TW201914993A - Novel triazine compound, composition thereof and preparation method thereof - Google Patents

Abstract

The present invention relates to novel triazine compounds, a process for their production and compositions comprising the compounds. Triazine compounds can be applied to a variety of organic materials to prevent UV damage, such as polyols, plastics, adhesives, coatings, sunscreens, textiles, and pharmaceutical applications. The triazine compounds of the present invention include propionate or propionamide functional groups, and/or polyoxyalkylenes, and/or polyesters, and thus have low extractability, low migration, and high compatibility. The compounds of the present invention may also contain reactive functional groups such as OH, SH, NH, NH2, etc., making the effects of low extractability, low migration, and high compatibility more pronounced.

Description

   Novel triazine compound, composition thereof and preparation method thereof   

The invention relates to a novel triazine compound, a composition composed thereof, a preparation method and application thereof, and belongs to the technical field of chemical materials. The triazine compound of the present invention can be used as an ultraviolet absorbent, and is applied to plastic, rubber, paint, dye, sunscreen, textile, or medicine.

Ultraviolet absorbers are substances that can absorb ultraviolet rays and convert high-energy ultraviolet rays into thermal energy and release them to protect the substances from being damaged by ultraviolet rays. UV absorbers can be used in plastics, rubbers, coatings, dyes, sunscreens, textiles, or drugs. As an ultraviolet absorbent, in addition to absorbing ultraviolet rays, it must also have good stability, high compatibility, low extraction, or low migration. Classified by chemical structure, UV absorbers can be divided into salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines. Many polymer additives, such as triazine UV absorbers, migrate outward from the protected polymer material, reducing its effectiveness. This migration problem is caused by a lack of compatibility between the polymer and the additive.

A triazine ring attached to a hydroxy-substituted aromatic ring is usually based on resorcinol. On such aromatic rings, the p-substituent with triazine is usually an ether. This type of p-alkoxy-o-hydroxyphenyltriazine exhibits poor compatibility. In addition, bondable triazines are known, for example, US 3423360 and US 5189084. These triazines carry double bonds and can be incorporated into polymers by chemical bonding. Although it can achieve low extraction or low migration, it is limited in application. Only applicable to polymerized monomers with double bonds, such as acrylic / ester monomers.

The triazine compound of the present invention has a propionate or propylammonium functional group, and / or a polyoxyalkylene, and / or a polyester. It has high compatibility with liquid materials, for example, it is used in the raw materials of polyurethane such as liquid polyether and polyester polyol. In addition, the compounds of the present invention may have reactive functional groups such as OH, SH, NH, and NH ₂ . Therefore, chemical bonding can occur during the polymerization of the polyurethane. This makes it difficult for the compounds of the present invention to migrate or be extracted from the polyurethane. The compound of the present invention has low extraction, low migration, and high compatibility, and therefore does not cause problems such as blooming. In addition, the operation of liquid antioxidants can also greatly improve convenience.

The compound of the present invention can effectively prevent the degradation of polymers and coatings due to actinic radiation. At present, none of the existing triazine ultraviolet light stabilizers simultaneously has the structural characteristics of the phenyltriazine compound propionate or propionamine of the present invention.

More specifically, the novel triazine of the present invention has the following general formula (I):

Wherein R ₁ is hydrogen or a capping group; R ₂ to R ₁₂ are each independently selected from the group consisting of hydroxyl, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonic, sulfate, phosphate, and phosphine Acid group, unsubstituted or substituted morpholinyl, benzamidine, unsubstituted or substituted straight or branched C _{1 to} C ₁₂ alkyl, C _{1 to} C ₁₂ alkenyl, C _{1 to} C ₁₂ fluorenyl, C _{1 to} C ₁₂ carbonyl, C ₁ to C ₁₂ aryl C ₁ to C ₁₂ heterocyclic group containing nitrogen, oxygen, sulfur, OR ₅ , SR ₅ , SO ₂ R ₅ , SO ₃ R ₅ , COOR ₅ , COR ₅ , OCOR ₅ , C (O) NR ₆ R ₇ , SO ₂ NR ₆ R ₇ or NR ₆ R ₇ , wherein R ₅ , R ₆ , R ₇ are independently selected from hydrogen, phenyl, straight chain or branched C _{1 ~} C ₆ alkyl group is, C _{1 ~} C ₆ alkenyl group, C _{1 ~} C ₆ alkoxy group of; R ₃ ~ R ₇ in R ₃ R ₄ or R ₄ R ₅ or R ₅ R ₆ or R ₆ R ₇ may be combined to form a five- or six-membered ring, R ₈ ~ R ₁₂ in R ₈ R ₉ or R ₉ R ₁₀ or R ₁₀ R ₁₁ or R ₁₁ R ₁₂ groups may be combined to form a five- or six-membered ring; R _{13 is} selected from hydrogen, a bond, a C ₁ to C ₂₀ alkyl group, a divalent C ₂ to C ₄₀ alkyl group interrupted by one or more oxygen, sulfur, or nitrogen, ; R ₁₄ and R ₁₅ are hydrogen or C ₁ ~ C ₁₀ alkyl; m = 0 ~ 100; n = 0 ~ 10; O = 0 ~ 100; p = 0 ~ 5; q = 0 ~ 5; r = 0 ~ 5; A is selected from one bond, H, O, OH, S, SH, NH, NHR ₁₆ , wherein R ₁₆ is hydrogen, C ₁ -C ₁₀ alkyl or

B is selected from a bond, H, O, OH, S, SH, NH, NH ₂ , NHR ₁₆ ; C is selected from a bond, H, O, S, NH, NHR ₁₆ ; D is hydrogen or a capping group or

The capping group is selected from the group consisting of C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ silyl group, C ₁ to C ₁₂ alkyl fluorenyl, and C ₁ to C ₁₂ phenyl fluorenyl. More preferably, the capping group is selected from C ₁ ~ C ₆ alkyl group, C ₁ ~ C ₆ alkyl Si, C ₁ ~ C ₆ alkyl acyl, C ₁ ~ C ₆ acyl phenyl.

Preferably, R _{1 is} selected from hydrogen; R ₂ to R ₁₂ are each independently selected from hydrogen, hydroxyl, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonic, sulfate, phosphate, Phosphonate, unsubstituted or substituted phenyl, morpholinyl, benzamidine, unsubstituted or substituted straight or branched C _1- C ₁₂ alkyl, C _1- C ₁₂ alkenyl, C _{1 ~} C ₁₂ fluorenyl, C _{1 ~} C ₁₂ carbonyl, OR ₅ , SR ₅ , SO ₂ R ₅ , SO ₃ R ₅ , COOR ₅ , COR ₅ , OCOR ₅ , C (O) NR ₆ R ₇ , SO ₂ NR ₆ R ₇ or NR ₆ R ₇ , wherein R ₅ , R ₆ , R ₇ are independently selected from hydrogen, phenyl, unsubstituted or substituted straight or branched C _{1 to} C ₆ alkyl , C _{1 ~} C ₆ alkenyl group of, C _{1 ~} C ₆ alkoxy group of; R ₁₃ is selected from hydrogen, C ₁ ~ C2 ₀ alkyl, interrupted by one or more oxygen, sulfur or nitrogen, or a divalent C ₂ ~ C ₂₀ alkyl, ; R ₁₄ and R ₁₅ are hydrogen or C ₁ ~ C ₆ alkyl; m = 0 ~ 50; n = 0 ~ 18; o = 0 ~ 50; p = 0 ~ 5; q = 0 ~ 5; r = 0 ~ 4; A is selected from O, S, NH; B is selected from one bond, H, O, OH, S, SH, NH, NH ₂ , NHR ₁₆ , where R ₁₆ is

C is selected from one bond, H, O, S, NH, NHR ₁₆ ; D is selected from H, C ₁ to C ₆ alkyl, C ₁ to C ₆ silyl, C ₁ to C ₆ alkylfluorenyl, benzyl醯 基.

More preferably, R ₁ is hydrogen; R ₂ is hydrogen or a linear or branched unsubstituted or substituted C ₁ to C ₁₂ alkyl group; R _{13 is} selected from hydrogen, C ₁ to C ₁₈ alkyl group, Or divalent C ₂ to C ₁₀ alkyl interrupted by oxygen or nitrogen or

m = 0 ~ 20; n = 1 ~ 6; O = 0 ~ 20; p = 0 ~ 3; q = 0 ~ 3; r = 0 ~ 2.

A is selected from O, NH; B is selected from one bond, H, O, OH, NH, NH ₂ , NR ₁₆ , where R ₁₆ is C is O or NH; D is H or C ₁ to C ₆ alkyl.

Particularly preferably, R ₁ is hydrogen; R ₂ is a linear or branched unsubstituted or substituted C ₁ to C ₈ alkyl group; and R ₃ to R ₁₂ are each independently selected from hydrogen, straight chain or branched chain Unsubstituted or substituted C ₁ ~ C ₄ alkyl, C ₁ ~ C ₄ alkoxy, C ₁ ~ C ₄ alkylamino, hydroxyl, halogen; R _{13 is} selected from hydrogen, C ₁ ~ C ₁₈ alkyl , Divalent C ₂ to C ₄ alkyl interrupted by one or more oxygen or nitrogen, ; R ₁₄ and R ₁₅ are hydrogen; A, B, and C are each independently O or NH; D is H or methyl; m = 0 ~ 10; n = 1 ~ 6; o = 0 ~ 10; p = 0 ~ 2; q = 1 ~ 2; r = 1 ~ 2.

Particularly preferably, R ₁ is hydrogen; R ₂ is a linear or branched unsubstituted or substituted C ₁ to C ₆ alkyl group; and R ₃ to R ₁₂ are each independently selected from hydrogen, straight chain or branched chain. Unsubstituted or substituted C ₁ ~ C ₄ alkyl, C ₁ ~ C ₄ methoxy, hydroxyl; R _{13 is} selected from hydrogen, C ₁ ~ C ₈ alkyl, R ₁₄ and R ₁₅ are hydrogen; A and B are each independently O or NH; C is O; D is H; m = 0 ~ 4; n = 1 ~ 5; o = 0 ~ 4; p = 1 ~ 2 ; Q = 1 ~ 2; r = 1 ~ 2. Most preferably, R ₁ is hydrogen; R ₂ is methyl or a linear or branched C ₁ to C ₄ or C ₁ to C ₅ alkyl; R ₃ to R ₁₂ are hydrogen, methyl, or methoxy ; R _{13 is} selected from hydrogen, methyl, R ₁₄ and R ₁₅ are hydrogen; A and B are each independently O or NH; m = 0 ~ 4; n = 1 ~ 5; o = 0 ~ 4; p = 2; q = 2; r = 2.

AR ₃ -B may be a divalent C ₂ -C ₄₀ alkyl group interrupted by oxygen or sulfur or nitrogen. Preferably, AR ₃ -B is a divalent alkyl group interrupted by oxygen. Polyethylene glycol amino polyethylene glycol compounds (CASRN: 32130-27-1) can be prepared from Methoxy PEG (CASRN: 9004-74-4) of various molecular weights and diamines such as ethylenediamine (CASRN: 107-15-3) by reaction (US5846703). Alternatively, it can be prepared from 1,2-Ethanediol homopolymer (CASRN: 25322-68-3) of various molecular weights and p-methylphenylsulfonium chloride and lithium azide (US55858660). Also commercially available, such as compounds (CASRN: 32130-27-1). Other compounds of commercial origin include: 2- (2-aminoethoxy) ethanol (2- (2-Aminoethoxy) ethanol), 2- [2- (2-hydroxyethoxy) ethoxy] ethylamine (2 -[2- (2-Hydroxyethoxy) ethoxy] ethylamine), Tetra-ethylene glycol monoamine, 1-Amino-hexa-ethylene glycol, polyethylene glycol- Polyamino glycol-2-aminoethyl ether has a molecular weight of up to 10,000, or amine polyethoxythiol (HS-PEG-NH2) with a molecular weight of up to 10,000. Among the A-R3-B compounds, another Alkanolamine compound, such as ethanolamine, propanolamine, etc., has a molecular weight of more than 300 from commercial sources. Boc-protected compounds of formula (IV) can be prepared and are also commercially available, for example (CASRN: 159156-95-3).

A composition of the present invention includes: component a: at least one organic material susceptible to oxidation, heat, and / or light-induced degradation, and component b: at least one compound represented by formula (I).

Preferably, the quality of component b is 0.0001% to 10% of the quality of component a. More preferably, in the composition, the quality of component b is 0.01% to 5% of the quality of component a. In the composition, organic materials include polyols, polyurethanes, polyesters, polyamides, polyolefins, polyesters, polyethers, polyketones, natural and synthetic rubbers, polyacrylates, polymethacrylates, polyacetals, Polyacrylonitrile, polybutadiene, acrylonitrile / butadiene / styrene copolymer, styrene / acrylonitrile copolymer, acrylate / styrene / acrylonitrile copolymer, cellulose polymer, polyimide, Polyammonium sulfide imine, polyether sulfide imine, polyphenylene sulfide, polyphenylene ether, polyfluorene, polyether sulfide, polyvinyl chloride, polycarbonate, polyketone, phenol / formaldehyde resin, urea / formaldehyde resin, At least one of an alkyd resin, a urea resin, an epoxy resin, and a polysiloxane.

The compound of the present invention can be synthesized as described below. Path 1:

Among them, Rn substituted benzene is a starting material. The starting material may be of any commercial source, for example, unsubstituted, substituted with one or more hydroxyl, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonic, sulfate, phosphate, or phosphonic acid groups Of benzene. It may also be unsubstituted or substituted alkylbenzene, alkenylbenzene, alkynylbenzene, alkylaminobenzene, alkoxybenzene, alkylfluorenylbenzene, sulfonatebenzene, sulfatebenzene, Sulfonylbenzene, Sulfonylbenzene. Preferably, it may be methylbenzene, methoxybenzene, hydroxybenzene, t-butylbenzene, alkylaminobenzene, m-dimethylbenzene, m-dimethoxybenzene, m-dihydroxybenzene, m-di-t-butyl Benzene, m-dialkylaminobenzene.

R _n substituted 3- (3-tert-butyl-4-hydroxyphenyl) propionate is one of the starting materials. It can be prepared by using 3- (4-hydroxyphenyl) -propionic acid methyl ester as raw material through various Friedel Craft alkylation or halogenation reactions. Or through various nitration, sulfonation, halogenation, hydroxylation, oxidation, reduction, addition, substitution reactions to prepare various R _n substituted 3- (3-tert-butyl-4-hydroxyphenyl) propionate. Preferably, the R _n substituent may be a linear or branched unsubstituted or substituted C ₁ -C ₁₂ alkyl group.

Specifically, melamine and m-dimethylbenzene are added to an inert solvent such as chlorobenzene, and then a Lewis acid is added for reaction. For example, the compound (5) of Example 4 is reacted with the compound (3) to synthesize the compound (7).

Route 2: Performed by Suzuki reaction. For example, compound (8) reacts with compound (4) to synthesize a compound of formula (7).

Among them, cyanuric chloride and dimethylbenzene are added to a passive chlorobenzene solvent to synthesize compound (6) first. Add n-butyl lithium dropwise at -78 ° C and add trimethyl borate, and react at room temperature to obtain compound (8). Compound (8) is subjected to a Suzuki reaction, and potassium carbonate and tetra- (triphenylphosphine) palladium are added to dioxane and heated under the catalyst to obtain compound (7).

Route 3: Compound (III) and AR ₃ -B compound give compound (I) and compound (II), respectively. The dimer (compound (II)) and compound (I) can usually be obtained from unprotected compound (III). Protected compounds of formula (III) give compounds (I).

X is an arbitrary leaving group, and is preferably OR ₁₇ , halogen, or sulfonyl. Wherein R ₁₇ is a C ₁ to C ₁₀ alkoxy group, preferably, R ₁₇ is a methoxy group.

Example 1 Preparation of methyl 3- (3- (tert-butyl) -5-chloro-4-hydroxyphenyl) propanoate (compound 4)

3- (3- (tert-butyl) -4-hydroxyphenyl) propanoic acid methyl ester (compound 3) is an industrial raw material.

Take 50g of methyl 3- (3- (tert-butyl) -4-hydroxyphenyl) propionate, 34g of N-chlorobutanediimide, 200ml of N, N-dimethylformamide, and add them to the reaction bottle in. The temperature was further raised to 65 ° C, and the reaction was performed for 4 hrs. After distillation under reduced pressure, washing with water was carried out to obtain methyl 3- (3- (tert-butyl) -5-chloro-4-hydroxyphenyl) propanoate (compound 4). MS (m / z): 270.1.

Preparation of - (xylyl 2 ', 4') -1,3,5-triazine (Compound 5) Example 2 2-Chloro-4,6-bis

Under nitrogen, 18.7 g of cyanuric acid and 24 g of m-dimethylbenzene were added to the chlorobenzene solvent, and the mixture was stirred at room temperature, and then 35 g of anhydrous aluminum trichloride was added. after silica gel column chromatography to give 2-chloro-4,6-bis (2 ', 4' - dimethylphenyl) -1,3,5-triazine. MS (m / z): 323.1. The coupled form (6H, DD) in H1-NMR indicates that the benzene ring is 2,4 substituted.

Example 3 Preparation of 2-chloro-4,6-bis (p-tert-butylphenyl) -1,3,5-triazine (compound 6)

9.4 g of cyanuric chloride was added to 130 mL of tert-butylbenzene under room temperature nitrogen, and then 10 g of aluminum chloride was added. The reaction mixture is then warmed, HPLC monitoring of the reaction, after the completion of the reaction, was filtered under reduced pressure, after column chromatography over silica gel to give 2-chloro-4,6-bis (2 ', 4' - dimethylphenyl) - 1,3,5-triazine. MS (m / z): 379.2. The coupling type (8H, DD) in H1-NMR indicates that the benzene ring is para-substituted.

Example 4 3- (3- (tert-butyl) -5- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -4- Preparation of hydroxyphenyl) methyl propionate (compound 7)

16g of 2-chloro-4,6-bis (2 ', 4' - phenyl) -1,3,5-triazine (Compound 5), 15g of 3- (3- (tert-butyl) -4- Methyl hydroxyphenyl) propionate (compound 3) was dissolved in 150 mL of chlorobenzene, 10 g of anhydrous aluminum trichloride was added, and the mixture was dissolved by heating and stirring. The temperature was raised to 90 ° C and the reaction was monitored by HPLC. After completion of the reaction, distillation under reduced pressure and silica gel column chromatography gave compound (7). MS (m / z) = 523.3.

Example 5 3- (3- (tert-butyl) -5- (bis (4,6-dimethylphenyl) -1,3,5-triazin-2-yl) -4-hydroxyphenyl) Preparation of isooctyl propionate (compound 9)

52 g of compound 7 was dissolved in toluene. In a flask equipped with a condensate trap, heat to reflux at 110-120 ° C. To the toluene solution were added 50 g of isooctanol and 1.5 g of p-toluenesulfonic acid. During the process, the reaction was monitored by HPLC. When the reaction slowed down, it was concentrated under reduced pressure (transesterification reaction was performed at the same time). After completion of the reaction, the temperature was raised and isooctanol was removed by vacuum distillation to obtain compound 9. MS (m / z): 621.4. In H1-NMR, the chemical shift of 3.6 disappeared (compound 7, -COO- CH3 singlet), and the chemical shift of 0.9 was regenerated (compound 9, -CH2- CH3 triplet).

Example 6 3- (3- (tert-butyl) -5-bis (4,6-dimethylphenyl) -1,3,5-triazin-2-yl) -4-hydroxyphenyl) propane Preparation of octadecyl acid (compound 10)

Compound (10) was prepared in the manner of Example 5. Compound (7) was used as the starting material, but stearyl alcohol was used instead of isooctanol. The product was subjected to silica gel column chromatography to obtain compound 10. MS (m / z) = 761.6.

Example 7 3- (3- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5- (tert-butyl) -4- Preparation of hydroxyphenyl) -N- (2-hydroxyethyl) propanamine (compound 11)

Compound (11) was prepared in the manner of Example 5. 52 g of the compound (7) was dissolved in toluene, and the mixture was heated to reflux at 110 ° C. in a flask equipped with a condensation trap. To the toluene solution was added 10 grams of monoethanolamine. The reaction was monitored by HPLC. After completion of the reaction, vacuum distillation was performed. Wash with water and dry to get compound 11. MS (m / z) = 552.3.

Example 8 3- (3- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5- (tert-butyl) -4- Preparation of hydroxyphenyl) -N- (2- (2-hydroxyethoxy) ethyl) propanamide (compound 12)

The compound of formula (12) was prepared in the same manner as in Example 7 except that 2- (2-aminoethoxy) ethanol was used instead of ethanolamine to obtain compound 12. MS (m / z) = 596.3.

Example 9 3- (3- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5- (tert-butyl) -4- Preparation of hydroxyphenyl) -2-hydroxyethyl propionate (compound 13)

The compound of formula (13) was prepared in the manner of Example 5. 52 g of compound (7) was dissolved in toluene in a flask equipped with a condensate trap, and the mixture was heated to reflux at 110 ° C. To the toluene solution was added 10 grams of ethylene glycol. The reaction was monitored by HPLC. A mixture of compound 13 and compound 20 was obtained by vacuum distillation (Example 18). MS (m / z) = 553.3.

Example 10 3- (3- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5- (tert-butyl) -4- Preparation of 2- (2-hydroxyethoxy) ethyl propanoate (Compound 14)

Compound 14 was prepared in the same manner as in Example 9, but 2- (2-hydroxyethoxy) ethanol was used instead of ethylene glycol to obtain compound 14 and its dimer mixture. MS (m / z) = 597.3 (compound 14).

Example 11 1- (3- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5- (tert-butyl) -4- Preparation of hydroxyphenyl) -3,8,15,22-tetraoxo-7,14,21-trioxo-4-azaheptose-27-yl-6-hydroxyhexanoate (compound 15)

12.1 g of compound (11) was dissolved in toluene, and 11.3 g of caprolactone and 0.018 g of tin monobutyltriisooctanoate catalyst were added dropwise. Under nitrogen at 140 ° C. The polymerization was observed during the reaction, and purified by GPC (colloidal permeation chromatography). The degree of polymerization by H1-NMR chemical shift (- CH2 -CH2-CONH-) 2.7-3.0 (triplet) and the chemical shift 1.6-1.7 (O = C-CH2- CH2 -CH2- CH2 -CH2-O) of hydrogen Conversion of integral area ratio. It is estimated that the degree of polymerization is m = 4. The structure of the obtained compound (15) is as follows.

Example 12 1- (3- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2yl) -5- (tert-butyl) -4-hydroxyl Preparation of phenyl) -3,8,15,22-tetraoxo-4,7,14,21-tetraoxaheptyl-27-yl-6-hydroxyhexanoate (compound 16)

A compound of formula (16) was prepared in the same manner as in Example 11, but a compound of formula (13) was replaced by a compound of formula (13) to obtain a compound of formula (16).

Example 13 Preparation of compound 17

A compound of formula (17) was prepared in the same manner as in Example 11, but a compound of formula (12) was replaced by a compound of formula (12) to obtain a compound of formula (17).

Example 16 Preparation of compound 18

Compound (18) was prepared in the manner of Example 13. However, the compound (14) is used instead of the compound (13) to obtain a compound of the formula (18).

Example 17 3- (3- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5- (tert-butyl) -4- Preparation of hydroxyphenyl) -N, N-bis (2-hydroxyethyl) propanamine (compound 19)

A compound of formula (19) was prepared in the manner described in Example 7 but using bis (2-ethanol) amine instead of ethanolamine. A compound of formula (19) is obtained.

Example 18 1,2-Diyl-bis (3- (3- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5 -(Tert-butyl) -4-hydroxyphenyl) propionate) ethane (compound 20)

Compound (20) was prepared in the manner of Example 5. 52 g of the compound (7) was dissolved in toluene in a flask equipped with a condensing water separator, and heated to reflux at 110 ° C. To the toluene solution were added 56 g of compound (13), and 1.5 g of p-toluenesulfonic acid. The reaction was monitored by HPLC. After the reaction was completed, the compound 20 was obtained by vacuum distillation. The impurities of compound 20 and compound 13 of Example 9 were compared by HPLC, and the retention times were the same.

Example 19 ((oxybis (ethane-2,1-diyl)) bis (oxy)) bis (ethane-2,1-diyl) bis (3- (3- (4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5- (tert-butyl) -4-hydroxyphenyl) propionate) (Compound 21) preparation

Compounds of formula (21) were prepared in the manner of Examples 10 and 11, but PEG200 (molecular weight about 194) was used instead of ethylene glycol. A mixture of the compound (21) and the compound (22) is obtained, and the compound 21 is obtained by silica gel column chromatography.

Methoxy Polyethylene Glycol-350 was used instead of ethylene glycol to obtain the single product of compound (23). After the reaction, it was purified by GPC. Compare the chemical shift of compound (23) for H1-NMR, 2.7-3.0, triplet, (-CH2- CH2 -COO-) and chemical shift 4.1-4.3, triplet, (-COO- CH2 - CH2 -O-). The integral area ratio of the two hydrogens is 1: 1, indicating that the product structure is shown by the compound of formula (23).

Example 20 Capping and Uncapping Tests

Capping: 18 g of compound (12) was added to 100 ml of dimethylformamide and stirred. Then 7 ml of triethylamine and 6 g of trimethylchlorosilane were added. Stir for 60 minutes. After distillation, washing with water, and filtration, H1-NMR (DMSO-d6 ) was measured. The occurrence of a chemical shift of 0.2 (Si (CH ₃ ) ₃ ) indicates that the capping was successful and compound (24) was obtained. Deblocking: After dissolving compound (24) (with or without KF) through a SiOH column, the Si (CH ₃ ) ₃ group can be directly removed. The chemical shift of 0.2 (Si (CH ₃ ) ₃ ) disappears, indicating that the end-capping group has been removed. After removing the end-capping group, it can be used directly as an anti-ultraviolet agent, which has industrial applicability.

Example 21 UV absorption test

150 g of butyl acrylate, 95 g of methyl methacrylate, 15 g of acrylic acid, 7-8 g of UV absorbent (Example 4-20), 6 g of benzoyl peroxide, were mixed in an ethyl acetate / toluene solvent, and added to a reaction kettle After heating to 75 ° C, the reaction was carried out for 2 hours. An additional 6 g of benzamidine peroxide (in a solvent) was slowly added dropwise, the viscosity was monitored, and the reaction was continued for about 6 hours. After the reaction is completed, the temperature is coated on the PET film. The solvent was removed by drying to obtain a blue light-proof film (100 μm) of a blue light-proof agent. The transmittance (UV350nm) was measured, and the results are shown in Table 1.

Example 20: Precipitation test

Polyether polyols are polyurethane raw materials. 2,4-bis- (2,4-dimethylphenyl) -6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine is a control compound (UV 1164 GL ). 50 weight parts of polyether polyol (triol, molecular weight 3000), 2.0 weight parts of water, 0.1 weight part of triethyldiamine, and 1.0 weight part of silicone oil were mixed. Pour into a mixture comprising 0.2 parts by weight of stannous octoate, 50 parts by weight of toluene diisocyanate, 50 parts by weight of a polyether polyol (triol, molecular weight 3000), and 0.15 parts by weight of the example compound or the control compound. After mixing, pour into the box for foaming reaction. Let stand at room temperature for 1 hour and mature in an oven. A 1 gram sample was cut from the polyurethane and placed in a covered glass jar. 100 ml of ethanol was added for extraction, and the concentrated solution was extracted for HPLC analysis. The extraction amount of the control compound was 100%, and the extraction amount of the sample without additives was 0%. The smaller the amount of extraction, the less likely it is to precipitate. The results are summarized in Table 2.

Claims (10)

A triazine compound and a salt thereof are characterized in that the structural formula is represented by formula (I): Wherein R ₁ is hydrogen or a capping group; R ₂ to R ₁₂ are each independently selected from hydrogen, hydroxyl, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonic, sulfate, and phosphate , Phosphonate, unsubstituted or substituted morpholinyl, benzamidine, unsubstituted or substituted straight or branched C _1- C ₁₂ alkyl, C _1- C ₁₂ alkenyl, C _{1 ~} C ₁₂ fluorenyl, C _{1 ~} C ₁₂ carbonyl, C ₁ ~ C ₁₂ aryl, C ₁ ~ C ₁₂ heterocyclic group containing nitrogen, oxygen, sulfur, OR ₅ , SR ₅ , SO ₂ R ₅ , SO ₃ R ₅ , COOR ₅ , COR ₅ , OCOR ₅ , C (O) NR ₆ R ₇ , SO ₂ NR ₆ R ₇ or NR ₆ R ₇ , wherein R ₅ , R ₆ , R ₇ are independently selected from hydrogen and benzene group, an unsubstituted or substituted linear or branched C _{1 ~} C ₆ alkyl group is, C _{1 ~} C ₆ alkenyl group of, C _{1 ~} C ₆ alkoxy group of; R ₃ ~ R ₇ in R ₃ R ₄ or R ₄ R ₅ or R ₅ R _6, or R ₆ R ₇ may be combined to form a five- or six-membered ring, R ₈ ~ R ₁₂ in R ₈ R ₉ or R ₉ R ₁₀ or R ₁₀ R ₁₁ or R ₁₁ R ₁₂ Groups can be combined to form a five or six ring; R _{13 is} selected from hydrogen, a bond, a C ₁ to C ₂₀ alkyl group, a divalent C ₂ to C ₄₀ alkyl group interrupted by one or more oxygen or sulfur or nitrogen, ; R ₁₄ and R ₁₅ are hydrogen or C ₁ ~ C ₁₀ alkyl; m = 0 ~ 100; n = 0 ~ 10; O = 0 ~ 100; p = 0 ~ 5; q = 0 ~ 5; r = 0 ~ 5; A is selected from one bond, H, O, OH, S, SH, NH, NHR ₁₆ , where R ₁₆ is hydrogen, C ₁ ~ C ₁₀ alkyl or B is selected from a bond, H, O, OH, S, SH, NH, NH ₂ , NHR ₁₆ ; C is selected from a bond, H, O, S, NH, NHR ₁₆ ; D is hydrogen, a capping group or Capping group is selected from C ₁ ~ C ₁₂ alkyl group, C ₁ ~ C ₁₂ alkyl Si, C ₁ ~ C ₁₂ acyl group, C ₁ ~ C ₁₂ acyl phenyl. According to claim 1, R _{1 is} selected from hydrogen or a capping group; R ₂ to R ₁₂ are each independently selected from hydrogen, hydroxyl, halogen, amino, nitro, nitroso, cyano, carboxy, sulfonic, and sulfuric acid. Group, phosphate group, phosphonic acid group, unsubstituted or substituted phenyl group, morpholinyl group, benzamidine group, unsubstituted or substituted linear or branched C _{1 ~} C ₁₂ alkyl group, C _{1 ~} C ₁₂ alkenyl, C _{1 ~} C ₁₂ fluorenyl, C _{1 ~} C ₁₂ carbonyl, OR ₅ , SR ₅ , SO ₂ R ₅ , SO ₃ R ₅ , COOR ₅ , COR ₅ , OCOR ₅ , C (O) NR ₆ R ₇ , SO ₂ NR ₆ R ₇ or NR ₆ R ₇ , wherein R ₅ , R ₆ and R ₇ are independently selected from hydrogen, phenyl, unsubstituted or substituted straight or branched C _{1 ~} C ₆ alkyl, C _{1 to} C ₆ alkenyl, C _{1 to} C ₆ alkoxy; R _{13 is} selected from hydrogen, C ₁ to C ₂₀ alkyl, interrupted by one or more oxygen or sulfur or nitrogen Divalent C ₂ ~ C ₂₀ alkyl, ; R ₁₄ and R ₁₅ are hydrogen or C ₁ ~ C ₆ alkyl; m = 0 ~ 50; n = 0 ~ 18; o = 0 ~ 50; p = 0 ~ 5; q = 0 ~ 5; r = 0 ~ 4; A is selected from O, S, NH; B is selected from one bond, H, O, OH, S, SH, NH, NH ₂ , NHR ₁₆ , where R ₁₆ is C is selected from a bond, H, O, S, NH, NHR ₁₆ ; D is H or a capping group; the capping group is selected from C ₁ to C ₆ alkyl, C ₁ to C ₆ silyl, C ₁ to C ₆ alkylfluorenyl, benzamidine. The 3-arylbenzofuranone-propanamine compound according to claim 1, wherein R ₁ is hydrogen; R ₂ is hydrogen or a linear or branched unsubstituted or substituted C ₁ to C ₁₂ R ₃ to R ₁₂ are each independently selected from hydrogen, hydroxyl, halogen, amino, nitro, unsubstituted or substituted phenyl, morpholinyl, benzamidine, unsubstituted or substituted straight C _{1 ~} C ₆ alkyl, C _{1 ~} C ₆ alkenyl, C _{1 ~} C ₆ fluorenyl, C _{1 ~} C ₆ carbonyl, OR ₅ , SR ₅ , SO ₂ R ₅ , SO ₃ R ₅ , COOR ₅ , COR ₅ , OCOR ₅ , C (O) NR ₆ R ₇ , SO ₂ NR ₆ R ₇ or NR ₆ R ₇ , wherein R ₅ , R ₆ , R ₇ are independently selected from hydrogen, phenyl , Unsubstituted or substituted straight or branched C _{1 to} C ₄ alkyl, C _{1 to} C ₄ alkenyl, C _{1 to} C ₄ alkoxy; R _{13 is} selected from hydrogen, C ₁ to C ₁₈ alkyl, divalent C ₂ to C ₁₀ alkyl interrupted by one or more oxygen or nitrogen, or m = 0 ~ 20; n = 1 ~ 6; O = 0 ~ 20; p = 0 ~ 3; q = 0 ~ 3; r = 0 ~ 2. A is selected from O, NH; B is selected from one bond, H, O, OH, NH, NH ₂ , NR ₁₆ , where R ₁₆ is C is O or NH; D is H, C ₁ to C ₆ silane or C ₁ to C ₆ alkyl. The method according to claim 1, characterized in that R ₁ is hydrogen; R ₂ is a linear or branched unsubstituted or substituted C ₁ to C ₈ alkyl group ; and R ₃ to R ₁₂ are each independently selected from hydrogen and hydroxyl. , Halogen, linear or branched unsubstituted or substituted C ₁ ~ C ₄ alkyl, C ₁ ~ C ₄ alkoxy, C ₁ ~ C ₄ alkylamino; R _{13 is} selected from hydrogen, C ₁ ~ C ₁₈ alkyl, divalent C ₂ ~ C ₄ alkyl interrupted by one or more oxygen or nitrogen, or R ₁₄ and R ₁₅ are hydrogen; A, B, and C are each independently O or NH; D is H or methyl; m = 0 ~ 10; n = 1 ~ 6; o = 0 ~ 10; p = 0 ~ 2; q = 1 ~ 2; r = 1 ~ 2. According to any one of claims 1 to 4, characterized in that R ₁ is hydrogen; R ₂ is a linear or branched unsubstituted or substituted C ₁ to C ₅ alkyl group ; and R ₃ to R ₁₂ are each independent Ground is selected from hydrogen, straight chain or branched unsubstituted or substituted C ₁ ~ C ₄ alkyl, methoxy, hydroxyl; R _{13 is} selected from hydrogen, C ₁ ~ C ₁₈ alkyl, R ₁₄ and R ₁₅ are hydrogen; A and B are each independently O or NH; C is O; D is H; m = 0 ~ 4; n = 1 ~ 5; o = 0 ~ 4; p = 1 ~ 2 ; Q = 1 ~ 2; r = 1 ~ 2. A method for preparing a 3-arylbenzofuranone compound (I) according to claim 1, comprising a step of reacting a compound of formula (III) with a compound of formula (IV), wherein, formula (III) ) Compound: R ₁ to R _{13 are the} same as defined in formula (I); X is a leaving group; formula (IV) is: AR ₃ -B , wherein A and B are each independently selected from a protected group or unprotected or protected OH, SH, NH ₂ , NHR ₁₆ , wherein R _{16 is the} same as defined for the compound of formula (I). The method for preparing the compound (III) according to claim 6, wherein the leaving group is OR ₁₇ , halogen, or sulfonyl, and R ₁₇ is a C ₁ to C ₁₀ alkoxy group.     A composition, comprising: component a: at least one organic material susceptible to oxidation, heat, and / or light-induced degradation; and component b: at least one compound represented by formula (I), and the component The quality of b is 0.0001% to 10% of the quality of component a.         The composition according to claim, wherein the quality of component b is 0.01% to 5% of the quality of component a.         The composition according to claim 9, the organic material comprises a polyol, polyurethane, polyester, polyamide, polyolefin, polyester, polyether, polyketone, natural and synthetic rubber, polyacrylate, polymethyl Acrylate, polyacetal, polyacrylonitrile, polybutadiene, acrylonitrile / butadiene / styrene copolymer, styrene / acrylonitrile copolymer, acrylate / styrene / acrylonitrile copolymer, cellulose polymerization Compounds, polyimide, polyimide, imine, polyether, imine, polyphenylene sulfide, polyphenylene ether, polyfluorene, polyether, polyvinyl chloride, polycarbonate, polyketone, phenol / formaldehyde At least one of resin, urea / formaldehyde resin, alkyd resin, urea resin, epoxy resin, and polysiloxane.