KR930005006B1 - Method for preparing glycoluril derivative - Google Patents

Abstract

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Description

[Name of invention]

Method for preparing glycoluril derivative

Detailed description of the invention

2,2,6,6-tetraalkylpiperidine derivatives are known as light stabilizers for organic polymers. The compatibility with polyolefins, the color of the material and the tendency to volatilize during the protective reactions were sometimes unsatisfactory.

The present invention relates to compounds of the general formula (I) and to ammonium salts of these compounds:

Wherein n is 1 to 70, and R ¹ and R ² are each hydrogen, C ₁ -C ₆ -alkyl, C ₇ -C ₁₂ -alalkyl, allyl or carboxyl ester group, or R ¹ and R ² are Together form a tetramethylene or pentamethylene group, R ³ , R ⁴ , R ⁵ and R ⁶ are each alkyl, X are each directly bonded or bridged, Y and Z are each oxygen, sulfur or NR ⁸ , R ⁷ is hydrogen, chlorine, bromine, hydroxyl, alkoxy, carboxyl, carboxyester group or unsubstituted or substituted carbamyl and R ⁸ is hydrogen or unsubstituted or substituted alkyl.

Preferred compounds are those wherein n is 1 to 20, in particular 1.

Specific examples of R ¹ and R ² besides hydrogen include methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl, methylbenzyl, phenyl, toryl, carbomethoxy, carboethoxy, Carbopropoxy and carbobutoxy.

R ¹ and R ² are each preferably ethyl, benzyl, carbomethoxy or carboethoxy, particularly preferably hydrogen, methyl or phenyl.

Examples of alkyl groups R ³ , R ⁴ , R ⁵ , R ⁶ are C ₁ -C ₄ -alkyl, ie methyl, ethyl, propyl or butyl. Furthermore two adjacent groups form tetramethylene or pentamethylene groups.

As R <^3> , R <^4> , R <^5> and R <^6> , methyl is preferable respectively.

Dalimember X is a divalent aliphatic or allyl aliphatic comprising oxygen, nitrogen or sulfur as a hetero atom or having a double or triple bond.

Specific examples include alkylene, cycloalkylene, allalylene, allylene, or allyl group and alkenylene and alkynylene substituted by CO or SO ₂ , each of which may be interrupted by the aforementioned hetero atoms. .

Specific examples of bridge members are as follows.

Where p is 1 to 20 and m is 0 to 4.

Examples of preferred leg members are as follows.

Specifically, is directly bonded or -CH _2- .

In addition to the specific groups described above, examples of R ⁷ groups include

COOH ₃ , COOC ₂ H ₅ , COOC ₃ H ₇ , COOC ₄ H ₉ , COOC ₈ H ₁₇ , CONH ₂ , CONHCH ₃ , CONHC ₂ H ₅ , CONHC ₃ H ₇ , CONHC ₄ H ₉ , CONHC ₆ H ₁₃ , CONHC ₈ H ₁₇ , CON (CH ₃ ) ₂ , CON (C ₂ H ₅ ) ₂ , CON (C ₃ H ₇ ) ₂ , CON (C ₄ H ₉ ) ₂ , CON (C ₆ H ₁₃ ) ₂ , CON (C ₈ H ₁₇ ) ₂ , OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ and C ₄ H ₉ .

As R ⁷ , COOH, CONH ₂ , COOCH ₃ or COOC ₂ H ₅ are preferred, but hydrogen is particularly preferred.

Examples of R ⁸ groups besides hydrogen are C ₁ -C ₄ -alkyl and benzyl.

Tetramethylolacetylenediurea (II) was reacted with 4-amino-2,2,6,6-tetraalkylpiperidine in a manner similar to that described in French Patent 2,291,203 to prepare the compound of formula (I). can do.

See also J. Org. Chem. 50 (1985), the compound of formula (I) in a single container method by reacting glycoluril, formaldehyde and 4-amino-2,2,6,6-tetraylkipiperidine in a similar manner as set forth in 50 (1985), 60 Can be prepared.

When XR ⁷ is hydrogen, the compound of formula (I) is converted to a compound wherein XR ⁷ is CH ₃ by methods commonly shown in the literature, for example, amino reduction reactions.

In addition, the compound of the following formula (III) is converted into a compound of the formula (I) which is not hydrogen of XR ⁷ by a method usually shown in literature such as an alkylation reaction or an acylation reaction.

The compounds according to the invention are in the form of bases or in the form of salts. Examples of suitable anions are derived from inorganic acids and especially from organic carboxylic acids and euphonic acids.

The new compounds have extremely good stability, have no color, and are well matched with organic polymers with low medium pressure.

Examples of inorganic anions are chlorine, bromine, sulfate, methosulfate, tetrafluoroborate, phosphate and thiocyanate.

Examples of carboxylic acids, anions include formate, acetate, propionate, hexanoate, cyclohexanoate, lactate, stearate, dodecylbenzoate, benzoate, acrylate, methacrylate, citrate, Anions of polycarotenic acid containing malate and succinate and up to 3000 COOH.

Examples of sulfonic acid anions are benzenesulfonate and tosylate.

The compounds according to the invention are useful for stabilizing organic substances, in particular plastics, which are decomposed by light and heat. During or before the formation of the polymer, the compound to be stabilized is added to a concentration of 0.01 to 5% by weight, preferably to a concentration of 0.02 to 1% by weight.

The mixing of the plastic and the novel compound to be stabilized can be carried out using conventional apparatus and methods for mixing other additives or stabilizers with the polymer.

Plastics stabilized by one of the new compounds may, if desired, include other additives such as antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, pigments and fillers.

Antioxidants and stabilizers that can be added to the plastics to which the new compounds have been added are, for example, compounds based on sterically obscured phenols or auxiliary stabilizers containing sulfur or phosphorus.

Examples of phenolic antioxidants of this type include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-β- (3,5-di-3-tert-butyl-4-hydroxy Phenyl) -propionate, 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butyltylphenyl) -butane, 1,3,5-trimethyl-2,4,6- Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocy Anurate, 1,3,5-tris- [β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyloxyethyl] isocyanurate, 1,3,4-tris -(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, pentaerythritol tetrakis- [β- (3,5-di-tert-butyl-4- Hydroxyphenyl) -propionate].

Examples of phosphorus-containing antioxidants include tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphate, tris- (2,4-di-tert-butylphenyl) phosphite, tris- (2- Tert-l-butyl-4-methylphenyl) phosphite, bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphate, tetrakis- (2,4-di-tert-butylphenyl ), 4,4'-diphenylene diphosphate, and the like.

Examples of sulfur-containing sulfating agents include dilaurylthiodipropionate, dimyristyl thiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis- (β-laurylthio-propionate), pentaene Rititolitol tetrakis- (β-hexylthiopropionate), and the like.

Other antioxidants and light stabilizers that may be used with the novel compounds include, for example, 2- (2'-hydroxyphenyl) -benzotriazole, 2-hydroxybenzophenone, hydroxybenzoic acid allyl ester, α-cyanosi Namsan derivatives, nickel compounds and oxalic acid dianilide.

Examples of organic polymers that can be stabilized using novel compounds include mono and diolefins such as low or high density polyethylene, linear low density polyethylene, polypropylene, polyisobutylene, 1-butene polymer, polyisoprene or polybutadiene. Copolymers of polymers and mono- or diolefins or mixtures of such polymers; Copolymers of mono- or diolefins with other vinyl monomers such as ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinylacetate copolymers or ethyle / acrylic acid copolymers; Polystyrene; Styrene / butadiene, styrene / acrylonitrile, styrene / ethylmethacrylate, styrene / butadiene / ethylacrylate or styrene / acrylonitrile / methacrylate or copolymers of α-methyl styrene with diene or acrylyl derivatives ; ABS, MBS and similar polymers; Halogen-containing polymers such as vinyl chloride polymer, vinyl fluoride polymer, vinylidene fluoride polymer and copolymers thereof; Polymers derived from α, β-unsaturated acids such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles and derivatives thereof; Polymers derived from unsaturated alcohols and amines such as polyvinyl alcohol or polyvinylacetate and acrylyl derivatives or acetals thereof; Polyurethanes, nylons, polyureas, polyesters, polycarbonate polysulfones, polyethersulfones and polyetherketones.

Another organic polymer that can be stabilized with the compound according to the invention is an industrial coating. Of particular note is a heated finish that includes automotive finishes and a double clad finish is preferred.

In addition, the antioxidant and light stabilizer shown above were added and used.

The solid compound according to the invention can be added to the coating in solid or dissolved form, while the liquid compound according to the invention can be added as it is. Good solubility in coating systems is particularly advantageous.

As the novel compounds, polyolefins are preferably used, with ethylene and propylene polymers being preferred.

Of particular importance are compounds of the general formula (Ia):

Wherein R is hydrogen, methyl, ethyl, propyl, butyl, allyl, hydroxymethyl, acetyl, benzoyl or benzyl.

Example 1a

15.6 g (0.1) mole of 4-amino-2,2,6,6-tetramethyl pyreridine and 13.1 g (0.05) mole of tetramethylolacetylenediurea are added to 100 ml of n-butanol and the mixture is Reflux for time. The solvent was blown off to give 23.2 g (92%) of a colorless solid with a melting point of 250-252 ° C.

Calculated Value: C; 62.2, H; 9.2, N; 22.3

Found: C; 62.6, H; 9.1, N; 21.7

Water was added to boil to remove impurities, and then the melting point was increased to 280-283 ° C.

Example 1b

65.7 kg of 4-amino-2,2,6,6-tetramethylpyridine and 104.8 kg of tetramethylolacetylenediurea 50% aqueous solution are added to 300 water. The mixture is heated at 80-90 ° C. for 2 hours and left to cool at room temperature, the product is filtered under reduced pressure, washed with water and dried under reduced pressure. 89.5 kg (90%) of a colorless solid with a melting point of 280-283 ° C was obtained.

Calculated Value: C; 62.2, H; 9.2, N; 22.3

Found: C; 62.6, H; 9.4, N; 22.3

Example 1c

25 ml of 56.8 g (0.4 mole) of acetylenediurea, 160 g (1.6 mole) of 30% aqueous formaldehyde solution and 124.8 g (0.8 mole) of 4-amino-2,2,6,6-tetramethylpyridine In water and heated at 90-95 ° C. for 2 hours. After cooling the mixture, the product was filtered under reduced pressure, washed with water and dried to give 186.9 g (93%) of a colorless solid.

Melting point and IR and elemental analysis are the same as the product of Example 1a.

Example 2

26.2 g (0.05 mole) of 50% tetramethylolacetylenediurea aqueous solution was added to 17.0 g (0.1 mole) of 4-amino-1,2,2,6,6-pentamethylpyridine, dissolved in 200 ml water. And the mixture is kept at 80 ° C. for 2 hours. The mixture was filtered under reduced pressure at room temperature to give 23.8 g (90%) of colorless crystals having a melting point of 257-261 占 폚. Purification by recrystallization from ethanol.

Calculated Value: C; 63.4, H; 9.4, O; 6.0, N; 21.1

Found: C; 63.1, H; 9.4, O; 6.0, N; 21.1

Example 3

4.95 g (0.019 mol) of tetramethylolacetylenediurea and about 70% of 4-amino-1-benzyl-2,2,6,6-tetramethylpyriridine in n-butanol (0.057 mol) Was refluxed for 6.5 h. The precipitate that precipitated was filtered under reduced pressure at room temperature, washed with n-butanol and recrystallized with ethanol. The dibenzyl compound was separated into colorless crystals having a melting point of 283 ° C.

Calculated Value: C; 70.4, H; 8.5, O; 4.7, N; 16.4

Found: C; 70.1, H; 8.5, O; 4.8, N; 16.5

Example 4

25 g (0.05 mole) of the product obtained in Example 1 and 4.08 g (0.4 mole) of acetic anhydride are boiled in 200 ml xylene for 5 hours. Precipitated precipitate is filtered under reduced pressure at room temperature, dried and dissolved in water. The aqueous solution is made alkaline with sodium hydroxide solution, filtered under reduced pressure, dried and recrystallized with isopropanol. The diacetyl compound was obtained as a colorless solid with a melting point of 280 ° C.

Calculated Value: C; 61.4, H; 8.5, O; 10.9, N; 19.1

Found: C; 61.1, H; 8.7, O; 11.1, N; 19.2

Example 5

8.5 g (0.50 mmol) of 1,5-dimethyl-2,4,6,8-tetraazabicyclo [3.3.0] octane-3,7-dione, 20 ml of 30% aqueous formaldehyde solution in 200 ml of isopropanol and Boil 15.5 g (100 mmol) 4-amino-2,2,6,6-tetramethylpiperidine for 7 hours. Blow off the solvent, boil the residue in water. After recrystallization with ethylene glycol dimethyl ether, the product of colorless crystals having a melting point of 279-281 占 폚 was separated.

Calculated Value: C; 63.4, H; 9.4, O; 6.0, N; 21.1

Found: C; 63.2, H; 9.4, O; 6.4, N; 21.1

Example 6

16.0 g (0.08 mol) of 1,5-dimethyl-2,4,6,8-tetraazabicyclo [3.3.0] octane-3-thione-7-one, 32 ml of 30% formaldehyde solution in 200 ml isopropanol And 24.8 g (0.16 mole) of 4-amino-2,2,6,6-tetramethylpiperidine are heated at the boiling point for 7 hours. The solvent is blown off and the residue is suspended in water and the product is filtered under reduced pressure and dried and then recrystallized from ethylene glycol dimethyl ether. The product was isolated as a colorless solid with a melting point of 243-245 ° C.

Calculated Value: C; 61.5, H; 9.2, O; 2.9, N; 20.5, S; 5.9

Found: C; 61.3, H; 9.4, O; 3.1, N; 20.4, S; 6.0

Example 7

14.7 g (0.05 mole) of 1,5-diphenyl-2,4,6,8-tetraazabicyclo [3.3.0] octane-3,7-dione, 20 ml in 200 ml of isopropanol and 150 ml of dimethyl sulfoxide 30% formaldehyde solution and 15.5 g (0.1 mol) of 4-amino-2,2,6,6-tetramethylpyriridine are heated at the boiling point for 7 hours. The product is filtered under reduced pressure at room temperature, stirred in 250 ml of dichloromethane and filtered under reduced pressure again. 23.2 g (71%) of a product having a melting point of 310 ° C. or more as a colorless solid was obtained.

Calculated Value: C; 69.7, H; 8.2, O; 4.9, N; 17.1

Found: C; 69.5, H; 8.3, O; 5.0, N; 17.1

Example 8

16.3 g (0.05 mole) of 1,5-diphenyl-2,4,6,8-tetraazabicyclo [3.3.0] octane-3,7-dithion, 30% of 20 ml in 150 ml of dimethyl sulfoxide The aqueous formaldehyde solution and 15.5 g (0.1 mol) of 4-amino-2,2,6,6-tetramethylpiperidine are heated at 80 ° C. for 7 hours and at 150 ° C. for 10 hours. The product is filtered under reduced pressure at room temperature and washed with water. A compound was obtained which was colorless and had a melting point of 255-256 ° C.

Calculated Value: C; 66.5, H; 7.9, N; 16.3, S; 9.3

Found: C; 66.5, H; 7.8, N; 16.0, S; 9.1

Example 9

A salt of the compound of Example 1 with 1 mole of adipic acid.

5.0 g of the product of Example 1 and 1.64 g of adipic acid were dissolved in 150 ml of methanol and evaporated to dryness to obtain a salt, and crystallized from 2 moles of methanol to give a compound as a colorless solid having a melting point of 230-232 ° C. Got it.

Example 10

A salt of the compound of Example 1 and 2 moles of 2,5-dimethylfuran-3-carboxylic acid.

5.0 g of the product of Example 1 and 2.78 g of 2,5-dimethylfuran-3-carboxylic acid are reacted similarly to Example 9. A salt crystallized from 2 moles of methanol was obtained as a colorless solid with a melting point of 258-260 ° C.

Calculated Value: C; 59.6, H; 8.3, O; 18.9, N; 13.2

Found: C; 59.6, H; 8.34, O; 18.0, N; 13.7

Example 11

A salt of the compound of Example 1 and two moles of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid.

5 g of the product of Example 1 and 5.7 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid are reacted similarly to Example 9. Salts crystallized from 4 moles of methanol obtained a colorless solid with a melting point of 208-210 占 폚.

Calculated Value: C; 64.7, H; 9.4, O; 16.1, N; 9.4

Found: C; 64.4, H; 9.4, O; 15.9, N; 9.8

[Examples]

1. Stability of polyethylene when using the compound of Example 1.

a) 0.25 parts of the compound obtained in Example 1 were extruded twice at 180 ° C., mixed with 100 parts of low density polyethylene (1840D manufactured by BASF), and pressed to form a polyethylene 200 μm thick plate. After storage for 14 days in the dark at 25 ° C., the surface of the plate was uncoated.

b) Weathering stability of the plates produced as presented in a) was tested with a QUV accelerated weathering tester. Aging was determined by measuring the CO number after a certain time interval. Softens when CO is 10 The test results are summarized in Table 1.

Samples containing compounds from Examples 1 and 2 and stabilizers of Formula (IV) were prepared similarly to Example 1a) and tested similarly to Example 1b). The results are summarized in Table 1.

TABLE 1

CO water (polyethylene) exposed to weathering test equipment by QUV

2. Stability of polypropylene.

a) 0.25 parts of a compound of a suitable example were extruded twice at 220 ° C., mixed with 100 parts of polypropylene (1320H from BASF), and the polypropylene was pressed to obtain a 200 μm thick plate. After storage for 14 days in the dark at 25 ° C., the surface of the plate was uncoated.

b) Weathering stability of the plates produced as presented in a) was tested with a QUV accelerated weathering tester. Aging was determined by measuring the CO number after a certain time interval. The onset of softening was determined mechanically. The test results are summarized in Table 2.

TABLE 2

CO water exposed with QUV accelerated weathering tester (polypropylene)

Claims (10)

A compound of formula (I) obtained by reacting a compound of formula (II) with a 4-amino-2,2,6,6-tetraalkylpyriridine compound of formula (III) and an ammonium salt thereof:

Wherein n is 1 to 70, and R ¹ and R ² are each hydrogen, —C ₁ -C ₆ -alkyl, C ₇ -C ₁₂ -alalkyl, alkyl or carboxyl ester group, or R ¹ and R ² Together form a tetramethylene or pentamethylene group, R ³ , R ⁴ , R ⁵ and R ⁶ are each alkyl, X groups are each directly bonded or bridged, Y and Z are each oxygen, sulfur or NR ⁸ And R ⁷ is hydrogen, chlorine, bromine, hydroxyl, alkoxy, carboxyl, carboxyester group or unsubstituted or substituted alkyl and R ⁸ is hydrogen or unsubstituted or substituted alkyl. The method of claim 1 wherein n is 1-20. The method of claim 1 wherein n is one. The method of claim 1 wherein R ¹ and R ² are each hydrogen. The method of claim 3 wherein R ¹ and R ² are each hydrogen. The method of claim 3, wherein R ¹ or R ² is methyl or phenyl or R ¹ and R ² are methyl or phenyl, respectively. The method of claim 3 wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each CH ₃ and XR ⁷ is hydrogen. The method of claim ³ , wherein R ³ , R ⁴ , R ⁵ and R ⁶ and XR ⁷ are each CH ₃ . The method of claim 1, wherein the compound of formula (I) is of the following formula (Ia):

Wherein B ¹ and B ² are each hydrogen, methyl or phenyl and R is hydrogen, methyl, ethyl, propyl, butyl, allyl, hydroxymethyl, acetyl, benzoyl or benzyl. 10. The method of claim 9, wherein R is hydrogen or methyl.