as a stabilizer for synthetic resins, and also It has been found that the stabilizing ability does not decrease even when It has also been found that the compound represented by the following general formula () has two hydroxyl groups and is therefore extremely useful as a reactive stabilizer for polyurethane. (In the formula, R ₁ represents a hydrogen atom, oxyl or an alkyl group, and X represents a group CH—O,

【formula】 or

[Formula] is shown. R ₂ represents a hydrogen atom or an alkyl group, and R ₃ represents a lower alkyl group. ) The compound of the present invention represented by the above general formula () will be explained in detail below. In the above general formula (), the alkyl groups represented by R ₁ and R ₂ include methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, 2
- Examples include those having 1 to 18 carbon atoms, such as ethylhexyl, decyl, dodecyl, octadecyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, and phenylmethyl. Examples of the lower alkyl group represented by _R3 include those having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl. The bis(2-hydroxyethyl)aminotriazine compound of the present invention is obtained, for example, by the reaction of cyanuric chloride with diethanolamine.
Bis(2-hydroxyethyl)amino-4,6-
dichloro-triazine and

It can be easily produced by reacting a piperidine compound represented by the formula in the presence of a base. In addition, bis(2-hydroxyethyl) of the present invention
The aminotriazine compound can also be produced by reacting cyanuric chloride with 2 moles of a piperidine compound and then reacting with diethanolamine, or by simultaneously reacting 1 mole of diethanolamine with 2 moles of a piperidine compound. Representative examples of the compounds of the present invention represented by the general formula () are shown in Table 1 below. In addition, in the table,

【ceremony

[Formula] is shown. The present invention will be explained in more detail below with reference to Examples. Example 1 2-bis(2-hydroxyethyl)amino-
4,6-bis(2,2,6,6-tetramethyl-
4-piperidylamino)triazine (No. 1 in Table 1)
1 compound). 2-bis(2-hydroxyethyl)amino-
4,6-dichlorotriazine 5.4g, 2,2,6,
6-tetramethyl-4-aminopiperidine 7.0g,
Take 2.3g of sodium carbonate and 60ml of toluene,
The mixture was stirred under reflux in a nitrogen stream for 40 hours. The reaction mixture was filtered, and the filtered residue was added to 85 ml of a 2% NaOH aqueous solution and stirred for 30 minutes, followed by filtering, washing with water, and drying. The obtained product was dissolved in tetrahydrofuran, and insoluble materials were separated. The liquid was removed under reduced pressure to obtain a white powder product with a melting point of 115-120°C. Elemental analysis C% H% N% Calculated value 60.98 9.76 22.76 Actual value 60.83 9.77 22.85 Example 2 2-bis(2-hydroxyethyl)amino-
4,6-bis(N-butyl-N-2,2,6,6
-Tetramethyl-4-piperidylamino)-triazine (Compound No. 2 in Table 1). 2-bis(2-hydroxyethyl)amino-
Take 1.8 g of 4,6-dichlorotriazine, 3.2 g of N-butyl-N-2,2,6,6-tetramethyl-4-piperidylamine, 0.8 g of sodium carbonate, and 20 ml of toluene, and reflux in a nitrogen atmosphere. Stirred for 20 hours. Filter the reaction mixture and remove 2%
It was added to 30 ml of NaOH aqueous solution and stirred for 30 minutes. The obtained product was separated, washed with water, dried, and then recrystallized from a methanol/acetone mixed solvent to give a melting point of 280.
The product was obtained as a white powder with a temperature above .degree. Elemental analysis C% H% N% Calculated value 65.56 10.60 18.54 Actual value 65.70 10.55 18.43 Example 3 2-bis(2-hydroxyethyl)amino-
4,6-bis(1,2,2,6,6-pentamethyl-4-piperidylamino)triazine (Table 1
No. 3 compound). 1,2,2,6,6- instead of 7.0 g of 2,2,6,6-tetramethyl-4-aminopiperidine
The same procedure as in Example 1 was carried out except that 7.6 g of pentamethyl-4-aminopiperidine was used, and the melting point was 137 to 145.
The product was obtained as a white powder at . Elemental analysis C% H% N% Calculated value 62.31 10.00 21.54 Actual value 62.43 9.93 21.50 Example 4 2-bis(2-hydroxyethyl)amino-
4,6-bis(2,2,6,6-tetramethyl-
4-piperidyloxy)triazine (No. 1 in Table 1)
4 compound). Sodium 1.4g, 2,2,6,6-tetramethyl-4-piperidinol 6.3g and toluene 100g
ml was taken and stirred under reflux for 24 hours. Add 2-bis(2-hydroxyethyl)-4,6 to the cooled solution.
- 5.0 g of dichlorotriazine was added, and the mixture was stirred under reflux for 8 hours. After separating the reaction mixture, it was added to 90 ml of 2% aqueous sodium hydroxide solution and stirred for 30 minutes. The obtained product was separated, washed with water, dried, and then recrystallized from ethyl acetate to obtain a white powder product with a melting point of 103-107°C. Elemental analysis C% H% N% Calculated value 60.73 9.31 17.00 Actual value 60.79 9.33 16.87 Example 5 2-bis(2-hydroxyethyl)amino-
4,6-bis(1-oxyl-2,2,6,6-
Production of tetramethyl-4-piperidyloxy)triazine (Compound No. 5 in Table 1). Same as Example 4 except that 6.9 g of 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl was used instead of 6.3 g of 2,2,6,6-tetramethyl-4-piperidinol. Similarly,
The product was obtained as a light orange powder with a melting point of 97-102°C. Elemental analysis C% H% N% Calculated value 57.25 8.40 16.03 Actual value 57.17 8.42 16.09 Example 6 2-bis(2-hydroxyethyl)amino-
4,6-bis(1-octyl-2,2,6,6-
Production of tetramethyl-4-piperidyloxy)triazine (Compound No. 6 in Table 1). Instead of 6.3 g of 2,2,6,6-tetramethyl-4-piperidinol, 1-octyl-2,2,
6,6-tetramethyl-4-piperidinol 10.8
A white waxy solid product was obtained in the same manner as in Example 4 except that g was used. Elemental analysis C% H% N% Calculated value 68.52 10.86 11.70 Actual value 68.40 10.84 11.75 Example 7 2-bis(2-hydroxyethyl)amino-
4,6-bis(9-aza-3-ethyl-8,8,
Production of 10,10-tetramethyl-1,5-dioxaspiro[5,5]-3-undecylmethoxy)triazine (Compound No. 7 in Table 1). Dianuric chloride 0.93g, 9-aza-3-ethyl-
3.4 g of 3-hydroxymethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane, 0.44 g of sodium hydroxide and 30 ml of toluene were taken and stirred under reflux for 24 hours. After cooling, diethanolamine 0.58g and sodium hydroxide
0.22 g was added, and the mixture was further stirred under reflux for 15 hours. The reaction mixture was washed with water, dried, and the solvent was removed. The obtained product was purified by preparative liquid chromatography to obtain a glassy solid product. Elemental analysis C% H% N% Calculated value 61.50 9.14 11.63 Actual value 61.73 9.21 11.48 Example 8 2-bis(2-hydroxyethyl)amino-
4,6-bis(9-aza-3-ethyl-8,8,
Production of 9,10,10-pentamethyl-1,5-dioxaspiro[5.5]-3-undecylmethoxy)triazine (Compound No. 8 in Table 1). 9-aza-3-ethyl-3-hydroxymethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5] instead of 3.4 g of undecane, 9
-Aza-3-ethyl-3-hydroxymethyl-
A glassy solid product was obtained in the same manner as in Example 7, except that 3.6 g of 8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5,5]undecane was used. Elemental analysis C% H% N% Calculated value 62.40 9.33 11.20 Actual value 62.53 9.27 11.09 The compound of the present invention is extremely useful as a stabilizer for organic materials such as synthetic resins. Organic materials stabilized by the compounds of the present invention include, for example, α-olefin polymers such as low-density and high-density polyethylene, polypropylene, polybutene, poly-3-methylbutene, or ethylene-vinyl acetate copolymers. , polyolefins such as ethylene-propylene copolymer, ethylene-butene-1 copolymer, and copolymers thereof,
Polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer Polymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, Vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, Vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-
Acrylonitrile copolymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, petroleum resins, coumaron resins, polystyrene, polyvinyl acetate, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) ), acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene copolymer, methacrylate resin such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl Formal, polyvinyl butyral, linear polyester, polyphenylene oxide, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. be able to.
Furthermore, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-
Rubbers such as butadiene copolymer rubber or blends of these resins may also be used. Also included are crosslinked polymers such as crosslinked polyethylene crosslinked by peroxide or radiation, and foamed polymers such as expanded polystyrene foamed with a foaming agent. In addition, oils and fats, fragrances, mineral oil, soaps, creams,
Natural and synthetic waxes, synthetic ester-based oils are also stabilized by the addition of the compounds of the invention. When the compound of the present invention is added to an organic material, the amount added is 0.001 to 10% by weight, preferably 0.01 to 3% by weight, based on the organic material. In addition to the compound of the present invention, if necessary, a phenolic antioxidant, a thioether antioxidant, an organic phosphite compound, an ultraviolet absorber, a heavy metal deactivator, a nucleating agent, a metallic soap, an organic tin compound, and a plasticizer are added. , epoxy compounds, pigments, fillers,
Foaming agents, antistatic agents, flame retardants, lubricants, processing aids, etc. can be added in combination. Next, the effect of the compound of the present invention as a light stabilizer will be specifically explained with reference to the following examples. Example 9 Polypropylene 100 parts by weight Stearyl-β-3,5-di-tert-butyl-4
-Hydroxyphenylpropionate
0.2 Stabilizer (Table 2) 0.3 A press sheet with a thickness of 0.3 mm was prepared using the above formulation, and a light resistance test was conducted using a high-pressure mercury lamp. A light resistance test was also conducted on the sheet after being irradiated with light for 100 hours and immersed in hot water at 80°C for 15 hours.
The results are shown in Table-2.

[Table] Example 10 It is known that ordinary stabilizers lose their effectiveness significantly due to volatilization, decomposition, etc. during high-temperature processing of resins. In this example, the effect of high-temperature processing was confirmed by repeatedly performing extrusion processing. After mixing the resin and additives in a mixer for 5 minutes according to the following formulation, a compound was prepared using an extruder. After extrusion was repeated five times (cylinder temperature: 230°C, 240°C, head die temperature: 250°C, rotation speed: 20 rpm), a test piece was made using an injection molding machine using this compound. (Cylinder temperature
240° C., nozzle temperature 250° C., injection pressure 475 Kg/cm ² ) Using the obtained test piece, a light resistance test was conducted using a high-pressure mercury lamp. In addition, the same test was conducted for a sample that had been extruded once. The results are shown in Table-3. <Composition> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0.2 parts by weight Stearyl-β-3,5-di-tert-butyl-4
-Hydroxyphenylpropionate
0.1 Dilaurylthiodipropionate 0.2 Stabilizer (Table-3) 0.2

[Table] Example 11 Polyethylene 100 parts by weight Ca-stearate 1.0 Tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Methane 0.1 Distearylthiodipropionate 0.3 Stable Agent (Table 4) 0.2 The above mixture was kneaded and pressed to form a sheet with a thickness of 0.5 mm. Using this sheet, the light resistance was measured in a weatherometer, and the time until it became brittle was measured. The results are shown in Table 4.

[Table] Example 12 ABS resin 100 parts by weight 4,4'-butylidene bis(2-tert-butyl-m
-Cresol) 0.1 Stabilizer (Table-5) 0.3 Roll knead the above mixture and press it to a thickness of 3 mm.
A sheet was created. Using this sheet, the residual tensile strength after 800 hours of irradiation was measured using a weatherometer. The results are shown in Table-5.

[Table] Example 13 Ethylene-vinyl acetate copolymer 100 parts by weight 2,6-di-tert-butyl-p-cresol
0.1 Ca-stearate 0.1 Zn-stearate 0.1 Diisodecyl phenyl phosphite 0.2 Stabilizer (Table 6) 0.2 After kneading the above mixture on a roll at 130℃, press it at 140℃ to form a sheet with a thickness of 0.4mm. Created. The residual tensile strength of this sheet was measured after 500 hours of irradiation in a weatherometer. The results are shown in Table-6.

[Table] Example 14 Polyvinyl chloride 100 parts by weight Dioctyl phthalate 48 Epoxidized soybean oil 2 Trisnonylphenyl phosphite 0.2 Ca-stearate 1.0 Zn-stearate 0.1 Stabilizer (Table 7) 0.3 Roll the above mixture A sheet with a thickness of 1 mm was prepared by kneading the mixture above. Using this sheet, a light resistance test was conducted in a weatherometer. Display the results.
7.

[Table] Example 15 100.0 g (0.05 mol) of polytetramethylene ether glycol with a molecular weight of 2000 was mixed with 150 g of chlorobenzene.
Diphenylmethane diisocyanate dissolved in ml
20.0g (0.08mol) was added and reacted at 120°C for 30 minutes. Then 1,4-butylene glycol
2.25g (0.025mol) and the stabilizer listed in Table 8
0.005 mol was added and reacted at 110°C for 2 hours. The resulting solution was dry-spun using a conventional method to obtain a 40-denier elastic yarn. Furthermore, Comparative Examples 15-1 and 15
-2 is 1,4-butylene glycol 2.7
g (0.03 mol) and 0.005 mol of stabilizer was added before spinning. Using the obtained elastic yarn, 72 on the fade meter
The residual elongation rate after time irradiation was measured. Elastic threads extracted with carbon tetrachloride for 2 hours were also tested in the same manner. The results are shown in Table 8 below.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A bis(2-hydroxyethyl)aminotriazine compound represented by the following general formula (). (In the formula, R ₁ represents a hydrogen atom, oxyl or an alkyl group, and X represents a group CH—O—,
Indicates [formula] or [formula]. R ₂ represents a hydrogen atom or an alkyl group,
R ₃ represents a lower alkyl group. )