TWI513762B - Stabilizers with hindered phenolic group and hindered amine, and their compositions - Google Patents

Description

Bifunctional stabilizer and its constituents

The present invention relates to a stabilizer for improving the weather resistance of an organic material, and in particular, the same structure relates to a hindered amine compound stabilizer containing a hindered phenol structure.

Generally, organic polymeric materials (such as plastics, resins, cosmetics, colorants, coatings, textiles) are susceptible to damage by light, heat, acids, alkalis, or nitrogen oxides (NO _x ), which in turn causes discoloration or decomposition of materials. If a suitable organic additive (such as an antioxidant or a light stabilizer) can be added to the organic polymeric material, the material can be protected to reduce damage. For example, if a chemical with anti-oxidation or ultraviolet absorption properties is added, the energy of the ultraviolet light can be absorbed or converted to maintain the gloss and durability of the material.

At present, the weathering property of organic polymer materials is generally promoted in the industry by adding additives as described above, and the additives are mostly hindered phenol type antioxidants or phosphorus-containing organic antioxidants or light stabilizers. For example, Chinese Patent Publication No. 103694686, Taiwan Patent Publication No. 201229214, US Patent Publication No. 20120252931, and Soviet Patent No. 1659437 all use hindered amine stabilizers or hindered phenol type antioxidants to enhance weather resistance. However, these hindered phenol type antioxidant and a hindered amine type stabilizer and dried, although the antioxidant ability can be improved when the organic polymeric material in a high-temperature thermal processing or drying but for denaturation temperature yellowing resistance (anti-NO _x) and alkali Sex is obviously insufficient. Therefore, the present invention is to introduce a hindered amine functional group to improve the structure of the hindered phenol compound which is not alkali resistant.

It is an object of the present invention to provide a stabilizer which enhances the yellowing resistance of organic polymers in various environments. The stabilizer for improving the weather resistance of an organic material comprises: a bifunctional compound represented by the following formula (IV):

In the formula (IV), R ² represents a C1 to C8 alkyl group; R ¹ represents hydrogen or a methyl group; and R ³ represents a C1 to C18 alkylene group, a cycloalkylene group, an arylene group, an arylene group or an alkylene group. Aryl; and X represents -NH-NH- or Y ¹ and Y ² are the same or differently represented by -O- or -NH- ; R represents a C ₁ to C ₆ alkylene group; and n represents 0 to 2.

Another object of the invention is to provide a modified polymer comprising an organic polymeric substrate, and a stabilizer as described above.

The beneficial effects of the present invention are: double in the stabilizer of the present invention Functional compounds help to enhance the yellowing resistance of organic polymers in a variety of different environments and can be used in combination with other additives.

The present invention will be described in detail below with reference to the embodiments:

Preferably, in the formula (IV), R ³ represents a C ₆ to C ₁₈ alkylene group or an alkylene aryl group. More preferably, R ³ represents or .

Preferably, in the formula (IV), R ¹ represents hydrogen.

Preferably, in the formula (IV), X represents and R ² represents a t-butyl group.

Preferably, in the formula (IV), R represents an ethylene group.

Preferably, the difunctional compound is obtained by reacting a hindered phenol compound, a polyisocyanate and a hydrazine compound represented by the following formula (I):

In the present invention, the hindered phenol compound represented by the above formula (I) is obtained by subjecting a methyl ester compound represented by the following formula (I') to a one-side condensation demethylation reaction in the presence or absence of a catalyst:

Preferably, the catalyst may be selected from the group consisting of organotin compounds, sodium methoxide, organic bases or inorganic bases.

Preferably, it is selected from the group consisting of hydrazine hydrate (H ₂ N-NH ₂ ‧H ₂ O), ethanolamine (H ₂ NCH ₂ CH ₂ OH) or triethylene glycol (HO-C ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ -OH).

Preferably, the polyisocyanate is represented by the following formula (II): OCN-R ³ -NCO (II).

In the present invention, the polyisocyanate represented by the above formula (II) may be selected from the group consisting of 1,4-phenylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate (IPDI). ), methylene-bis(4-cyclohexyl diocyanate), 1,6-hexamethylene diisocyanate (HDI), 4,4 '-Methylene bis(phenylphenylisocyanate) (4,4'-methylenediphenyl diisocyanate, MDI) or 4,4',4"-triphenylmethane-4,4',4"-triisocyanate ). Preferably, the polyisocyanate is MDI.

Preferably, the hindered amine compound is represented by the following formula (III):

It can be understood that the above-mentioned hindered phenol compound represented by formula (I), the polyisocyanate and the hindered amine compound (III) should be reacted to prepare a mixture. The bifunctional compound as shown in formula (IV) is only one aspect of the mixture. The present invention can be controlled by a reaction temperature, for example, by adding one of the hindered phenol compound or the hindered amine compound at a low temperature, and unilaterally reacting with the polyisocyanate, and after reacting to a certain extent, at room temperature. The hindered phenol compound or the other of the ruthenium compound is continuously added to the reaction, and most of the formed mixture is a bifunctional compound represented by the formula (IV).

Preferably, the difunctional compound is obtained by reacting a hindered phenol compound represented by the formula (I) with the polyisocyanate at a low temperature and then reacting with the hindered amine compound.

Preferably, the hindered phenol compound, the polyisocyanate, and the hindered amine compound are mixed in a molar ratio of approximately 1:1:1 to carry out the reaction.

In the present invention, the hindered phenol compound, the polyisocyanate, and the hydrazine compound are carried out under an organic solvent. Preferably, the organic solvent may be selected from the group consisting of alkanes (for example: toluene, xylene, benzene, n-hexane, n-heptane or cyclohexane), ethers (for example: diethyl ether or dibutyl ether), acetonitrile, tetrahydrofuran, acetone. , butanone or N,N-dimethylformamide (DMF). In a particular embodiment of the invention, the organic solvent is toluene.

It is to be noted that, in the synthesis step of the difunctional compound, the reaction sequence of the hindered amine compound and the hindered phenol compound and the polyisocyanate of the above raw materials does not affect the obtained bifunctional compound. Preferably, the hindered phenol compound is first reacted with the polyisocyanate at a low temperature, and then the hindered amine compound is added to carry out the reaction, because the hindered The amine compound is a solvent soluble in toluene. The advantage of this synthetic sequence is that the remaining material is less likely to remain in the product.

In the present invention, the reaction temperature for synthesizing the bifunctional compound ranges from -5 to 200 ° C, and the initial reaction temperature is usually preceded by a reaction at a low temperature or a normal temperature (below 25 ° C), and when the reaction reaches a certain level, the temperature is gradually raised to a predetermined temperature. Reaction temperature. Preferably, the reaction temperature for synthesizing the bifunctional compound ranges from 0 to 100 °C.

The stabilizer of the present invention can be added to an organic material to reduce changes in physical and chemical properties (such as yellowing) of the organic material due to environmental influences such as visible light, ultraviolet light, acid, alkali, high temperature or oxidation.

The organic material can be selected from the following organic polymer substrates:

Polyolefins: for example polyethylene, polypropylene, polyisobutylene, polyisoprene, polybutadiene or combinations thereof.

Olefin copolymers: for example ethylene/propylene copolymers, propylene/1-butene, propylene/isobutylene, propylene, butadiene, isobutylene/isopentene, ethylene/alkyl acrylate, ethylene/alkyl methacrylate , ethylene/acrylic acid copolymer or a salt thereof.

Polystyrene: for example, polystyrene, poly-p-methyl styrene or poly-α-methyl styrene.

Copolymer of styrene or α-methylstyrene with a diene or acrylic acid derivative: for example, a copolymer of styrene and butadiene, a copolymer of styrene and acrylonitrile, styrene/butadiene/alkylacrylic acid Ester copolymer, styrene/butadiene/acrylonitrile copolymer, styrene/maleic anhydride copolymer or styrene/acrylonitrile/methacrylate copolymer.

Graft copolymers of styrene or α-methylstyrene: for example styrene-grafted polybutadiene, styrene-grafted butadiene and acrylonitrile copolymers.

Halogen-containing polymers: for example, polychloroprene rubber, polyvinyl chloride, polyvinyl fluoride or a copolymer with a halogen-containing monomer (for example, a copolymer of vinyl chloride and vinyl acetate).

Homopolymers or copolymers of cyclic ethers: for example polyalkylethylene glycol, polyethylene oxide or polypropylene oxide.

Polyoxymethylene (POM).

Polyphenylene oxide or polyphenylene sulfide.

Polycyanuric urethane.

Polyamide and decylamine copolymer: a polymer obtained by condensation reaction of a diamine compound and a carboxyl group-containing compound, such as polyamine 6, polyamine 6/6, 6/10, 6/12 or 4/6, Polyamide 12 and the like.

Polyurea resin or polyurethane: A polymer or oligomer formed by reacting a diamine compound or a polyol with a diisocyanate.

Polycarbonate and polyester/carbonate.

Unsaturated polyester resin: a condensation reaction of a saturated or unsaturated dicarboxylic acid compound with a polyol, an olefin may be added as a crosslinking agent, or a halogen-containing compound may be added to reduce flammability.

The thermosetting acrylic resin or acrylic resin contains melamine resin, urea resin, polycyanate or epoxy resin.

a mixture of the above polymers: for example PP/EPDM, PC/ABS , PC/PBT, POM/thermoplastic PU or PA/PPO.

Preferably, the organic polymer substrate is a polyurethane.

Preferably, the stabilizer is contained in an amount ranging from 0.01 to 10% by weight based on 100% by weight of the total weight of the organic polymer substrate. More preferably, the stabilizer has a content ranging from 0.01 to 2% by weight to achieve an antioxidant effect.

The difunctional compound of the stabilizer of the present invention may be added to the above-mentioned organic material alone or may be added to the organic material in combination with other additives. The addition method may be carried out by extrusion or injection molding after being mixed with the organic polymer substrate before processing, or may be added during the production process of the organic material or used in the post-processing. For example, the stabilizer of the present invention may be added together with a polyol or an isocyanate starting material to form a polyurethane.

Preferably, the stabilizer of the present invention further comprises at least one additive to enhance the resistance to light, acid and alkali, high temperature or oxidation of the organic material.

The additive may be selected from one or more of the following:

Hindered phenolic antioxidant

Alkylated monophenols: for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4- Ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methyl Phenolic, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol or 2,6-di-indolyl-4-methylphenol.

Alkylated oximes: for example 2,6-di-tert-butyl-4-methoxyphenol or 2,5-di-tert-butyl hydroquinone.

Phenyl sulfide phenols: for example 2,2'-sulfurized-bis-(6-tert-butyl-4-methyl Phenol), 2,2'-sulfurized-bis-(4-octylphenol), 4,4'-sulfurized-bis-(6-tert-butyl-3-methylphenol) or 4,4'-vulcanized - bis-(6-tert-butyl-2-methylphenol).

Alkylene bisphenols: for example 2,2'-methylene-bis(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis(6-tert-butyl-4) -ethylphenol), 2,2'-methylene-bis[4-methyl-6-(α-methylcyclohexyl)-phenol], 2,2'-methylene-bis (4-methyl) -6-cyclohexylphenol), 2,2'-methylene-bis(6-mercapto-4-methylphenol), 2,2'-methylene-bis(4,6-di-tert Butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis-(6-tert-butyl-4-isobutyl) Phenol), 2,2'-methylene-bis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis[6-(α,α - dimethylbenzyl)-4-nonylphenol], 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-bis (3-tert Butyl-5-methyl-2-hydroxyphenyl)-4-methylphenol, 1,1,3-tri-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl-thiobutane or ethylene glycol-[3,3-bis-(3 '-tert-Butyl-4'-hydroxyphenyl)-butyl ester].

a benzyl compound: for example, 1,3,5(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide or 1,3,5-trimethyl-2,4,6-tris (3,5) -Di-tert-butyl-4-hydroxybenzyl)benzene.

Amidoxidinated phenols: for example, the product of the amidation of methyl β-(3,5-di-alkyl-4-hydroxyphenyl)acrylate reacted with octadecylamine.

--(3,5-Di-alkyl-4-hydroxyphenyl)acrylates: from β-(3,5-di-alkyl-4-hydroxyphenyl)acrylate or methyl acrylate and monohydric alcohol Or a polyol esterification reaction or a transesterification reaction, the monohydric alcohol or a polyhydric alcohol The alcohol may be selected from isooctanol, n-octanol or a mixed alcohol of C7 to C9, stearyl alcohol, 1,6-hexanediol, 1,4-butanediol, ethyl sulphide, diethyl ethane Glycol, triethyl glycol, pentaerythritol. For example, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate (CAS No. 229-722-6) or triethylene glycol di(3-(3) -tert-Butyl-5-methyl-4-hydroxyphenyl))propionate (CAS No. 36443-68-2).

醯-(3,5-di-alkyl-4-hydroxyphenyl) decylamine acrylate: for example, N,N-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropenyl)- Hexamethylenediamine, N,N-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropenyl)-propylenediamine, N,N-bis-(3,5-di-tert-butyl 4-hydroxyphenylpropenyl)-biamine, β-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid-octadecylamine or β-(3-methyl-5 -tert-Butyl-4-hydroxyphenyl)acrylic acid-octadecylamine.

UV absorber and light stabilizer

2-(2'-hydroxyphenyl)-benzotriazole compound: for example, a phenyl group having the following substituents such as 5'-methyl, 3', 5'-di-tert-butyl, 5'-tert-butyl Base, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5' -methyl, 3'-isobutyl-5'-tert-butyl, 3',5'-di-tert-amyl or 3',5'-bis-(α,α-dimethylbenzyl), etc. The benzotriazole compound or the 2'-hydroxyl position has a benzotriazole compound such as an ester derived from acrylic acid.

2-hydroxybenzophenone: a benzophenone bearing 4-hydroxy, 4-methoxy, 4-octyloxy, 4-alkoxy or 4-dodecyloxy.

Benzoic acid derived esters: for example 2,4-di-tert-butylphenyl, 3,5-di-tert-butyl-4-hydroxybenzoate.

Nickel-containing stabilizer: for example 2,2'-sulfurized-bis[4-(1,1,3,3-tetra Nickel complex of butyl butyl)-phenol].

Hindered amine photolabents: for example bis(2,2,6,6-tetramethylpiperidyl)sebacate, 2-(3,5-di-tert-butyl-4-hydroxy-benzylidene)- 2-(1,2,2,6,6-pentamethyl-4-piperidinyl) 2-butyl 1,3-malonate, bis(1,2,2,6,6-pentamethyl) 4-piperidinyl)-sebacate, 4,4'-bis(1,2,2,6,6-pentamethylpiperidinyl)bisphenylmethane [4,4'-diphenylmethane bis (1 , 2,2,6,6-pentamethyl piperidyl carbamate)], 4,4'-bis(2,2,6,6-tetramethylpiperidinyl)bisphenylmethane [4,4'-diphenylmethane bis ( 2,2,6,6-tetramethyl piperidyl carbamate)], polysuccinic acid (4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol) ester [poly-(N-β- Hydroxyethyl-2,2,6,6-tetramethyl piperidine-4-hydroxy-piperidyl succinate).

Metal deactivator: for example, N,N,-bis(3,5-di-tert-butyl-4-hydroxyphenylacrylic acid) hydrazine.

Phosphorus-containing organic antioxidants such as phosphates and phosphites: for example, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, Bis[2-methyl-4,6-bis(1,1-dimethylethyl)phenol]ethyl phosphate (CAS No. 14560-60-8), bisphenol A phosphite, tetra (2) , 4-di-tert-butylphenyl-4,4'-biphenyl)bisphosphate (CAS No. 38613-77-3), pentaerythritol diphosphite dioctadecyl ester (CAS No. 3806- 34-8), pentaerythritol bis(2,4-di-tert-butylphenyl) diphosphite, bis(2,6-di-tert-butyl-4-tolyl)pentaerythritol phosphite, 2,4, 6-tri-tert-butylphenyl pentaerythritol diphosphite, pentaerythritol diphosphite di(decyl) ester, pentaerythritol diphosphite di(dodecanol) ester, dipropylene glycol (DPG) and triphenyl phosphite Condensate (molar ratio 1:2) or oligomer (such as molar ratio 7:8) and the like.

Thioester antioxidants: for example, dilauryl thiodipropionate (CAS No. 123-28-4), di(tris) thiodipropionate (CAS No. 10595-72-9), sulfur Di(tetradecyl) dipropionate (CAS No. 16545-54-3) or di(octadecyl) thiodipropionate (CAS No. 693-36-7).

Alkaline co-stabilizers: unilateral or bilateral products of melamine, urea derivatives, hydrazine (H2N-NH2) reacted with isocyanate, unilateral or bilateral products of 1,1-dimethylhydrazine and MDI, An organic stabilizer such as an amine, a hydroxy-nitrogen bond organic compound, an alkali and an alkaline earth metal salt, a zeolite, a hydrotalcite, a calcium stearate, a zinc, a tin, or a magnesium.

Nucleating agent: for example 4-tert-butylbenzoic acid or adipic acid.

Fillers or fortifiers: for example calcium carbonate, diatomaceous earth, glass fibers, asbestos, talc, kaolin, mica, metal oxides or metal hydroxides, carbon black or graphite.

Other additives: for example, plasticizers, lubricants, emulsifiers, surfactants, colorants, fluorescent whitening agents, flame retardants, antistatic agents or foaming agents.

Preferably, the additive is selected from the group consisting of a hindered phenol type antioxidant, a phosphorus containing organic antioxidant, a thioester type antioxidant, a hindered amine type light stabilizer, or a combination thereof.

Preferably, the total weight of the organic polymer substrate is 100% by weight, and the content of the additive ranges from 0.01 to 10% by weight.

The invention is further described in the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

Example

[Preparation of Bifunctional Compounds]

<Example 1> Bifunctional Compound A

Add 250 mL of ethanol, 60 g of 80% hydrazine hydrate and 146 g of methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate to a 500 mL four-neck mechanical stirred bottle, and warm to reflux for 6 hours. TLC was detected to be free of methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate, and 150 mL of water was added thereto to cool the crystals, and the crystals were completely precipitated. After filtration and drying, 141 g of a white solid powder was obtained.

After another 500 mL four-neck mechanically stirred bottle was deoxygenated with nitrogen, 250 mL of toluene and 50 g (0.2 mol) of 4,4'-methylenebis(phenylisocyanate) (MDI) were added at 10-15 ° C. Slowly add 58.4g (0.2mol) of the above white solid powder, there will be an exothermic phenomenon during the addition process, so that the temperature naturally rises to 40-45 ° C, and after the reaction for 1 hour, add 31.4g (0.2mol) 2,2,6 , 6-tetramethylpiperidinol, solids are generated during the process, the temperature is raised to 55-60 ° C for 3 hours, and then heated to 90 ° C for 2 hours, then cooled to 10 ° C to filter out the crystals to obtain 131 g of white solid [ That is, the bifunctional compound A] represented by the following formula (A) has a yield of 94.2%.

<Example 2> Bifunctional Compound B

The synthesis method of Example 2 was the same as that of Example 1, except that MDI was replaced by 336 g of HDI to obtain 112 g of a white solid [i.e., a bifunctional compound B represented by the following formula (B)] in a yield of 90.8%.

<Example 3> Bifunctional Compound C

The synthesis method of Example 3 was the same as that of Example 1, except that 125 g of β-(3-methyl-5-tert-butyl-4-hydroxyphenyl)propionate was substituted for 146 g of β-(3,5- Methyl di-tert-butyl-4-hydroxyphenyl)propanoate was reacted with hydrazine hydrate in ethanol to give 101 g of an intermediate product. 50 g (0.2 mol) of the above intermediate product was sequentially reacted with MDI and 31.4 g (0.2 mol) of 2,2,6,6-tetramethylpiperidin (the same procedure as in Example 1) to obtain 123 g of a white solid. That is, the bifunctional compound C] represented by the following formula (C); the yield was 93.6%.

<Example 4> Bifunctional Compound D

250 mL of toluene, 61 g of ethanolamine and 146 g of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid methyl ester were added to a 500 mL four-neck mechanical stirring flask, and the mixture was heated to reflux for 18 hours, and detected by TLC. There was no methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate, and the crystals were completely precipitated by cooling. After filtration and drying, 143 g of a white solid powder was obtained, which had a melting point of 136-138 °C.

After another 500 mL four-neck mechanically stirred bottle was deoxygenated with nitrogen, 250 mL of toluene and 50 g (0.2 mol) of MDI were added, and 64.2 g (0.2 mol) of the above white solid powder was slowly added first at 20-25 ° C during the addition. There will be a micro-exothermic phenomenon. After the reaction for 5 hours, the temperature is raised to 40-45 ° C for 2 hours, and then 31.4 g (0.2 mol) of 2,2,6,6-tetramethylpiperidinol is added. The reaction was carried out and reacted at this temperature for 3 hours. During the process, solids were generated, and the temperature was raised to 55-60 ° C to stir the reaction for 3 hours. Finally, the temperature was raised to 80 ° C and then reacted for 2 hours, and then the temperature was lowered to 10 ° C to filter out the crystals. 134 g of a white solid [that is, the bifunctional compound F represented by the following formula (F)] was obtained in a yield of 92.4%.

<Comparative Example> Compound E

The synthesis method of the comparative example was the same as that of Example 1, except that 2,2,6,6-tetramethylpiperidinol was not added, and the relative amount of the intermediate product and MDI was changed to a molar ratio of 2.0:1.0. The obtained white solid was Compound E represented by the following formula (E).

[Preparation of modified polymer]

The bifunctional compound of the examples and the compound E of the comparative example were separately mixed with a thermoplastic polyurethane (TPU, purchased from Kunzhong, Taiwan, model 95A) according to the following Table 1 (to a total weight of TPU of 100 wt%), And adding the additive according to the ratio of Table 1 below, respectively, and obtaining the TPU composition containing the stabilizers E1-E6 and CE1 and CE2, respectively, and mixing and extruding at 195 ° C by a twin-screw extruder (China Taiwan Hongsheng Machinery Co., Ltd. test machine PSM20A) , and then injected into a 2mm modified TPU polymer (ASTM-D638) at 200 ° C by injection molding machine (China Taiwan Bai Plastics vertical injection machine V2-S) TYPE IV test strip).

The additive in Table 1 is produced by Taiwan Double Bond Chemical Co., Ltd., wherein Chinox 245 means "triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)] Propionate"; DLDTP means "dilauryl thiodipropionate".

[Yellow resistance test]

<Room and heat resistance test>

The above modified polymer was placed in a room temperature air and a 50 ° C oven (purchased from BINDER, Germany, model FD 53L), and the color change was measured [using HunterLab's color difference meter (model number ColorQuest XE) measures the YI value and calculates the amount of rise in YI value (ΔYI value). The results are shown in Table 2 below.

The smaller the ΔYI value is, the higher the yellowing resistance is. Therefore, it can be known from Table 2 that the stabilizer of the present invention has a hindered phenol compound (bifunctional compound) having a piperidinyl structure, so that the stabilizer E2 (compound) A) The modified TPU exhibits better yellowing resistance after 30 days or 60 days than the TPU composition modified with stabilizers CE1 and CE2 in the heat resistance test at room temperature and 50 °C. . In addition, it is modified by stabilizers E1, E3-E6 As can be seen from the test results of the TPU, the bifunctional compound in the stabilizer of the present invention, when used in combination with other additives, exhibits better yellowing resistance than the TPU modified by the stabilizers CE1 and CE2 after 60 days.

<Alkali resistance test>

The above modified polymer was placed in 500 mL of ultrapure water, and potassium carbonate was added to adjust the pH to 11, and then heated to 80 ° C. After maintaining the temperature for 1 hour, the mixture was taken out to room temperature air, and the color was measured. The change (ΔYI value), the results are shown in Table 3 below.

It can be seen from Table 3 that the TPU modified by the stabilizers E1-E6 of the present invention is modified in the alkali resistance test, whether after 30 days, 45 days, 60 days or 70 days, with respect to the stabilizers CE1 and CE2. The TPU composition exhibits better yellowing resistance after the treatment, especially when compared with E2 and CE1; it further reflects that the stabilizer of the present invention is a hindered phenol compound having a piperidinyl structure ( Bifunctional compounds), therefore, have a more pronounced alkali resistance.

In summary, the stabilizer of the present invention can significantly improve the yellowing resistance of the organic polymer at room temperature, 50 ° C and an alkaline environment due to the hindered phenol compound (bifunctional compound) having an amine urea structure, and can It is used in combination with other additives, so that the object of the present invention can be achieved.

However, the above is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made according to the contents of the present invention and the patent specification are still Within the scope of the invention patent.

Claims (12)

A stabilizer for improving the weather resistance of an organic material, characterized in that it comprises a bifunctional compound represented by the following formula (IV): In the formula (IV), R ² represents a C ₁ to C ₈ alkyl group; R ¹ represents hydrogen or a methyl group; and R ³ represents a C ₁ to C ₁₈ alkylene group, a cycloalkylene group, an arylene group, an aralkylene group. Or an alkylene aryl group; and X represents -NH-NH- or Y ¹ and Y ² are the same or differently represented by -O- or -NH- ; R represents a C ₁ to C ₆ alkylene group; and n represents 0 to 2. The stabilizer according to claim 1, wherein R ³ represents a C ₆ to C ₁₈ alkylene group or an alkylene aryl group. The stabilizer according to claim 1, wherein R ¹ represents hydrogen. The stabilizer according to claim 1, wherein X represents -NH-NH- and R ² represents a t-butyl group. The stabilizer according to any one of claims 1 to 3, wherein the difunctional compound is obtained by reacting a hindered phenol compound, a polyisocyanate and a hindered amine compound represented by the following formula (I): In the formula (I), R ² represents a C ₁ to C ₈ alkyl group; and X represents -NH-NH- or Y ¹ and Y ² are the same or differently represented by -O- or -NH- ; R represents a C ₁ to C ₆ alkylene group; and n represents 0 to 2. The stabilizer according to claim 5, wherein in the formula (I), X represents -NH-NH- and R ² represents a tert-butyl group. The stabilizer according to claim 1, characterized in that it further comprises at least one additive. The stabilizer according to claim 7, wherein the additive is selected from the group consisting of a hindered phenol type antioxidant, a phosphorus-containing organic antioxidant, a thioester antioxidant, a hindered amine type light stabilizer, or a combination thereof. A modified polymeric material characterized by comprising an organic polymeric substrate, and a stabilizer as claimed in claim 1 or 7. The modified polymer material according to claim 9, wherein the organic polymer substrate is a polyurethane. The modified polymer material according to claim 9, characterized in that the total weight of the organic polymer substrate is 100% by weight, and the content of the stabilizer is in the range of 0.01 to 2% by weight. The modified polymer material according to claim 9, wherein the stabilizer further comprises at least one additive, and the total weight of the organic polymer substrate is 100% by weight, and the content of the additive ranges from 0.01 Up to 10% by weight.