WO2019072202A1 - Novel triazine compound, composition thereof, and preparation method therefor - Google Patents

Abstract

Disclosed in the present invention are a novel triazine compound, a preparation method therefor, and a composition comprising said compound. The triazine compound can be used in a variety of organic materials to prevent UV damage, such as polyols, plastics, adhesives, coatings, sunscreen, textiles, and pharmaceutical applications. The triazine compound of the present invention comprises propionate or a propionamide functional group, and/or polyoxyalkylene, and/or polyester, and therefore has low extraction performance, low mobility, and high compatibility. The compound of the present invention may also comprise a reactive functional group such as OH, SH, NH, and NH2, so that the low extraction performance, low mobility, and high compatibility effects are more pronounced.

Description

Novel triazine compound, composition thereof and preparation method thereof Technical field

The invention relates to a novel triazine compound, a composition thereof, a preparation method and application thereof, and belongs to the technical field of chemical materials. The triazine compounds of the present invention are useful as ultraviolet absorbers for plastics, rubbers, coatings, dyes, sunscreens, textiles, or pharmaceuticals.

Background technique

Ultraviolet absorbers are substances that absorb ultraviolet light and convert high-energy ultraviolet rays into heat energy to release them to protect them from ultraviolet light. UV absorbers can be applied to plastics, rubber, paints, dyes, sunscreens, textiles, or pharmaceuticals. As the ultraviolet absorber, in addition to absorbing ultraviolet rays, it is necessary to have good stability, high compatibility, low extraction property, or low migration property. According to the chemical structure classification, the ultraviolet absorber can be classified into salicylate, benzophenone, benzotriazole, substituted acrylonitrile, triazine and the like. Many polymeric additives, such as triazine-based ultraviolet light absorbers, migrate outward from the protected polymeric material, thereby reducing its effectiveness. This migration problem is caused by a lack of compatibility between the polymer and the additive.

The triazine ring-linked hydroxy-substituted aromatic ring is usually based on resorcinol. On such aromatic rings, the para-substituents with the triazine are typically ethers. This type of p-alkoxy ortho-hydroxyphenyltriazine exhibits poor compatibility. In addition, bondable triazines are known, for example, from US 3,423,360 and US 5,189,084. These triazines have a double bond and can be incorporated into the polymer by chemical bonding. Although low extraction or low migration effects can be achieved, they are limited in application. It can only be applied to polymerized monomers which also have double bonds, such as acrylic acid/ester monomers.

Detailed ways

The triazine compound of the present invention has a propionate or propionamide functional group, and/or a polyoxyalkylene, and/or a polyester. It has high compatibility with liquid materials, such as raw materials for polyurethanes such as liquid polyethers and polyester polyols. Further, the compound of the present invention may have a reactive functional group such as OH, SH, NH, NH ₂ or the like. Therefore, chemical bonding can occur during the polymerization of the polyurethane. The compounds of the invention are not readily migrated or extracted from the polyurethane. The compound of the present invention has low extraction, low migration, and high compatibility, and thus does not cause problems such as blooming. In addition, the liquid antioxidant can greatly improve the convenience in operation.

The compounds of the present invention are effective in preventing degradation of polymers and coatings due to actinic radiation. At present, there is no existing triazine ultraviolet light stabilizer having the structural characteristics of the benzene triazine compound propionate or propionamide 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 blocking group; and R ₂ to R ₁₂ are each independently selected from the group consisting of a hydroxyl group, a halogen, an amino group, a nitro group, a nitroso group, a cyano group, a carboxyl group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, and a phosphine group. Acidic, unsubstituted or substituted morpholinyl, benzoyl, unsubstituted or substituted straight or branched C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkenyl, C ₁ -C ₁₂ Acyl group, C ₁ -C ₁₂ carbonyl group, C ₁ -C ₁₂ aryl group, C ₁ -C ₁₂ nitrogen group, heterocyclic group of 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, linear Or a branched C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkenyl group, a C ₁ -C ₆ alkoxy group; R ₃ -R ₇ 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 ring; R _{13 is} selected from the group consisting of hydrogen, a bond, a C ₁ -C ₂₀ alkyl group, a divalent C ₂ -C ₄₀ alkyl group interrupted by one or more oxygen or sulfur or nitrogen,

R ₁₄ and R ₁₅ are hydrogen or a C ₁ -C ₁₀ alkyl group;

m=0～100;

n=0~10;

O=0～100;

p=0~5;

q=0~5;

r=0~5;

A is selected from the group consisting of a bond, H, O, OH, S, SH, NH, NHR ₁₆ , wherein

R ₁₆ is hydrogen, C ₁ -C ₁₀ alkyl or

B is selected from the group consisting of a bond, H, O, OH, S, SH, NH, NH ₂ , NHR ₁₆ ;

C is selected from the group consisting of a bond, H, O, S, NH, NHR ₁₆ ;

D is hydrogen or a terminal group or

Wherein the blocking group is selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ silane, C ₁ -C ₁₂ alkyl acyl, C ₁ -C ₁₂ benzoyl, more preferably, the blocking group is selected from C ₁ a C ₆ alkyl group, a C ₁ -C ₆ silyl group, a C ₁ -C ₆ alkyl group, or a C ₁ -C ₆ benzoyl group.

Preferably, R _{1 is} selected from hydrogen; R ₂ to R ₁₂ are each independently selected from the group consisting of hydrogen, hydroxy, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonate, sulfate, phosphate, Phosphonic acid group, unsubstituted or substituted phenyl group, morpholinyl group, benzoyl group, unsubstituted or substituted straight or branched C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkenyl group, C ₁ to C ₁₂ acyl group, C ₁ -C ₁₂ carbonyl group, 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 of each other selected from hydrogen, phenyl, unsubstituted or substituted straight or branched C ₁ -C ₆ alkyl, C ₁ to C ₆ alkenyl group, C ₁ -C ₆ alkoxy group; R _{13 is} selected from hydrogen, C ₁ -C ₂₀ alkyl group, divalent C ₂ -C interrupted by one or more oxygen or sulfur or nitrogen ₂₀ alkyl,

R ₁₄ and R ₁₅ are hydrogen or a C ₁ -C ₆ alkyl group;

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 the group consisting of a bond, H, O, OH, S, SH, NH, NH ₂ , NHR ₁₆ , wherein R ₁₆ is

C is selected from the group consisting of a bond, H, O, S, NH, NHR ₁₆ ;

D is selected from H, C ₁ -C ₆ alkyl, C ₁ -C ₆ silyl, C ₁ -C ₆ alkyl acyl, benzoyl. More preferably, R ₁ is hydrogen; R ₂ is hydrogen or a linear or branched unsubstituted or substituted C ₁ -C ₁₂ alkyl group; R _{13 is} selected from hydrogen, C ₁ -C ₁₈ alkyl, Or a plurality of divalent C ₂ -C ₁₀ alkyl groups interrupted by oxygen or nitrogen or

m=0~20;

n=1～6;

O=0~20;

p=0~3;

q=0~3;

r = 0 to 2.

A is selected from O, NH;

B is selected from the group consisting of a bond, H, O, OH, NH, NH ₂ , NR ₁₆ , wherein R ₁₆ is

C is O or NH;

D is H or a C ₁ -C ₆ alkyl group.

More preferably, R ₁ is hydrogen; R ₂ is a linear or branched unsubstituted or substituted C ₁ -C ₈ alkyl group; and R ₃ to R ₁₂ are each independently selected from hydrogen, straight or branched. Unsubstituted or substituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylamino, hydroxy, halogen; R _{13 is} selected from hydrogen, C ₁ -C ₁₈ alkyl a divalent C ₂ -C ₄ alkyl group 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 methylalkyl; m = 0 to 10; n = 1 to 6; o = 0 to 10; p = 0 to 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 -C ₆ alkyl group; and R ₃ to R ₁₂ are each independently selected from hydrogen, straight or branched. Unsubstituted or substituted C ₁ -C ₄ alkyl, C ₁ -C ₄ methoxy, hydroxy; 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 to 4; n = 1 to 5; o = 0 to 4; p = 1 to 2; q=1～2; r=1～2. Most preferably, R ₁ is hydrogen; R ₂ is methyl or a linear or branched C ₁ -C ₄ or C ₁ -C ₅ alkyl group; R ₃ -R ₁₂ are hydrogen, methyl or methoxy ; R _{13 is} selected from the group consisting of hydrogen, methyl,

R ₁₄ and R ₁₅ are hydrogen; A and B are each independently O or NH; m = 0 to 4; n = 1 to 5; o = 0 to 4; p = 2; q = 2;

A-R ₃ -B may be a divalent C ₂ -C ₄₀ alkyl group interrupted by oxygen or sulfur or nitrogen. Preferably, A-R ₃ -B is a divalent alkyl group interrupted by oxygen. For example, polyethylene glycol amino polyethylene glycol compound

(CASRN: 32130-27-1) can be prepared by reacting various molecular weights of Methoxy PEG (CASRN: 9004-74-4) with diamines such as ethylenediamine (CASRN: 107-15-3) (US5846703) . Alternatively, it can be obtained by reacting various molecular weights of 1,2-Ethanediol homopolymer (CASRN: 25322-68-3) with p-methylphenylsulfonyl chloride and lithium azide (US55858660). Also commercially available, such as compounds

(CASRN: 32130-27-1). Other commercially available compounds include: 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- Polyethylene glycol-2-aminoethyl ether has a molecular weight of up to 10,000, or an amine polyethoxy thiol (HS-PEG-NH2) with a molecular weight of up to 10,000. Another Alkanolamine compound in the A-R3-B compound, such as ethanolamine, propanolamine, etc., has a commercially available compound having a molecular weight of up to 300 or more. The Boc protected compound of formula (IV) can be obtained or commercially available, for example.

(CASRN: 159156-95-3).

A composition of the invention comprising:

Component a: at least one organic material susceptible to oxidative, thermal and/or photoinduced degradation, and

Component b: at least one compound of the formula (I).

Preferably, the mass of component b is from 0.0001% to 10% by mass of component a. More preferably, the composition wherein the mass of component b is from 0.01% to 5% by mass of component a. In the composition, the organic material includes polyol, polyurethane, polyester, polyamide, polyolefin, polyester, polyether, polyketone, natural and synthetic rubber, polyacrylate, polymethacrylate, polyacetal, poly Acrylonitrile, polybutadiene, acrylonitrile/butadiene/styrene copolymer, styrene/acrylonitrile copolymer, acrylate/styrene/acrylonitrile copolymer, cellulose polymer, polyimide, poly Amide imide, polyetherimide, polyphenylene sulfide, polyphenylene ether, polysulfone, polyethersulfone, polyvinyl chloride, polycarbonate, polyketone, phenol/formaldehyde resin, urea/formaldehyde resin, alkyd At least one of a resin, a urea resin, an epoxy resin, and a polysiloxane.

The compound of the present invention can be synthesized in the following manner. Path 1:

Among them, Rn substituted benzene is the starting material. The starting material may be of any commercial origin, for example, unsubstituted, one or more hydroxyl, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonate, sulfate, phosphate, phosphonic acid groups Benzene. Also commercially available as unsubstituted or substituted alkylbenzenes, alkenylbenzenes, alkynylbenzenes, alkylaminobenzenes, alkoxybenzenes, alkyl acylbenzenes, sulfonate benzenes, sulfated benzenes, sulfonamides Benzobenzene, sulfonylbenzene. Preferably, it may be methylbenzene, methoxybenzene, hydroxybenzene, tert-butylbenzene, alkylaminobenzene, m-dimethylbenzene, m-dimethoxybenzene, m-dihydroxybenzene, m-tert-butyl Alkylbenzene, m-dialkylaminobenzene.

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

Specifically, cyanuric chloride, m-dimethylbenzene is added to a blunt solvent such as chlorobenzene, and then Lewis acid is added to carry out the reaction. For example, the compound (5) of Example 4 is reacted with the compound (3) to synthesize the compound (7).

Path 2: carried out in a Suzuki reaction. For example, compound (8) is reacted 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 the compound (6). n-Butyllithium was added dropwise at -78 ° C and trimethyl borate was added thereto, and the mixture was reacted at room temperature to obtain a compound (8). The compound (8) is subjected to a Suzuki reaction, and heating is carried out by adding potassium carbonate and tetrakis-(triphenylphosphine)palladium to dioxane to obtain a compound (7).

Path 3: Compound (III) and AR ₃ -B compound give Compound (I) and Compound (II), respectively. The unprotected compound (III) usually gives a mixture of a dimer (compound (II)) and a compound (I). Compound (I) can be obtained by protecting the compound of formula (III).

X is an arbitrary leaving group, preferably OR ₁₇ , halogen or sulfonyl. Wherein R ₁₇ is a C ₁ -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)

Methyl 3-(3-(tert-butyl)-4-hydroxyphenyl)propanoate (Compound 3) is an industrial raw material.

Take 50 g of methyl 3-(3-(tert-butyl)-4-hydroxyphenyl)propanoate, 34 g of N-chlorosuccinimide, 200 ml of N,N-dimethylformamide, and add to the reaction flask. . The temperature was raised to 65 ° C and the reaction was carried out for 4 hrs. After distillation under reduced pressure, it was washed with water to give methyl 3-(3-(tert-butyl)-5-chloro-4-hydroxyphenyl)propanoate (Compound 4). MS (m/z): 270.1.

Example 2.

Preparation of 2-chloro-4,6-bis(2',4'-dimethylphenyl)-1,3,5-triazine (Compound 5)

Under nitrogen, 18.7g of cyanuric chloride and 24g of m-dimethylbenzene were added to the chlorobenzene solvent, stirred at room temperature, and then anhydrous 35 ml of aluminum trichloride was added. The reaction was monitored by HPLC, and the reaction was concentrated and concentrated under reduced pressure. After silica gel column chromatography, 2-chloro-4,6-bis(2',4'-dimethylphenyl)-1,3,5-triazine was obtained. MS (m/z): 323.1. The coupled form (6H, DD) in H1-NMR indicates that the benzene ring is a 2,4 substitution.

Example 3.

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

9.4 g of cyanuric chloride was added to 130 mL of t-butylbenzene under nitrogen at room temperature, followed by the addition of 10 g of aluminum chloride. The reaction was mixed, then the temperature was raised, and the reaction was monitored by HPLC. After completion of the reaction, the mixture was filtered under reduced pressure and purified to silica gel column to give 2-chloro-4,6-di(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 a para-substitution.

Example 4.

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

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

Example 5.

3-(3-(tert-butyl)-5-(bis(4,6-dimethylphenyl)-1,3,5-triazin-2-yl)-4-hydroxyphenyl)propanoic acid Preparation of octyl ester (compound 9)

52 g of compound 7 was dissolved in toluene. The flask equipped with the condensate trap was heated 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 course, the reaction was monitored by HPLC. After the reaction was slowed down, it was concentrated under reduced pressure (simultaneously, transesterification). After completion of the reaction, the temperature was raised and isooctyl alcohol was removed by vacuum distillation to obtain Compound 9. MS (m/z): 621.4. The chemical shift 3.6 disappeared in H1-NMR (Compound 7, -COO- CH3 singlet) and the chemical shift was 0.9 nascent (Compound 9, -CH2- CH3 triplet).

Example 6.

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

Compound (10) was prepared in the same manner as in Example 5. Compound (7) was used as a starting material, but hexyl alcohol was replaced by stearyl alcohol. The product was subjected to silica gel column chromatography to give 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-hydroxyphenyl Preparation of -N-(2-hydroxyethyl)propanamide (Compound 11)

Compound (11) was prepared in the same manner as in Example 5. 52 g of the compound (7) was dissolved in toluene, and heated under reflux at 110 ° C in a flask equipped with a condensed water separator. To the toluene solution was added 10 g of monoethanolamine. The reaction was monitored by HPLC. After the reaction was completed, it was distilled under vacuum. Washed and dried to give 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-hydroxyphenyl Preparation of -N-(2-(2-hydroxyethoxy)ethyl)propanamide (Compound 12)

The compound of the formula (12) was prepared in the manner of Example 7, except that ethanolamine was replaced by 2-(2-aminoethoxy)ethanol to give the 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-hydroxy Preparation of phenyl)-2-hydroxyethyl propionate (Compound 13)

The compound of the formula (13) was prepared in the manner of Example 5. 52 g of the compound (7) was dissolved in toluene in a flask equipped with a condensed water separator, and heated under reflux at 110 °C. To the toluene solution was added 10 g of ethylene glycol. The reaction was monitored by HPLC. A mixture of Compound 13 and Compound 20 (Example 18) was obtained by vacuum distillation. 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-hydroxyphenyl Preparation of 2-(2-hydroxyethoxy)ethyl propionate (Compound 14) Compound 14 was prepared in the same manner as in Example 9, except that 2-(2-hydroxyethoxy)ethanol was used instead of ethylene glycol. 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-hydroxyphenyl Preparation of-3,8,15,22-tetraoxo-7,14,21-trioxa-4-azepanose-27-yl-6-hydroxyhexanoate (Compound 15)

Compound (11) 12.1 g was dissolved in toluene, and 11.3 g of caprolactone and 0.018 g of a monobutyl triisooctanoate catalyst were added dropwise. The reaction was carried out at 140 ° C under nitrogen. The polymerization was observed in the reaction and purified by GPC (colloidal permeation chromatography). The degree of polymerization can be determined by H1-NMR chemical shift (-CH2- CH2 -CONH-) 2.7-3.0 (triplet) and chemical shift 1.6-1.7 (O=C-CH2- CH2 -CH2- CH2- CH2 -O) The integral area ratio is converted. It is estimated that the degree of polymerization is m=4. The structure of the obtained compound (15) was as follows.

Example 12

1-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(tert-butyl)-4-hydroxyphenyl Preparation of -3,8,15,22-tetraoxo-4,7,14,21-tetraoxaheptanoyl-27-yl-6-hydroxyhexanoate (Compound 16)

The compound of the formula (16) was prepared in the same manner as in Example 11 except that the compound of the formula (13) was replaced by the compound of the formula (13) to give the compound of the formula (16).

Example 13 Preparation of Compound 17

The compound of the formula (17) was prepared in the same manner as in Example 11, except that the compound of the formula (11) was replaced by the compound of the formula (12) to give the compound of the formula (17).

Example 16 Preparation of Compound 18

Compound (18) was prepared in the manner of Example 13. However, the compound (14) is replaced by the compound (14) to give 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)propanamide (Compound 19)

The compound of formula (19) was prepared as described in Example 7, except that bis(2-ethanol)amine was used in place of ethanolamine. The 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 Preparation of -(tert-butyl)-4-hydroxyphenyl)propionate)ethane (Compound 20)

Compound (20) was prepared in the same manner as in Example 5. 52 g of the compound (7) was dissolved in toluene in a flask equipped with a condensed water separator, and heated under reflux at 110 °C. To the toluene solution were added 56 g of the compound (13), and 1.5 g of p-toluenesulfonic acid. The reaction was monitored by HPLC, and after completion of the reaction, the compound 20 was obtained by vacuum distillation. Compound 20 was subjected to HPLC alignment with the impurity of compound 13 of Example 9, and the residence time was the same.

Example 19

((oxybis(ethane-2,1-diyl))bis(oxy)) bis(ethane-2,1-diyl)bis(3-(3-(4,6-bis(2) Of 4-(4-methylphenyl)-1,3,5-triazin-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionate) (Compound 21)

The compound of formula (21) was prepared in the manners of Examples 10 and 11, except that PEG 200 (molecular weight about 194) was substituted for ethylene glycol. A mixture of the compound (21) and the compound (22) is obtained, which is obtained by silica gel column chromatography.

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

Example 20. End capping and deblocking test

Blocking: 18 g of compound (12) was added to 100 ml of dimethylformamide and stirred. Next, 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 the compound (24) was obtained. Deblocking: After dissolving compound (24) (with or without KF) through a silica gel column (SiOH column), the Si(CH ₃ ) ₃ group can be directly removed. The chemical shift of 0.2 (Si(CH ₃ ) ₃ ) disappeared, indicating that the end group had been removed. After the end-blocking group is removed, it can be directly used as an anti-UV agent, and 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 absorber (Example 4-20), 6 g of benzoyl peroxide, and mixed in ethyl acetate/toluene solvent, and added to the reaction kettle. The temperature was raised to 75 ° C and the reaction was carried out for 2 hours. An additional 6 g of benzoyl peroxide (in solvent) was slowly added dropwise, the viscosity was monitored, and the reaction was continued for about 6 hours. After the reaction was completed, the temperature was lowered and applied to the PET film. The solvent was removed by drying to obtain a blue light-proof film (100 μm) of the anti-blue light agent. The transmittance (UV 350 nm) was measured, and the results are shown in Table 1.

Table 1 UV penetration of the product of the example

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 compound of the control group (UV 1164) GL ). 50 parts by weight of a polyether polyol (triol, molecular weight 3000), 2.0 parts by weight of water, 0.1 part by weight of triethyldiamine, and 1.0 part by weight of a 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 polyether polyol (triol, molecular weight 3000), 0.15 parts by weight of the example compound or the control compound. After mixing, it is poured into a box to carry out a foaming reaction. It was allowed to stand at room temperature for 1 hour and aged in an oven. A 1 gram sample of the polyurethane was cut and placed in a covered glass jar. Extraction was carried out by adding 100 ml of ethanol, and the concentrated solution was extracted for HPLC analysis. The amount extracted from the control compound was 100%, and the amount of the additive-free sample was 0%. The less the amount extracted, the less likely it is to precipitate. The results are summarized in Table 2.

Table 2. Precipitation tests

Claims (10)

1. A triazine compound and a salt thereof, characterized in that the structural formula is as shown in formula (I):

   

   Wherein R ₁ is hydrogen or a terminal group; and R ₂ to R ₁₂ are each independently selected from the group consisting of hydrogen, hydroxy, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonate, sulfate, and phosphate. , phosphonic acid group, unsubstituted or substituted morpholinyl group, benzoyl group, unsubstituted or substituted straight or branched C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkenyl group, C ₁ - C ₁₂ acyl group, C ₁ -C ₁₂ carbonyl group, C ₁ -C ₁₂ aryl group, C ₁ -C ₁₂ nitrogen-containing, oxygen, sulfur heterocyclic group, 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 -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy; R ₃ -R ₇ 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 group May be combined into a five or six ring; R _{13 is} selected from the group consisting of hydrogen, a bond, a C ₁ -C ₂₀ alkyl group, a divalent C ₂ -C ₄₀ alkyl group interrupted by one or more oxygen or sulfur or nitrogen,

   

   R ₁₄ and R ₁₅ are hydrogen or a C ₁ -C ₁₀ alkyl group;

   m=0～100;

   n=0~10;

   O=0～100;

   p=0~5;

   q=0~5;

   r=0~5;

   A is selected from the group consisting of a bond, H, O, OH, S, SH, NH, NHR ₁₆ wherein R ₁₆ is hydrogen, C ₁ -C ₁₀ alkyl or

   

   B is selected from the group consisting of a bond, H, O, OH, S, SH, NH, NH ₂ , NHR ₁₆ ;

   C is selected from the group consisting of a bond, H, O, S, NH, NHR ₁₆ ;

   D is hydrogen, a terminal group or

   

   The terminal group is selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ silane, C ₁ -C ₁₂ alkyl acyl, C ₁ -C ₁₂ benzoyl.
2. According to claim 1, R _{1 is} selected from hydrogen or a blocking group; and R ₂ to R ₁₂ are each independently selected from the group consisting of hydrogen, hydroxy, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonic acid, sulfuric acid. , phosphate, phosphonic acid, unsubstituted or substituted phenyl, morpholinyl, benzoyl, unsubstituted or substituted straight or branched C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkenyl, C ₁ -C ₁₂ acyl, 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 of each other selected from hydrogen, phenyl, unsubstituted or substituted straight or branched C ₁ -C ₆ Alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy; R _{13 is} selected from hydrogen, C ₁ -C ₂₀ alkyl, interrupted by one or more oxygen or sulfur or nitrogen Price C ₂ - C ₂₀ alkyl,

   

   R ₁₄ and R ₁₅ are hydrogen or a C ₁ -C ₆ alkyl group;

   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 the group consisting of a bond, H, O, OH, S, SH, NH, NH ₂ , NHR ₁₆ , wherein R ₁₆ is

   

   C is selected from the group consisting of a bond, H, O, S, NH, NHR ₁₆ ;

   D is H or a capping group;

   The terminal group is selected from the group consisting of C ₁ -C ₆ alkyl, C ₁ -C ₆ silyl, C ₁ -C ₆ alkyl acyl, benzoyl.
3. The 3-arylbenzofuranone propionamide compound according to claim 1, wherein R ₁ is hydrogen; and R ₂ is hydrogen or a linear or branched unsubstituted or substituted C ₁ -C ₁₂ Alkyl; R ₃ to R ₁₂ are each independently selected from hydrogen, hydroxy, halogen, amino, nitro, unsubstituted or substituted phenyl, morpholinyl, benzoyl, unsubstituted or substituted straight chain or Branched C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ acyl, 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 -C ₄ alkyl, C ₁ -C ₄ alkenyl, C ₁ -C ₄ alkoxy; R _{13 is} selected from hydrogen, C ₁ -C ₁₈ alkane a divalent C ₂ -C ₁₀ alkyl group 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 to 2.

   A is selected from O, NH;

   B is selected from the group consisting of a bond, H, O, OH, NH, NH ₂ , NR ₁₆ , wherein R ₁₆ is

   

   C is O or NH;

   D is H, a C ₁ -C ₆ silyl group or a C ₁ -C ₆ alkyl group.
4. According to claim 1, wherein R ₁ is hydrogen; R ₂ is a linear or branched unsubstituted or substituted C ₁ -C ₈ alkyl group; and R ₃ to R ₁₂ are each independently selected from hydrogen and hydroxy. , halogen, straight 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 a _C18 alkyl group, a divalent C ₂ -C ₄ alkyl group 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 methylalkyl; m = 0 to 10; n = 1 to 6; o = 0 to 10; p = 0 to 2 ;q=1~2; r=1~2.
5. The method according to any one of claims 1 to 4, wherein R ₁ is hydrogen; R ₂ is a linear or branched unsubstituted or substituted C ₁ -C ₅ alkyl group; and R ₃ to R ₁₂ are each independently Is selected from hydrogen, linear or branched unsubstituted or substituted C ₁ -C ₄ alkyl, methoxy, hydroxy; 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 to 4; n = 1 to 5; o = 0 to 4; p = 1 to 2; q=1～2; r=1～2.
6. A process for producing a 3-arylbenzofuranone compound (I) according to claim 1, which comprises a step of reacting a compound of the formula (III) with a compound of the formula (IV), wherein III) Compound:

   

   R ₁ to R _{13 are the} same as defined in the formula (I);

   X is the leaving group;

   Formula (IV) is: AR ₃ -B,

   Wherein A, B are each independently selected from a protected group or unprotected or protected OH, SH, NH ₂ , NHR ₁₆ wherein R _{16 is} as defined for the compound of formula (I).
7. A process for the preparation of a compound of the formula (III) according to claim 6, wherein the leaving group is OR ₁₇ , halogen or a sulfonyl group, wherein R ₁₇ is a C ₁ - C ₁₀ alkoxy group.
8. A composition comprising:

   Component a: at least one organic material susceptible to oxidative, thermal and/or photoinduced degradation, and

   Component b: at least one compound of formula (I),

   And the mass of component b is 0.0001% to 10% of the mass of component a.
9. The composition according to claim 1, wherein the mass of component b is from 0.01% to 5% by mass of component a.
10. The composition according to claim 9, which comprises a polyol, a polyurethane, a polyester, a polyamide, a polyolefin, a polyester, a polyether, a polyketone, a natural and synthetic rubber, a polyacrylate, a polymethacrylic acid. Ester, polyacetal, polyacrylonitrile, polybutadiene, acrylonitrile/butadiene/styrene copolymer, styrene/acrylonitrile copolymer, acrylate/styrene/acrylonitrile copolymer, cellulose polymer , polyimide, polyamideimide, polyetherimide, polyphenylene sulfide, polyphenylene ether, polysulfone, polyethersulfone, polyvinyl chloride, polycarbonate, polyketone, phenol/formaldehyde resin, At least one of a urea/formaldehyde resin, an alkyd resin, a urea resin, an epoxy resin, and a polysiloxane.