JPH02285A - Piperidyl-triazine derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R<1> is H, 1-18C alkyl, etc.; R<2> is H, 2018C acyl, etc.; X is a group having O or Nr<5> (R<5> is 1-4C alkyl, etc.); R<3> is 1-6C alkylene which can be interrupted with O; Y is a group having OCO, COO, etc.; n is 2-4; Z is S, etc., when n is 2, 4-8C alkanetriyl which can be interrupted with N when n is 3 and alkanetetrayl which can be interrupted with O when n is 4]. EXAMPLE:Bis [2-2,4-bis [N-ethyl-N-(2,2,6,6-tetramethyl-4-piperidyl)-amino]-1, 3, 5-triazin-6-yl]-oxyethyl]succiniate. USE:A stabilizer for synthetic polymer materials. PREPARATION:A compound expressed by formula II (Q is halogen) is reacted with a compound expressed by formula III (Y' is OH, etc.) to provide a com pound expressed by formula IV, which is then reacted with a compound expressed by formula V (R<1>' is R<1>; R<2>' is R<2> other than 2-8C acyl). The resultant compound is subsequently reacted with a compound expressed by the formula (Y'')n-Z (Y'' is NCO, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION OBJECTS OF THE INVENTION The present invention relates to novel biridyl-triazine derivatives and acid addition salts thereof useful as stabilizers for synthetic polymeric materials.

The inventors of the present application have conducted extensive research over many years on the anti-deterioration effects of lysine compounds on polymeric materials, and have found that the following new piperidyl-lyazine derivatives have the ability to prevent photo- and thermal deterioration of polymeric materials. The present invention was completed based on the discovery that it is a stabilizer that has an excellent preventive effect, low heat volatility, and low elution.

<Structure of the invention> The novel biiridyl-triazine derivative of the present invention has the following formula (
1) Denoted by K.

Formula In the above formula, R1 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxyalkyl group having 3 to 22 carbon atoms, an acyl group having 2 to 18 carbon atoms, or an optionally substituted aralkyl group. or indicates a group.

R2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 18 carbon atoms, or a substituted alkyl group having 1 to 4 carbon atoms. ] indicates a group having

R3 has 1 to 6 carbon atoms, which may be interrupted by an oxygen atom
represents an alkylene group.

Y represents a group having the formula -0CO-, a group having the formula -coo-t-, a group having the formula -CONH-, or a group having the formula -0CONH-.

n represents an integer from 2 to 4.

When n is 2, 2 is an alkylene group having 1 to 18 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, or a group having the formula, a group having the formula, a group having the formula, or a group having the formula ( In the above formula, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p represents 1 to 4, and q and r represent the same -
Or it shows 0 to 3 differently. ) When n is 3, 2 represents an alkantriyl group having 3 to 8 carbon atoms which may be interrupted by a nitrogen atom.

When n is 4, 2 represents an alkantetrayl group having 4 to 8 carbon atoms which may be interrupted by an oxygen atom.

The alkyl group having 1 to 18 carbon atoms represented by R may be linear or branched, such as methyl, ethyl, n-propyl, impropyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl. , n-decyl, n-dodecyl, n-octadecyl to obtain sb, preferably having 1 to 8 carbon atoms.
number of alkyl groups.

The alkoxy portion of the alkoxyalkyl group having 3 to 22 carbon atoms represented by R1 has 1 to 18 carbon atoms, and the alkyl portion has 2 to 4 carbon atoms.

The alkyl moiety of alkoxy having 1 to 18 carbon atoms is the above R
Suitable alkoxy moieties are alkyl groups having 1 to 8 carbon atoms, such as methoxy, ethoxy, n-propoxy, inpropoxy, n-butoxy, n-hexitoxy, and n-octoxy. The alkyl moiety having 2 to 4 carbon atoms can be, for example, ethyl, n-propyl, inpropyl, n-butyl, isobutyl, preferably ethyl.

The acyl group having 2 to 18 carbon atoms represented by R', R2 and R4 is, for example, acetyl, f-ropionyl, acryloyl, n-butyryl, n-hexanoyl, benzoyl, n-
- Octanoyl, lauroyl, 9-lumitoyl, stearoyl, preferably aliphatic acyl having 2 to 4 carbon atoms, particularly preferably acetyl.

The optionally substituted aralkyl group represented by R', R2, and R4 may be an alkyl-phenyl group having 1 to 4 carbon atoms, and the phenyl ring may have a substituent, and the substituent The group is, for example, alkyl having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl; alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy; or fluorine, chlorine. , and halodane atoms such as bromine. For example, it can be benzyl, phenethyl, propylphenyl, butylphenyl, p-methylbenzyl, p-chlorobenzyl, preferably benzyl.

The alkyl group having 1 to 18 carbon atoms represented by R2 and R4 may be the same as the alkyl group exemplified for R above,
Preferably alkyl having 1 to 4 carbon atoms, such as methyl,
Ethyl, n-propyl, isopropyl, n-butyl are preferred, and methyl is particularly preferred.

The alkylene group having 1 to 6 carbon atoms which may be interrupted by an oxygen atom represented by R3 is 1, for example, methylene, ethylene,
Ethylidene, trimethylene, f-propylene, ingropylidene, tetramethylene, (tamethylene, hexamethylene, 3-oxapentalene) can be used, and methylene, ethylene, and ethylidene are preferable.

The alkyl group having 1 to 4 carbon atoms represented by R5 or R may be straight-branched or branched, and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl, and is preferably a methyl group.

2 has 1 to 18 carbon atoms, which may be interrupted by an oxygen atom, a sulfur atom, or a group having the formula
Examples of alkylene groups include methylene, ethylene, trimethylene, glopylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene, hexadecamethylene, formula -(CH2)2-0-(CH2 )2-,-(CH2
)2-8-(CH2)2--(CH2)2-0-(CH
2) 2-0-(CH2)2-, -(CH2)3-0-(
CH2), -.

and preferably an alkylene group having 2 to 8 carbon atoms.

The alkantriyl group having 3 to 8 carbon atoms and optionally interrupted by a nitrogen atom represented by 2 may be a group having the formula %, preferably a group having the formula %. .

The alkantetrayl group having 4 to 8 carbon atoms which may be interrupted by an oxygen atom represented by 2 is -CH2-CH2-
C-CH2-CH2--CH2-CH-CH-CH2- -CH2-CH-CH2-0-CH2-CH-CH2-
It can be a group having the formula %, preferably a group having the formula %.

In the present invention, preferred compounds are those of formula (I).

3. Compounds in which R3 is a fullkylene group having 1 to 4 carbon atoms which may be interrupted by an oxygen atom, 4. Compounds in which X is an oxygen atom, - group or -NCR, - group, 5, Y is a group having the formula -0CO--CONH- or -COO-, 6. an alkylene group having 1 to 10 carbon atoms, where n is 2 and 2 is optionally interrupted by an oxygen atom; In the formula, R
6 is a hydrogen atom or a methyl group, p is a compound (wherein R4 is a hydrogen atom, a methyl group, or a pennol group), 2, R2 is a hydrogen atom, a methyl group, or a benzyl group (wherein the formula 7. A compound in which R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; 8. A compound in which R is a hydrogen atom or a methyl group. A certain compound, 9,
Compounds in which X is Ichishuichi or -NCH3-, 10,
A compound in which R3 is a methylene group, an ethylene group, or an ethylidene group; 11. A compound in which n is 2 and 2 is an alkylene group having 2 to 8 carbon atoms; 12. A compound in which R' is an alkylene group having 1 to 4 carbon atoms; Alkyl group.

R2 is a hydrogen atom, X is one, n is 2, and 2 is an alkylene group having 2 to 8 carbon atoms, R3
is a methylene group, and Y is a group having the formula -〇〇〇-; 13. R' is an alkyl group having 1 to 4 carbon atoms;

R2 is a hydrogen atom, X is a single plate, n is 2, and 2 is a fullylene group having 2 to 8 carbon atoms, R3
is an ethylene group, and Y is a group having the formula -OC〇-.

Also included within the scope of the invention are acid addition salts of compounds of formula (I). Such acid addition salts are not particularly limited as long as they do not inhibit the stabilization of the polymer; for example, sulfuric acid,
Inorganic acids such as hydrochloric or phosphoric acid; formic, acetic, valeric, stearic, oxalic acids.

Adipic acid, sepatic acid, maleic acid, benzoic acid, p-
Carboxylic acids such as t-butylbenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, salicylic acid, terephthalic acid; sulfonic acids such as methanesulfonic acid, benzenesulfonic acid; or phenyl It may be a salt of a phosphonic acid such as phosphonic acid.

Individual pyridyl-triazine derivatives having the formula (1) are listed below in Table 1, without limitation. The numbers assigned to the compounds in this list refer to the numbers given to the compounds in the following Examples.Compounds having the formula (1)'t- according to the present invention can be produced according to the method shown below.

Method B (To) [Phase] (To) (l (Foundation) In the above formula, R11 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxyalkyl group having 3 to 22 carbon atoms, or a substituted Indicates a good aralkyl group.

R2' represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an optionally substituted aralkyl group.

Indicates the group. ) or -○H group.

Showing 1 to 4 alkoxy groups or halogen atoms,
) or isocyanate group.

2 represents a group as defined above, and Q represents a halogen atom such as chlorine, bromine, or iodine (preferably a chlorine atom).

The first step of method A is a step of producing a compound having the general formula (to), and is achieved by reacting a compound having a hole and a compound having an ω under catalytic reduction conditions.

The catalyst used in the reaction is not particularly limited as long as it is used in ordinary catalytic reduction reactions, but preferred examples include radium-on-carbon, palladium black, platinum oxide, and Raney nickel; particularly preferred catalysts include oxidized nickel. It is platinum.

The solvent used is not particularly limited as long as it does not participate in the reaction, but usually water, methanol, ethanol, -,60
Alcoholic beverages such as panol are used.

The hydrogen pressure used is usually from normal pressure to 10 atm, the reaction temperature is from room temperature to 1,000 yen, and the time required for the reaction varies depending on the type of raw material compound or catalyst or reaction temperature, but is usually 30 minutes to 5 hours. It is.

Compound ■ can also be used in the form of a salt, such as mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid; acetic acid,
Carboxylic acids such as trifluoroacetic acid, adipic acid, benzoic acid; unasulfones such as methanesulfonic acid, P-)luenesulfonic acid? Salts with phosphonic acids such as ffl or 1d phenylphosphonic acid can be mentioned.

The second and third steps of method A are based on the general formulas ■ and ■, respectively.
In the step of producing a compound having general formula (V) and a compound having general formula (b) in an inert solvent, or a compound having general formula (to) and a compound having general formula (This is achieved by reacting the compounds having 1) with each other.

The inert solvent used in the reaction is not particularly limited as long as it does not participate in this reaction, but suitably includes water, acetone, ketones such as methyl ethyl ketone; ethers such as ether, tetrahydrofuran, and dioxane; benzene, toluene, Aromatic hydrocarbons such as xylene; n-
Examples include saturated hydrocarbons such as hebutane, n-octane, isooctane, cyclohexane, and ethylcyclohexane; or mixed solvents of the above-mentioned organic solvents and water; particularly preferred is aqueous acetone.

The reaction temperature is 0°C to 200°C, preferably room temperature to 150°C, and the time required for the reaction varies depending on the type of raw material compound or reaction temperature, but is usually 30 minutes to 30 hours.

Further, the reaction is suitably carried out in the presence of a deoxidizing agent, and examples of the deoxidizing agent include sodium hydroxide, potassium hydroxide,
Inorganic bases such as sodium carbonate, potassium carbonate or organic bases such as triethylamine, pyridine, N,N-dimethylaniline, 1.8-S7 azabicyclo[4,3,0]undec-7-ene (DBU). Preferred are sodium hydroxide, potassium hydroxide, and sodium carbonate.

It is potassium carbonate.

The fourth step of method A is a step of producing a compound having the general formula (Ia), which is achieved by reacting an appropriate amount of the compound having the general formula (■) and the compound having the general formula (2) in an inert solvent. be done.

Indicates an alkyl group having 1 to 4 prime numbers. ), Y〃is 10H
group or -NF2 group, the reaction is carried out in an inert solvent in the presence of a base, usually at a reaction temperature of 80°C to 150°C and a reaction time of 30 minutes to 5 hours, by distilling off the lower alcohol produced. It will be done.

As a base, for example sodium methylate.

Alkali metal compounds such as sodium ethylate, potassium t-butyrad, sodium hydroxide, potassium hydroxide, lithium amide or titanic acid compounds such as tetraisozolopyl titanate and preferably tetrabutyl are used, but preferably are sodium ethylate, potassium hydroxide, and titanic acid compounds. As the inert solvent, hydrocarbons such as benzene, toluene, xylene, n-hebutane, n-octane, isooctane, cyclohexane, and ethylcyclohexane are preferably used. )
When , the reaction is carried out in an inert solvent in the presence or absence of a deoxidizer, usually at a reaction temperature of room temperature to 130°C, and a reaction time of 3.
It takes between 0 minutes and 3 hours.

Examples of deoxidizers include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

Alkali metal carbonates such as sodium carbonate and potassium carbonate; organic bases such as triethylamine and pyridine are preferably used.

Preferred examples of inert solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; unahalotanated aliphatic hydrocarbons such as chloroform and trichloroethane; and ethers such as diethyl ether, tetrahydrofuran, and dioxane. be done.

In the compound, when Y' is a 10H group and Y is an isocyanate group, the reaction is usually carried out in an inert solvent at a reaction temperature of room temperature to 160°C and a reaction time of 30 minutes to 5 hours. . As inert solvents, aromatic hydrocarbons such as evabenzene, toluene, xylene; hydrocarbons such as n-hebutane, n-octane, isooctane, cyclohexane, ethylcyclohexane are preferably used.

A compound in which one or both of R1 and R2 in the general formula (1) is an acyl group may be prepared by the general formula (Ia
) can be obtained by performing an acylation reaction on a compound in which one or both of R and R2' is a hydrogen atom.

The acylation reaction can be carried out in the same manner as in the fourth step of method A described above, using the corresponding carboxylic acid activated ester (acid halide, acid anhydride or acid lower alkyl ester) as the acylating agent.

After the reaction is completed, the target product of each step can be collected from the reaction mixture according to a conventional method. For example, if necessary, if unbathable substances are present in the reaction mixture, they are filtered out, or if the reaction mixture is acidic or alkaline, they are neutralized, and then water is added and extracted with a water-miscible organic solvent. It can be obtained by drying the extracted liquid and distilling off the solvent from the extracted liquid.

Furthermore, the obtained target compound can be purified by conventional methods such as column chromatography, preparative thin layer chromatography, distillation method, recrystallization method, etc., if necessary.

Method B is a method in which a compound having the general formula (1) is separately produced by changing the reaction order.

The first step is a step of producing a compound having the general formula (2), and the second step is a step of producing a compound having the general formula (2). These can be achieved by reacting the compound (to) and the compound (4), or the compound (to) and the compound (t), respectively, in the same manner as in the second and third steps of Method A.

<Effects of the Invention> The piperidyl-triazine derivative having formula (1) and its addition salt according to the present invention have excellent compatibility with polymers,
It has low volatility and surface migration, and has excellent light and heat stabilizing effects, so it can be used to stabilize a wide range of synthetic polymers.

Synthetic polymers stabilized in this manner include:

Olefin and diene polymers Homopolymers of olefins and dienes (e.g., tertiary, low density, linear low density, high density and crosslinked polyethylene)
, mixtures of such homopolymers (e.g. mixtures of y1?lipropylene and polyethylene, polypropylene and polypuden-1. or polypropylene and polyisobutylene), copolymers of olefins (e.g. -1 copolymers, ethylene-butene-l copolymers), and copolymers of hyolefins and dienes (e.g. terpolymers of ethylene and propylene with butadiene, hexadiene, dicyclopentadiene or tsene such as ethylidene nordernene): styrene Polymers polystyrene, copolymers of styrene or α-methylstyrene (e.g., taba, styrene-maleic anhydride copolymers, styrene-butadiene copolymers, i?lima, styrene-
acrylonitrile-methyl methacrylate coprimer,
styrene-acrylonitrile-acrylic ester copolymers, styrene-acrylonitrile copolymers modified with acrylic ester polymers to impart impact strength and styrene polymers modified with EPDM to impart impact strength) and graft copolymers of styrene (e.g. Graft copolymers of styrene and acrylonitrile to polybutadiene, commonly referred to as acrylonitrile-butadiene-styrene or ABS f-lastics, and mixtures thereof with the above-mentioned styrene copolymers): Vinyl halide and hyponylidene polymer polychlorides Vinyl, polyvinylidene chloride. Polyvinyl fluoride, polychlorogrene, vinyl chloride-vinylidene chloride copolymer,
Vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinylidene chloride-vinyl acetate copolymer: polymers of α, β-unsaturated acids and their acid derivatives polyacrylic esters and polymethacrylic esters, polyacrylamide and polyacrylonitrile: Polymer of saturated alcohol and unsaturated amine or its acyl derivative or acetal? vinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polymelamine allyl, and copolymers of the above monomers with other vinyl compounds (e.g. Ethylene-vinyl acetate copolymers): epoxy polymers Homopolymers and copolymers of epoxy compounds (e.g. polyethylene oxide) and polymers of bisglycidyl ether compounds: polyacetals, polyalkylene oxides and polyphenylene oxides polyoxymethylene, oxymethylene-ethylene oxyto copolymers poly Oxyethylene, polyglopylene oxide, priisobutylene oxide and polyphenylene oxide: polyurethanes and polyureas polycarbonates polysulfones polyamides and copolyamides derived from diamines and fatty acids or aromatic dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams Derivative polyamides and copolyamides: e.g. nylon-6, nylon-6/6, nylon 6/1
0. Nylon 11, Nylon 12: Polyesters derived from dicarboxylic acids and dialcohols and/or from oxyacids or their corresponding lactones: For example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane-1,4-dimethylene terephthalate: Crosslinked polymers Crosslinked polymers derived from aldehydes on the one hand and 7-enols, urea or melamine on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins and diaryl phthalate resins: alkyd resins, e.g. glycerol -7 Talic acid resin and its mixture with melamine-formaldehyde resin: an unsaturated polyester resin in which the saturated and unsaturated radicals are derived from coryesters of phosphoric acid and polyhydric alcohols, obtained using vinyl compounds as crosslinking agents. unsaturated polyester resin and its flame-retardant modified material by chlorination.

The amount of stabilizer of the present invention required for effective stabilization of the polymer is:
It depends on various factors, such as the type and nature of the polymer in question, its intended use, and the presence of other stabilizers.

Typically, the stabilizer of the present invention is added at 0.00% based on the weight of the polymer.
It is sufficient to use a weight range of 01 to 5, but the most effective range varies depending on the type of polymer; i.e., olefins,
0 for diene and styrene polymers. Ol~2
．． 0% by weight, preferably 0.02 to 1.0% by weight: 0.0 for vinyl chloride and vinylidene chloride polymers
1 to 1.0% by weight, preferably 0.02 to 0.5% by weight: and for polyurethanes and polyamides 0.01 to 5.0% by weight, preferably 0.02 to 2% by weight.
．． It is 0% by weight. If desired, two or more stabilizers of the present invention can be used together. For example, the stabilizer can be mixed with the polymer in liquid or dry powder form, or a suspension or emulsion of the stabilizer can be mixed with a solution, suspension or emulsion of the polymer. .

The stabilizer for polymers of the present invention can appropriately contain various additives commonly used in the field of polymer technology.

Examples of such additives include the following:

Phenolic antioxidants 2.6-di-t-butyl-p-cresol: Stearyl-β-(4-hydroxy-3,5-X)-t-butylphenyl)propionate; sostearyl (4-hydroxy-3-methyl -5-t-butyl]Hensilma0ne-)
;2,2'-methylenebis(4-methyl-6-t-butylphenol) ;4,4'-methylenebis(2,6
-di-t-butylphenol); 2,2'-methylenebis(6-(1-methylcyclohexyl) p-cresol); bis[3,3-bis(4-hydroxy-3-t-butylphenyl]butyric acid) Glycol ester; 4,4'-butylidene bis(6-t-butyl-m-
cresol); 1,1.3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane;
1,3,5-tris(3,5-not-butyl-4-
hydroxybenzyl)-2,4,6-)limethylbenzene; 3,9-bis[l,1-tmethyl-2-(3,5
-di-t-butyl-4-hydroxyphenyl)ethyl]
-2,4゜8, lO-tetraoxaspiro(5,5]
undecane; tera2kismethylene-3-(3,5-not-butyl-4-hydroxyphenyl)propionate)methane;
-butyl-4-hydroxypennor)in cyanurate and 1,3.5-)lis[3,5-sheet t-butyl-
4-hydroxyphenyl) phlopionyloxyethyl coin cyanurate; bis(3-(3,5-di-1'-
I-4-hydroxyphenyl)f-robionyl]oxamide.

Phosphite stabilizers tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite; tris(nonylphenyl) phosphite; distearylpentaerythritol (diphosphite); 4,4-bunalidene bis(3-
Methyl-6-t-butylphenyl-twotridecyl) phosphite; bis(2,4-di-t-butylphenyl)
Pentaerythritol diphosphite.

UV absorber 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-n-octoxybenzophenone; 2,
4-dihydroxybenzophenone; 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5
10 Lopensotriazole; 2-(2'-hydroxy-
3',5'-di-t-butylphenyl-5-chloropenttriazole;2-(2'-hydroxy-5'-methylphenyl)benzotriazole; 2- (2'-
Hydroxy-3',5'-di-1-amylphenyl)penzotriazole: phenyl salicylate; 2,4-
Di-t-7”terphenyl-3,5-di-t-butyl-
4-Hydroxybenzoate.

Nickel stabilizer Ni-monoethyl-3,5-di-t-butyl-4-hydroxybenzylphos7onate; butylamine-Ni
-2,2'-thiobis(4-t-octylferrate) complex; Ni-dibutyl-dithiocarbamate; Ni-
3,5-di-t-butyl-4-hydroxybenzoate.

Metal salts of fatty acids Calcium, magnesium, barium, zinc.

Cadmium, lead or nickel stearate, calcium, magnesium, cadmium, barium or zinc laurate.

If necessary, it can be used in combination with heavy metal deactivators, nucleating agents, organic tin compounds, plasticizers, epoxy compounds, pigments, fillers, foaming agents, antistatic agents, lubricants, processing aids, and the like.

Glasses stabilized in this way can be used in a wide variety of forms, for example as films, fibers, tapes, compression molding materials, coating compositions or paints.

The present invention is further illustrated in the following Reference Examples and Examples, in which all parts and percentages are by weight.

Reference Example 1 2,2,6,6-titramethyl-4-(butylamino)bilysine 2,2,6,6-tetramethyl-4-piperidone 155
After dissolving I and n-butylamine so, o, y in methanol 300-, platinum oxide 2. Add Og,
The mixture was shaken in a medium-pressure hydrogenation apparatus at room temperature for 5 hours with 3 atm of hydrogen. After the reaction, the platinum catalyst was filtered off and the solvent was distilled off under reduced pressure, followed by purification by distillation to obtain 201.5 g of the target compound as an oil with a boiling point of 100-101° C. and 15 volts of Hg.

Similarly, the following compound was obtained from the corresponding piperidone and an amino compound.

Piridine boiling point 80-83℃ 15■Hg Piperisine boiling point 68-70℃ / 3.5 mgReference example 2 1.3.5-) Lyazine cyanuric chloride 18.49"ff In a solution dissolved in nidioxane 200-, 2, 2,6.6-thitramethyl-4-
A solution of (butylamino)piperidine 43.6.9 dissolved in dioxane 100 was added dropwise at 20-25° C. while stirring. After stirring at the same temperature for 2 hours, add 6
Stir at 0-70°C for 2 hours.

After the reaction was completed, dioxane was distilled off, and the resulting residue was poured into a 10% potassium carbonate water bath and extracted with ethyl acetate. The oily substance obtained by drying with potassium carbonate and distilling off ethyl acetate was subjected to silica dull column chromatography [eluent: ethyl acetate:ethanol:triethylamine (20:1:1
) to obtain the desired product 52.5.9.

Melting point: 40-42℃ Similarly. The following compound was obtained from the corresponding piperidine and cyanuric chloride.

Melting point 126-127°C Melting point 179-188°C Reference example 3 Azine Reference example 2-2-chloro-4,6-bis(N-(2,2,6,6-tetramethyl-4) obtained in (B) -Piperidyl]ethylamino:) -1,3,5-triazine 12.0I, ethanolamine 2.3y and potassium carbonate 2.0y were heated under reflux in dioxane 50 for 5 hours.

After the reaction, dioxane was distilled off under reduced pressure and ethyl acetate was added.
A mixed solvent of water was added and the mixture was shaken. The residue obtained by separating, drying, and concentrating the ethyl acetate was recrystallized from ethyl acetate.
The target object 11.6f1 was obtained as crystals.

Melting point: 184-185°C According to the above method, the following compound was obtained from the reaction of the corresponding chlorotriazine compound with the corresponding amino compound or alcohol compound.

Tetramethyl-4-piperidyl]amino]-6-azine Melting point 157-159 °C Azine melting point 192-193 °C Lyazine melting point 150-152 °C Melting point 127-128 °C Melting point 75 °C Azine melting point 130-132 °C Azine melting point reference example 4 166 -168℃ Ethyl N -(2,4-Sochloro1,3.5-
) 36.9 g of cyanuric chloride, 27.9 F of ethyl glycinate hydrochloride and 33.6 g of sodium bicarbonate were heated under reflux in dioxane 200 for 30 minutes.

After the reaction, dioxane was distilled off under reduced pressure and ethyl acetate was added.
A mixed solvent of water was added and the mixture was shaken. The ethyl acetate layer was separated, dried, and concentrated, and the resulting residue was recrystallized from a mixed solvent of hexane and ethyl acetate to obtain the desired product 45. as crystals. (I got l.

Melting point: 82-87℃ Luprobionate The desired product was obtained according to the method of Reference Example 4.

Melting point 114-119℃ Ethyl N-(2,4-dichloro-
1,3,5-)riazin-6-yl)-glycine)2
．． 36g, 2,2,6.6-titramethyl-4-(butylamino)biyridine obtained in Reference Example 1 (8) 4.191
and 2.779 g of sodium bicarbonate were heated under reflux in 20 mm of xylene for 29 hours. After the reaction was completed, xylene was distilled off under reduced pressure, a mixed solvent of dichloromethane and water was added, and the mixture was shaken. The dichloromethane layer was separated, dried, and concentrated, and the resulting residue was subjected to silica column chromatography [eluent: mixed solvent of hexane dinoethyl ether: ethanol: triethylamine (20:10:1:1)] with K to obtain the desired product. 5.461 was obtained.

Melting point: 40℃ The following compound was obtained according to the method of Reference Example 4(C).

Methyl 2-[N-(2,
4-fuchloro1,3.5-triazin-6-yl]
-Amino-2-methylpropionate and Reference Example 1-(B
The desired product was obtained from 2,2.6.6-titramethyl-4-(ethylamino)piperidine obtained in ) according to the method of Reference Example 4 (C').

Melting point 231-232℃ Hydrochloride 2. '79fi and sodium bicarbonate 3.36
was heated to reflux in dioxane 100°C for 1 hour. After the reaction was completed, dioxane was distilled off under reduced pressure, a mixed solvent of ethyl acetate and water was added, and the mixture was shaken. Residue obtained by separating, drying and concentrating the ethyl acetate layer, 2 and 2 obtained in Reference Example 1-(C)
．． 6.809 g of 6,6-titramethyl-4-(methylamino)piperidine and 3.36 g of sodium bicarbonate were heated under reflux for 4 hours in 100 TIt of xylene. After the reaction was completed, xylene was distilled off under reduced pressure, a mixed solvent of dichloromethane and water was added, and the mixture was photographed. The dichloromethane layer was separated, dried, and the resulting residue was subjected to silica glu column chromatography [eluent: mixed solvent of ethyl acetate: ethanol: triethylamine (15:1:1)] to obtain 8.03 g of the desired product. I got it.

Melting point 140-141°C Lanate cyanuric chloride 3.69g, methyl DL-alanate] Caprolactam 2.26.9 and 35%! 1!2.9 was heated under reflux in methanol 5 for 20 hours. After the reaction is complete,
1.84 I of the residue obtained by distilling off methanol under reduced pressure, 1.84 g of cyanuric chloride, and 1.7 g of sodium hydrogen carbonate were heated under reflux in dioxane for 1 hour.

After the reaction, dioxane was distilled off under reduced pressure and ethyl acetate was added.
A mixed solvent of water was added and the mixture was shaken. The ethyl acetate layer was separated, dried, and concentrated, and the resulting residue was recrystallized from hexane to obtain the desired product 1. I got s OI k.

Melting point: 60-61°C After 7 days, xylene was distilled off under reduced pressure, a mixed solvent of ethyl acetate and water was added, and the mixture was shaken. Separate and dry ethyl acetate N.
The residue obtained by concentration was subjected to silica dull column chromatography [eluent: mixed solvent of ethyl acetate: ethanol: triethylamine (28:l:1)] to obtain the desired product 1.15.
, lil' was obtained.

Melting point 48°C Example 1 Methyl obtained in Reference Example 4 (6) [: 6-N-(2,4
,-dichloro-1,3,5-)riazin-6-yl)-
Reference Example 2.21 g of the 2,2,6,6-tetramethyl-4-butylaminopiperidine obtained in ICA) and 0.91 sodium bicarbonate were mixed in xylene 10 for 20 hours. The mixture was heated to reflux. 2,4-bis[N-ethyl-N-(2,4-bis[N-ethyl-N-(2,
2,6,6-titramethel-4-piperidyl]amino]
-6-(2-hydroxyethoxy) -1゜3.5-)
1.60 g of riazine, 0.22 g of dimethyl succinate
．． 9 to toluene 20m7! First, Zoo-10
Stir at 5°C for 3 hours, distill off the methanol produced,
Then, the mixture was heated to 130° C. and toluene was distilled off. After the reaction was completed, a mixed solvent of ethyl acetate and water was added and the mixture was shaken.

The ethyl acetate layer was separated, dried, and concentrated, and the resulting residue was subjected to silica dull column chromatography [eluent: diethyl ether: ethanol: triethylamine (10:3:1)]
mixed solvent] to obtain 920 mg of the desired product.

Melting point: 85℃ The following compound was obtained according to the above method.

Example 2 Example 4 Minoethyl Succinate (Compound No. 27) Melting point 90°C Example 5 Melting point Example 3 90°C Melting point 70-75°C Example 6 Melting point 80°C Melting point 55-60°C Example 7 Bis[ [2] , 4 Bis[N-butyl-N [N-butyl-N 7 0 ℃ Example 1 Compound No. 5 Melting point 0 ℃ Melting point ℃ Example 1 Example 1 °C ] Example l Melting point °C Example 1 Compound No. 8 Melting point 0 °C No. 6 Example 1 Melting point 0 °C Example 1 No. 58 Melting point °C Melting point °C Example l Example 1 Bis [ [ [ 2,4 Bis] [ N - Butyl-N Amino] 1,3.5 Triazin--yl]-a Melting point °C Melting point °C Example 2 Melting point °C Example 2 Melting point 0 °C Example 2 l Melting point 0 °C Melting point °C Example 2 Example 2 Bis [ [ 2 ,4 Bis[N-methyl-N-2,2,6.6-tetramethyl-1-piberisol)-glycyyl]-ethylenediane (compound number thi-biperidyl)-amino]1,3.5 t] Melting point °C No. l] Implementation Example 2 Melting point l °C Example 2 Product number 2 Melting point °C Number 3 Example 2 Melting point °C Example 3 Product number l Melting point °C Product number 1] Example 2 Melting point l 0 °C Example 3 Bis[N-ethyl-N 2. 2.6.6-Tetramethyhexane-1.6 diolpisu [N [2.4 No. 1l Melting point °C No. 1 Example 3 Melting point °C Example 3 No. 20 ] Melting point °C Product number 1 Example 3 Melting point °C Example 3 Compound No. 1 Melting point 7 °C] (Compound No. 1 l) Example 3 Melting point °C Example 3 Melting point O °C Example 4 Nate] (Compound No. 1 l Melting point °C Example 3 Melting point °C Example 4 No. 15 Melting point °C Implementation Example 3 Melting point °C Example 4 No. 1 No. 107) Melting point 232 °C Example 43 Glycyloxy]ethyl] -4-CN -C2,4-
No. 157) Melting point 218-224°C Example 44 1-Tet2-methylbi(lysine (Compound No. 118) Melting point
135-145°C Example 46 Nate] (Compound No. 126) Melting point 90°C Example 45 Undecane (Compound No. 108) Melting point 130°C Example 47 Chil] -2,4,8,10-tetraoxaspiro[5
, 5) Undecane (Compound No. 35) Melting point 120°C Example 48 Bionate (Compound No. 125) Melting point 264-265°C Example 49 (Compound No. 148) Melting point 58°C Example 50 Unstabilized polypropylene powder (MFR=10- 15)1
00 parts, stearyl 3- (3,5-
0.3 parts of di-tert-butyl-4-hydroxyphenyl)propionate and 0.25 parts of the stabilizer of the invention were homogenized in a Prabender glass decoder at 200 DEG C. for 10 minutes. The resulting mass was rolled into a 2-3 inch thick sheet in a laboratory press. A portion of this sheet was pressed with a hydraulic press at 260° C. for 6 minutes, and then immediately placed in cold water to obtain a sheet with a thickness of 0.5 mm. In the same way, 0
．． A 0.1 m thick film was formed from a 5 mm thick sheet and the film was cut into test pieces of 50 x 120 wm.

The specimen was exposed to light in a sunshine car at a blackboard temperature of 63±3°C. The exposed samples were periodically subjected to a tensile test, and the time for each sample's elongation to drop to 50% of its initial value was defined as the deterioration time. The test results are expressed as the ratio of the deterioration time of the stabilizer of the present invention to the deterioration time of a control sample to which the stabilizer of the present invention was not added.

These results are shown in Table 2. In addition, the compound number represents the compound shown in the above-mentioned compound example.

Exemplary compound number Light resistance (ratio) Example 51 Polypropylene obtained in Example 50 0.5ms+Ji
A 1010x100 test piece was created from the sheet.

The specimens were left open at 150° C. and the number of days until whitening due to embrittlement was determined. These results are shown in Table 3.

Claims (1)

[Claims] 1) A piperidyl-triazine derivative or an acid addition salt thereof having the formula ▲ Numerical formula, chemical formula, table, etc. ▼. In the above formula, R^1 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxyalkyl group having 3 to 22 carbon atoms, an acyl group having 2 to 18 carbon atoms, or an optionally substituted aralkyl group. Group or formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^4 has the same meaning as R^2 described later.) Indicates a group having the following. R^2 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
It represents an acyl group having 2 to 18 carbon atoms or an optionally substituted aralkyl group. X represents an oxygen atom or a group having the formula -NR^5- (wherein R^5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). R^3 represents an alkylene group having 1 to 6 carbon atoms which may be interrupted by an oxygen atom. Y represents a group having the formula -OCO-, a group having the formula -COO-, a group having the formula -CONH-, or a group having the formula -OCONH-. n represents an integer from 2 to 4. When n is 2, Z is an oxygen atom, a sulfur atom, or an alkylene group having 1 to 18 carbon atoms, which may be interrupted by a group having the formula ▲ Numerical formula, chemical formula, table, etc. ▼ Formula ▲ Numerical formula, chemical formula , tables, etc. ▼ Groups having the formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Groups or formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Groups having the (In the above formula, R^6 is a hydrogen atom or represents an alkyl group having 1 to 4 carbon atoms, p represents 1 to 4, and q and are the same or different and represent 0 to 3). When n is 3, Z represents an alkantriyl group having 3 to 8 carbon atoms which may be interrupted by a nitrogen atom. When n is 4, Z represents an alkantetrayl group having 4 to 8 carbon atoms which may be interrupted by an oxygen atom. 2) The compound according to claim 1, wherein R^1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 3) The compound according to claim 1, wherein R^2 is a hydrogen atom or a methyl group. 4) The compound according to claim 1, wherein X is -NH- or -N(CH_3)-. 5) The compound according to claim 1, wherein R^3 is a methylene group or an ethylene group. 6) The compound according to claim 1, wherein Y is a group having the formula -OCO-, a group having the formula -COO-, or a group having the formula -CONH-. 7) The compound according to claim 1, wherein n is 2 and Z is an alkylene group having 2 to 8 carbon atoms. 8) R^1 is an alkyl group having 1 to 4 carbon atoms, and R
The compound according to claim 1, wherein ^2 is a hydrogen atom, X is -NH-, n is 2, and Z is an alkylene group having 2 to 8 carbon atoms. 9) The compound according to claim 8, wherein R^3 is a methylene group and Y is a group having the formula -COO-. 10) The compound according to claim 8, wherein R^3 is an ethylene group and Y is a group having the formula -OCO-.