Phthalate-type benzofuranone compounds, preparation method and application thereof

Abstract

The present invention provides a phthalate ester type benzofuranone compound, a preparation method and application thereof. The phthalate ester type benzofuranone compound has a structure shown in Formula I. Wherein, R 1 , R 2 Each independently selected from a C1 to C8 straight chain or branched alkyl group, n R 3 They are independently hydrogen or C1-C4 alkyl, and n is an integer from 1 to 4. The phthalate-type benzofuranone compound provided by the present invention has good carbon free radical scavenger function, and has the advantages of high antioxidant efficiency, good compatibility with the matrix, high molecular weight and not easy to migrate and escape, and has good application performance in polymer materials, especially in the field of plastic processing. #imgabs0#

Description

Technical Field

[0001] The invention relates to the field of polymer material additives, and in particular to a phthalate-type benzofuranone compound, a preparation method and application thereof. Background Art

[0002] During the manufacturing, storage, processing and use of polymer materials, oxidation may cause the performance of polymer materials such as plastics and their products to decline or lose, leading to the aging of polymer materials. Adding antioxidants can give polymer materials the necessary antioxidant capacity.

[0003] Under extrusion processing conditions, polymers are usually in an oxygen-deficient state, and the system contains a large number of carbon free radicals rather than alkoxy free radicals and hydroxyl free radicals. Therefore, an ideal processing stabilizer should be able to effectively capture carbon free radicals. The main carbon free radical capture agents on the market include hydroxylamine, bisphenol monoacrylate, ortho-propenyl substituted phenols, and benzofuranone. The use of benzofuranone stabilizers in conjunction with phenolic antioxidants can not only effectively capture carbon free radicals, but also regenerate hindered phenols by providing active hydrogen, thereby reducing the discoloration caused by the oxidation of phenols. It is an ideal carbon free radical capture stabilizer. However, due to its potential reproductive toxicity, the development and application of this type of product is limited. At present, the market mainly uses BASF Irganox HP-136 and Qitai Technology Revonox 501 (an improved version that complies with FDA, and the thermal decomposition temperature is nearly 100°C higher than HP-136, which is not only suitable for polyolefins, but also nylon products). In the structure of benzofuranone stabilizers, the α-H atom has high activity due to the "steric effect" of its structure. It can be used to "quench" the alkyl free radicals generated in the initiation stage of the polymer chain. The stabilization effect on the polymer is based on the so-called "pull-push effect". Revonox 501 is a carbon-neutral free radical ion scavenger and a lactone-type thermal stabilizer. It can inhibit oxidation caused by processing at the initial stage and is a stabilizer with processing stability and long-term thermal stability. It is superior to traditional antioxidant systems, especially in improving melt flow index (MFI) control, good color maintenance and long-term thermal stability. Revonox 501 is used in various polymers such as PP, PE, PBT, PA, styrene-ethylene and adhesives, especially engineering plastics, and provides excellent performance. In practical applications, Revonox 501 is used in combination with primary and secondary antioxidants. As a product of the "ternary compound antioxidant system", it has the advantages of less addition, excellent antioxidant performance and less ash content compared with traditional binary antioxidant stabilizers.

[0004] However, in practical applications, the above-mentioned BASF Irganox HP-136, QiTi Technology Revonox 501, etc. all belong to the monobenzofuranone class, and their antioxidant performance and efficiency have room for improvement. More importantly, they are not compatible with some matrices and have low molecular weight, which makes them easy to migrate and escape in polymer materials.

[0005] The benzofuranone antioxidants in the prior art generally have the above-mentioned problems. There is an urgent need to develop antioxidants with new structures that have good carbon free radical scavenger functions and can have the advantages of high antioxidant efficiency, good compatibility with the matrix, high molecular weight and not easy to migrate and escape. Summary of the invention

[0006] The main purpose of the present invention is to provide a phthalate-type benzofuranone compound, a preparation method and application thereof, so as to solve the problems that the benzofuranone antioxidants in the prior art cannot take into account both good antioxidant efficiency and compatibility with the matrix, and are not easy to migrate and escape.

[0007] In order to achieve the above object, according to one aspect of the present invention, a phthalate-type benzofuranone compound is provided, which has a structure shown in Formula I:

[0008]

[0009] Among them, R 1 , R 2 Each independently selected from a C1 to C8 straight chain or branched alkyl group, n R 3 Each is independently hydrogen or a C1-C4 alkyl group, and n is an integer from 1 to 4.

[0010] Furthermore, R 1 , R 2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl or isooctyl; preferably, R 1 , R 2 are all tert-butyl; preferably, n R 3 are independently selected from hydrogen, methyl, ethyl, n-propyl or isopropyl; more preferably, n R 3 are each independently selected from hydrogen or methyl.

[0011] Furthermore, the compound has a structure shown in Formula I-1 or Formula I-2:

[0012]

[0013]

[0014] Furthermore, the phthalate-type benzofuranone compound is one of the following compounds:

[0015] Compound 1,

[0016] Compound 2,

[0017] According to another aspect of the present invention, a method for preparing the above-mentioned phthalate-type benzofuranone compound is also provided, which comprises the following steps: reacting a first substrate represented by formula II and a second substrate represented by formula III in an organic solvent in the presence of a base to obtain a phthalate-type benzofuranone compound;

[0018]

[0019] Among them, R 1 , R 2 , R 3 and n have the same meaning as in any one of claims 1 to 4.

[0020] Further, the molar ratio of the first substrate to the second substrate is 1:(2-4); preferably, the base is selected from an organic base and / or an inorganic base, preferably the organic base is selected from one or more of 4-dimethylaminopyridine, triethylamine and tri-n-butylamine, and the inorganic base is selected from one or more of sodium bicarbonate, sodium carbonate and potassium carbonate; more preferably, the base includes at least 4-dimethylaminopyridine; further preferably, the base is a mixture of 4-dimethylaminopyridine and triethylamine, and the molar ratio of the two is 1:(10-20); preferably, the molar ratio of the base to the second substrate is 1:1-3; preferably, the organic solvent is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile and toluene.

[0021] According to another aspect of the present invention, a polymer material antioxidant is also provided, which includes the above-mentioned phthalate-type benzofuranone compound.

[0022] Furthermore, the polymer material antioxidant also includes at least one of a hindered amine antioxidant, a phosphite antioxidant, and a thioester antioxidant; preferably, the hindered phenol antioxidant is tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (iso)octyl ester, One or more of 2,2-oxalylamino-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide); preferably, the phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, triisodecyl phosphite , one or more of pentaerythritol diisodecyl diphosphite, tetraphenyl dipropylene glycol diphosphite, diphenyl monoisodecyl phosphite, triphenyl phosphite, monophenyl diisodecyl phosphite, tris(nonylphenyl) phosphite; preferably, the thioester antioxidant is one or more of pentaerythritol tetrakis(3-dodecyl thiopropionate), distearyl thiodipropionate, didodecanol thiodipropionate, ditetradecyl thiodipropionate, and ditridecyl thiodipropionate; more preferably, the polymer material antioxidant includes phthalate-type benzofuran Ketone compounds, hindered phenol antioxidants and phosphite antioxidants; preferably, the weight ratio of phthalate-type benzofuranone compounds, hindered phenol antioxidants and phosphite antioxidants is 1:(2-4):(2-4); further preferably, the polymer material antioxidant is a mixture of phthalate-type benzofuranone compounds, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite in a weight ratio of 1:(2-4):(2-4).

[0023] According to another aspect of the present invention, a polymer material is provided, comprising a polymer material matrix and an antioxidant dispersed in the polymer material matrix, wherein the antioxidant is the above-mentioned polymer material antioxidant.

[0024] Further, the polymer material matrix is ​​a resin or rubber; preferably, the resin is polyolefin, polyurethane, polyether, polyketone, polystyrene, polycarbonate, polyacrylate, polymethacrylate, polyacetal, halogen-containing polymer, polyamide, polyoxymethylene, polyphenylene ether, polyethylene terephthalate, polysuccinate terephthalate, polyacrylonitrile, polybutadiene, polystyrene, HIPS, ABS, MBS, epoxy resin or epoxy resin cross-linked acrylic resin; preferably, the rubber is natural rubber, styrene-butadiene rubber, chloroprene rubber, butadiene rubber, isoprene rubber, nitrile rubber or thermoplastic TPU; more preferably, the polymer material is PP, and the antioxidant comprises the phthalate-type benzofuranone compound of any one of claims 1 to 4, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris(2,4-di-tert-butylbenzene) phosphite; preferably, the added amount of the antioxidant is 0.01 to 0.15% of the weight of PP.

[0025] The phthalate-type benzofuranone compounds provided by the present invention have good carbon free radical scavenger function, and have the advantages of high antioxidant efficiency, good compatibility with the matrix, high molecular weight and low migration and escape, and are used in polymer materials, especially in the field of plastic processing, and have good application performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0027] Figure 1 The NMR spectrum of the benzofuranone monomer Aa prepared according to Example 1 of the present invention is shown;

[0028] Figure 2 The NMR spectrum of the benzofuranone monomer Ab prepared according to Example 2 of the present invention is shown;

[0029] Figure 3 The NMR spectrum of the phthalate-type benzofuranone compound 1 prepared according to Example 3 of the present invention is shown;

[0030] Figure 4 The NMR spectrum of the phthalate-type benzofuranone compound 2 prepared according to Example 8 of the present invention is shown. DETAILED DESCRIPTION

[0031] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0032] As described in the background technology section, the benzofuranone antioxidants in the prior art cannot achieve both good antioxidant efficiency and compatibility with the matrix, and are prone to migration and escape.

[0033] In order to solve the above problems, the present invention provides a phthalate-type benzofuranone compound having a structure shown in Formula I:

[0034]

[0035] Among them, R 1 , R 2 Each independently selected from a C1 to C8 straight chain or branched alkyl group, n R 3 Each is independently hydrogen or a C1-C4 alkyl group, and n is an integer from 1 to 4.

[0036] The phthalate-type benzofuranone compounds provided by the present invention have good carbon free radical scavenger function, and have the advantages of high antioxidant efficiency, good compatibility with the matrix, high molecular weight and low migration and escape, and are used in polymer materials, especially in the field of plastic processing, and have good application performance.

[0037] The above R 1 , R 2 The straight or branched alkyl groups independently selected from C1 to C8 can make the phthalate-type benzofuranone compounds have good carbon free radical scavenging properties and better compatibility and mobility. In order to better exert the above effects, in a preferred embodiment, R 1 , R 2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl or isooctyl; preferably, R 1 , R 2 Compared with other alkyl substituents, benzofuranone symmetrically carries four tert-butyl groups, has better antioxidant properties, and has better effects in the field of plastic processing.

[0038] Preferably, n R 3 are independently selected from hydrogen, methyl, ethyl, n-propyl or isopropyl; more preferably, n R 3 are each independently selected from hydrogen or methyl.

[0039] In a preferred embodiment, the compound has a structure shown in Formula I-1 or Formula I-2:

[0040]

[0041] In formula I-1, the left and right benzofuranone substituents are bonded to the para position of the ester group, and in formula I-2, the left and right benzofuranone substituents are bonded to the ortho position of the ester group. The above two types of phthalate-type benzofuranone compounds have better performance in antioxidant properties, compatibility with polymer matrices, and resistance to migration and escape. More preferably, the phthalate-type benzofuranone compound is a compound shown in formula I-1.

[0042] Preferably, the phthalate-type benzofuranone compound is one of the following compounds:

[0043] Compound 1,

[0044] Compound 2,

[0045] According to another aspect of the present invention, a method for preparing the above-mentioned phthalate-type benzofuranone compound is also provided, which comprises the following steps: reacting a first substrate represented by formula II and a second substrate represented by formula III in an organic solvent in the presence of a base to obtain a phthalate-type benzofuranone compound;

[0046]

[0047] Among them, R 1 , R 2 , R 3 and n have the same definitions as described above.

[0048] The above substrate can react in the presence of a base according to the following route:

[0049]

[0050] The phthalate-type benzofuranone compound prepared by the above preparation method has good carbon free radical scavenger function, and has the advantages of high antioxidant efficiency, good compatibility with the matrix, high molecular weight and not easy to migrate and escape, and has good application performance in polymer materials, especially in the field of plastic processing. In addition, the preparation method has a simple process, mild reaction conditions, high yield, and is suitable for large-scale application in industrial production.

[0051] In order to further improve the reaction efficiency, in a preferred embodiment, the molar ratio of the first substrate to the second substrate is 1:(2-4).

[0052] Preferably, the base is selected from an organic base and / or an inorganic base, preferably an organic base is selected from one or more of 4-dimethylaminopyridine, triethylamine and tri-n-butylamine, and an inorganic base is selected from one or more of sodium bicarbonate, sodium carbonate and potassium carbonate. In the presence of the above base, the reaction process is more efficient. More preferably, the base includes at least 4-dimethylaminopyridine; further preferably, the base is a mixture of 4-dimethylaminopyridine and triethylamine, and the molar ratio of the two is 1: (10-20). Using the above mixture of 4-dimethylaminopyridine and triethylamine can promote a more complete reaction and has more advantages in terms of efficiency, conversion rate, etc. More preferably, the molar ratio of the base to the second substrate is 1: 1-3.

[0053] In order to make the reaction process more stable, preferably, the organic solvent is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile and toluene.

[0054] According to another aspect of the present invention, the present invention also provides a polymer material antioxidant, which includes the above-mentioned phthalate ester benzofuranone compound. The above-mentioned phthalate ester benzofuranone compound has a good carbon free radical scavenger function, and has the advantages of high antioxidant efficiency, good compatibility with the matrix, high molecular weight and not easy to migrate and escape, and is used for polymer materials, especially for the field of plastic processing, and has good application performance. Accordingly, using the phthalate ester benzofuranone compound as an antioxidant is also conducive to improving the anti-aging performance of polymer materials.

[0055] In a preferred embodiment, the polymer material antioxidant is also at least one of a hindered amine antioxidant, a phosphite antioxidant, and a thioester antioxidant. The combined use of the above-mentioned phthalate-type benzofuranone compound and the phosphite antioxidant and / or the thioester antioxidant is conducive to more fully exerting the synergistic effect between the antioxidants, and the polymer material has better anti-aging performance. The above hindered amine antioxidants, phosphite antioxidants, and thioester antioxidants may be commonly used types in the art. For example, hindered phenol antioxidants include, but are not limited to, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (isooctyl), 2,2-oxalyl-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine, N,N'-hexamethylenebis(3,5-di-tert-butyl- The phosphite antioxidants include, but are not limited to, one or more of tris(2,4-di-tert-butylbenzene) phosphite, bis(2,4-di-tert-butylbenzene) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, triisodecyl phosphite, diisodecyl pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, diisodecyl diphenyl phosphite, triphenyl phosphite, diisodecyl monophenyl phosphite, tris(nonylphenyl) phosphite; the thioester antioxidants include, but are not limited to, one or more of pentaerythritol tetrakis(3-dodecylthiopropionate), distearyl thiodipropionate, didodecanol thiodipropionate, didotetradecyl thiodipropionate, and didridecanol thiodipropionate.

[0056] More preferably, the polymer material antioxidant includes phthalate benzofuranone compounds, hindered phenol antioxidants and phosphite antioxidants; preferably, the weight ratio of phthalate benzofuranone compounds, hindered phenol antioxidants and phosphite antioxidants is 1:(2-4):(2-4); further preferably, the polymer material antioxidant is a mixture of phthalate benzofuranone compounds, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite in a weight ratio of 1:(2-4):(2-4). The combined use of the above antioxidants has a more significant antioxidant effect.

[0057] According to another aspect of the present invention, there is further provided a polymer material, comprising a polymer material matrix and an antioxidant dispersed in the polymer material matrix, wherein the antioxidant is the above-mentioned polymer material antioxidant.

[0058] Exemplarily, the polymer material matrix is ​​a resin or a rubber; preferably, the resin is a polyolefin, a polyurethane, a polyether, a polyketone, a polystyrene, a polycarbonate, a polyacrylate, a polymethacrylate, a polyacetal, a halogen-containing polymer, a polyamide, a polyoxymethylene, a polyphenylene ether, a polyethylene terephthalate, a polysuccinate terephthalate, a polyacrylonitrile, a polybutadiene, a polystyrene, HIPS, ABS, MBS, an epoxy resin or an epoxy-crosslinked acrylic resin; preferably, the rubber is a natural rubber, a styrene-butadiene rubber, a chloroprene rubber, a butadiene rubber, an isoprene rubber, a nitrile rubber or a thermoplastic TPU.

[0059] In a preferred embodiment, the polymer material is PP, and the antioxidant includes the above-mentioned phthalate-type benzofuranone compound, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite; preferably, the amount of the antioxidant added is 0.01-0.15% of the weight of PP; preferably 0.02-0.12%. More preferably, the weight ratio of the phthalate-type benzofuranone compound, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite is 1:(2-4):(2-4), preferably 1:2:4 or 1:2.8:2.8. The combined use of the above-mentioned antioxidants has a more significant antioxidant effect, especially for PP, the effect is better.

[0060] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0061] Embodiment 1:

[0062] Synthesis of benzofuranone monomer Aa

[0063]

[0064] Take a 100mL three-necked flask, add 20.6g 2,4-di-tert-butylphenol (0.1mol, 1eq), 30mL dichloroethane, 16.3g 50% glyoxylic acid aqueous solution (0.11mol, 1.1eq) and 0.1g monohydrated p-toluenesulfonic acid at room temperature, heat to reflux reaction (about 80-85℃) for 5-7h, reflux and separate water with a water separator, and control by TLC until the raw material is basically reacted. Cool to room temperature, remove dichloroethane by desolventizing, add 80mL n-hexane to dissolve, wash twice with water, extract the aqueous phase with 30mL n-hexane once, combine the organic phases, wash with saturated brine, and dry over anhydrous sodium sulfate. Filter and desolventize to obtain 25.8g of orange-red viscous liquid, and the crude product A is directly used for the next step reaction. Take a 100mL three-necked flask, add the above crude product 13.1g (0.05mol), 2,6-dimethylphenol 6.1g (0.05mol), 30mL glacial acetic acid and 0.6mL methanesulfonic acid at room temperature, heat to reflux reaction (about 115-120℃) for 3-5h, and control by TLC until the raw materials are basically reacted. Cool to 5℃, solid precipitates, filter, wash the filter cake with glacial acetic acid and water, beat with ethanol, and dry to obtain product Aa, a white solid, melting point: 228-229℃, yield 90%.

[0065]

[0066] 1H NMR (400MHz, CDCl3) δ7.31 (d, J = 1.4 Hz, 1H), 7.03 (dd, J = 1.9, 1.1 Hz, 1H), 6.82 (s, 2H), 4.69 (s, 1H), 2.22 (s, 6H), 1.44 (s, 9H), 1.29 (s, 9H).

[0067] Embodiment 2:

[0068] Synthesis of benzofuranone monomer Ab

[0069]

[0070] Take a 100mL three-necked flask, add 20.6g 2,4-di-tert-butylphenol (0.1mol, 1eq), 30mL dichloroethane, 16.3g 50% glyoxylic acid aqueous solution (0.11mol, 1.1eq) and 0.1g monohydrated p-toluenesulfonic acid at room temperature, heat to reflux reaction (about 80-85℃) for 5-7h, reflux and separate water with a water separator, and control by TLC until the raw material is basically reacted. Cool to room temperature, remove dichloroethane by desolventizing, add 80mL n-hexane to dissolve, wash twice with water, extract the aqueous phase with 30mL n-hexane once, combine the organic phases, wash with saturated brine, and dry over anhydrous sodium sulfate. Filter and desolventize to obtain 25.9g of orange-red viscous liquid, and the crude product A is directly used for the next step reaction. Take a 100mL three-necked flask, add the above crude product 13.1g (0.05mol), 4-methylphenol (0.05mol), 30mL glacial acetic acid and 0.6mL methanesulfonic acid at room temperature, heat to reflux reaction (about 115-120℃) for 3-5h, and control by TLC until the raw materials are basically reacted. After the reaction is completed, cool it down, add 200ml water, extract with 200ml dichloromethane, wash with brine, dry with sodium sulfate, desolventize and purify by rapid column chromatography (eluent: ethyl acetate / petroleum ether = 1 / 5, Rf value 0.4), and obtain the product Ab, a white solid, melting point: 172-173℃, and the yield is about 80%.

[0071]

[0072] 1 H NMR(400MHz, CDCl3)δ7.33(d,J=1.5Hz,1H),7.10(s,1H),7.07–6.96(m,1H),6.84( d,J=8.4Hz,2H),6.16(s,1H),5.12(s,1H),2.23(s,3H),1.43(s,9H),1.31(s,9H).

[0073] Example 3

[0074] Take a 100mL three-necked flask, add benzofuranone monomer Aa (3.3mmol, 2.2eq), 10mL dichloromethane, triethylamine (3.3mmol, 2.2eq) and 30mg 4-dimethylaminopyridine (DMAP, 0.25mmol, 0.17eq), protect with nitrogen, stir and cool down. Add terephthaloyl chloride (1.5mmol, 1eq, dissolved in 10mL dichloromethane) dropwise at 5-10°C, and naturally warm to room temperature for reaction after addition. Control the reaction of the raw materials in TLC. Add water to separate, extract with dichloromethane, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, and separate by column chromatography to obtain the product compound 1 (eluent: ethyl acetate / petroleum ether = 1 / 5, Rf value 0.5): white solid, melting point: 277-278°C, yield 75%.

[0075]

[0076] 1H NMR (400MHz, CDCl3) δ8.39(s,4H),7.35(d,J=1.5Hz,2H),7.11(d,J=0.8Hz,2H),7.01(s,4H),4.80(s,2H),2.20(s,12H),1.45(s,18H),1.32(s,18H).

[0077] Example 4

[0078] The difference from Example 3 is that the amount of substrate added is different:

[0079] Take a 100mL three-necked flask, add benzofuranone monomer Aa (3mmol, 2eq), 10mL dichloromethane, triethylamine (3.3mmol, 2.2eq) and 30mg 4-dimethylaminopyridine (DMAP, 0.25mmol, 0.17eq), protect with nitrogen, stir and cool down. Add terephthaloyl chloride (1.5mmol, 1eq, dissolved in 10mL dichloromethane) dropwise at 5-10°C, and naturally warm to room temperature for reaction after addition. Control the reaction of the raw materials in TLC. Add water to separate, extract with dichloromethane, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, and separate by column chromatography to obtain the product compound 1 (eluent: ethyl acetate / petroleum ether = 1 / 5, Rf value 0.5): white solid, melting point: 277-278°C, yield 72%.

[0080] Example 5

[0081] The difference from Example 3 is that the amount of substrate added is different:

[0082] Take a 100mL three-necked flask, add benzofuranone monomer Aa (6mmol, 4eq), 10mL dichloromethane, triethylamine (3.3mmol, 2.2eq) and 30mg 4-dimethylaminopyridine (DMAP, 0.25mmol, 0.17eq), protect with nitrogen, stir and cool down. Add terephthaloyl chloride (1.5mmol, 1eq, dissolved in 10mL dichloromethane) dropwise at 5-10°C, and naturally warm to room temperature for reaction after addition. Control the reaction of the raw materials in TLC. Add water to separate, extract with dichloromethane, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, and separate by column chromatography to obtain the product compound 1 (eluent: ethyl acetate / petroleum ether = 1 / 5, Rf value 0.5): white solid, melting point: 277-278°C, yield 77%.

[0083] Example 6

[0084] The difference from Example 3 is that the amount of catalyst is different:

[0085] Take a 100mL three-necked flask, add benzofuranone monomer Aa (3.3mmol, 2.2eq), 10mL dichloromethane, triethylamine (3.23mmol, 2.16eq) and 30mg 4-dimethylaminopyridine (DMAP, 0.32mmol, 0.21eq), protect with nitrogen, stir and cool down. Add terephthaloyl chloride (1.5mmol, 1eq, dissolved in 10mL dichloromethane) dropwise at 5-10°C, and naturally warm to room temperature for reaction after addition. Control the reaction of the raw materials in TLC. Add water to separate, extract with dichloromethane, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, and separate by column chromatography to obtain the product compound 1 (eluent: ethyl acetate / petroleum ether = 1 / 5, Rf value 0.5): white solid, melting point: 277-278°C, yield 74%.

[0086] Example 7

[0087] The difference from Example 3 is that the amount of catalyst is different:

[0088] Take a 100mL three-necked flask, add benzofuranone monomer Aa (3.3mmol, 2.2eq), 10mL dichloromethane, triethylamine (3.38mmol, 2.25eq) and 30mg 4-dimethylaminopyridine (DMAP, 0.17mmol, 0.12eq), protect with nitrogen, stir and cool down. Add terephthaloyl chloride (1.5mmol, 1eq, dissolved in 10mL dichloromethane) dropwise at 5-10°C, and naturally warm to room temperature for reaction after addition. Control the reaction of the raw materials in TLC. Add water to separate, extract with dichloromethane, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, and separate by column chromatography to obtain the product compound 1 (eluent: ethyl acetate / petroleum ether = 1 / 5, Rf value 0.5): white solid, melting point: 277-278°C, yield 76%.

[0089] Example 8

[0090] Take a 100mL three-necked flask, add benzofuranone monomer Ab (3.3mmol, 2.2eq), 10mL dichloromethane, triethylamine (3.3mmol, 2.2eq) and 30mg 4-dimethylaminopyridine (DMAP), protect with nitrogen, stir and cool down. Add terephthaloyl chloride (1.5mmol, 1eq, dissolved in 10mL dichloromethane) dropwise at 5-10°C, and naturally warm to room temperature for reaction after addition. Control the reaction of the raw materials in TLC. Add water to separate, extract with dichloromethane, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, and separate by column chromatography to obtain the product compound 2 (eluent: ethyl acetate / petroleum ether = 1 / 5, Rf value 0.52): white solid, melting point: 267-268°C, yield 60%.

[0091]

[0092] 1 H NMR(400MHz, CDCl3)δ8.01(d,J=9.9Hz,4H),7.26(t,J=3.8Hz,2H),7.18–7.06(m,6H),6.97(d,J=0.9H z, 2H), 4.91 (d, J = 6.5Hz, 2H), 2.39 (d, J = 1.7Hz, 6H), 1.25 (d, J = 2.8Hz, 18H), 1.18 (d, J = 12.3Hz, 18H).

[0093] Application performance characterization:

[0094] Applied to PP anti-oxidation:

[0095] The polymer melt flow rate (MFR) is an important parameter reflecting the antioxidant performance of the antioxidant, and its change is an important parameter reflecting the processing stability of the polymer. Table 1 lists the effects of extrusion temperature and stabilizer on the MFR of polypropylene PP after multiple extrusions. Specific method: Compound 1 synthesized in Example 3, Compound 2 synthesized in Example 8, Irganox 1010, an antioxidant commonly used in the market, and antioxidant 168 (tris[2.4-di-tert-butylphenyl]phosphite), as well as the comparative compound All of them are added at the specified mass fraction ratio in the table and applied to the stabilization effect experiment of polypropylene PP (10 kg, homopolymer MI=2, PP contains 0.05% calcium stearate). After the materials are mixed evenly, they are put into a single screw extruder for extrusion, and the extrusion temperature is specified. After cooling, drying, pelletizing and sieving, the modified polypropylene is obtained; processing conditions: multiple extrusions, 20mm diameter single screw extruder, L / D=25. The MFR (g / 10min) of these modified polypropylenes is investigated, and the MFR is determined according to ISO1133: the conditions are 230℃ and 2.16kg. The results are shown in Table 1 below. It can be seen from Table 1 that with the increase of extrusion temperature, the effect of adding the ternary antioxidant system is better and better than the binary antioxidant system without adding compounds 1 and 2, and its total amount of addition (0.07%) is lower than the binary antioxidant system without adding compounds 1 and 2 (0.1%), which shows that compounds 1 and 2 play an important role in the stabilization process of PP. Moreover, compared with compound D1, although the only difference is in the benzofuranone ring substituent, it has a significant impact on its antioxidant properties. Compounds 1 and 2 in the present invention play a more favorable and significant role in the PP stabilization process.

[0096] Table 1

[0097]

[0098] Discoloration of polymers is a serious problem in practical applications of polymers. Table 2 lists the changes in the yellowness index (YI) of polypropylene PP after multiple extrusions. Specific method: Compound 1 synthesized in Example 3, Compound 2 synthesized in Example 8, commercially available antioxidant Irganox 1010, antioxidant 168 (tris[2.4-di-tert-butylphenyl]phosphite), and comparative compound

[0099] All of them are added in the proportion specified in the table according to the mass fraction, and are applied to the stabilization effect experiment of polypropylene PP (10 kg, homopolymer MI=2, PP contains 0.05% calcium stearate). After the materials are mixed evenly, they are put into a single screw extruder for extrusion, and the extrusion temperature is specified to be 280°C. After cooling, drying, pelletizing and sieving, modified polypropylene is obtained; processing conditions: multiple extrusions, 30mm diameter single screw extruder, L / D=25. The YI of these modified polypropylenes was investigated and determined according to ASTM1925-77. The results are shown in Table 2 below. It can be seen from Table 2 that with the increase in the number of extrusions, the degradation of PP is aggravated, and the color of the system gradually becomes heavier, but the control of PP color by the ternary antioxidant system with the addition of compounds 1 and 2 is significantly improved than that of the binary antioxidant system without the addition of compounds 1 and 2, and compared with compound D1, the improvement effect of compounds 1 and 2 of the present invention is particularly obvious.

[0100] Table 2

[0101]

[0102] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A phthalate-type benzofuranone compound, characterized in that: The compound has a structure shown in Formula I: Formula I Among them, R 1 , R 2 All are tert-butyl, n R 3 are each independently a methyl group, and n is an integer from 1 to 4.

2. The phthalate-type benzofuranone compound according to claim 1, characterized in that: The compound has a structure shown in Formula I-1 or Formula I-2: Formula I-1; Formula I-2.

3. The phthalate-type benzofuranone compound according to claim 1, characterized in that: The phthalate-type benzofuranone compound is one of the following compounds: ； 。 4. A method for preparing the phthalate-type benzofuranone compound according to any one of claims 1 to 3, characterized in that: The following steps are involved: In the presence of a base, reacting the first substrate represented by formula II and the second substrate represented by formula III in an organic solvent to obtain the phthalate-type benzofuranone compound; Formula II, Formula III Among them, R 1 , R 2 , R 3 and n have the same meaning as described in any one of claims 1 to 3.

5. The preparation method according to claim 4, characterized in that: The molar ratio of the first substrate to the second substrate is 1:(2-4); and / or, the base is selected from organic bases and / or inorganic bases; And / or, the molar ratio of the base to the second substrate is 1:1-3; And / or, the organic solvent is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile and toluene.

6. The preparation method according to claim 5, characterized in that: The organic base is selected from one or more of 4-dimethylaminopyridine, triethylamine and tri-n-butylamine, and the inorganic base is selected from one or more of sodium bicarbonate, sodium carbonate and potassium carbonate.

7. The preparation method according to claim 6, characterized in that: The base includes at least the 4-dimethylaminopyridine.

8. The preparation method according to claim 7, characterized in that: The base is a mixture of the 4-dimethylaminopyridine and the triethylamine, and the molar ratio of the two is 1: (10-20).

9. A polymer material antioxidant, characterized in that: The invention comprises the phthalate-type benzofuranone compound according to any one of claims 1 to 3.

10. The polymer material antioxidant according to claim 9, characterized in that: The polymer material antioxidant also includes at least one of a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant.

11. The polymer material antioxidant according to claim 10, characterized in that: The hindered phenol antioxidant includes one or more of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (isooctyl), 2,2-oxalyl-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine, and N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide); And / or, the phosphite antioxidant is one or more of tris(2,4-di-tert-butylbenzene) phosphite, bis(2,4-di-tert-butylbenzene) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, triisodecyl phosphite, diisodecyl pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, diisodecyl diphenyl phosphite, triphenyl phosphite, diisodecyl monophenyl phosphite, and tris(nonylphenyl) phosphite; And / or, the thioester antioxidant is one or more of pentaerythritol tetrakis (3-dodecylthiopropionate), distearyl thiodipropionate, didodecanol thiodipropionate, didetradecyl thiodipropionate, and distridecanol thiodipropionate.

12. The polymer material antioxidant according to claim 11, characterized in that: The polymer material antioxidant includes the phthalate ester type benzofuranone compound, the hindered phenol antioxidant and the phosphite antioxidant.

13. The polymer material antioxidant according to claim 12, characterized in that: The weight ratio of the phthalate-type benzofuranone compound, the hindered phenol antioxidant and the phosphite antioxidant is 1:(2-4):(2-4).

14. The polymer material antioxidant according to claim 13, characterized in that: The polymer material antioxidant is a mixture of the phthalate-type benzofuranone compound, the pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and the tris(2,4-di-tert-butylphenyl) phosphite in a weight ratio of 1:(2-4):(2-4).

15. A polymer material, comprising a polymer material matrix and an antioxidant dispersed in the polymer material matrix, characterized in that: The antioxidant is the polymer material antioxidant according to any one of claims 9 to 14.

16. The polymer material according to claim 15, characterized in that: The polymer material matrix is ​​resin or rubber.

17. The polymer material according to claim 16, characterized in that: The resin is polyolefin, polyurethane, polyether, polyketone, polycarbonate, polyacrylate, polymethacrylate, polyacetal, halogen-containing polymer, polyamide, polyoxymethylene, polyphenylene ether, polyethylene terephthalate, polysuccinate terephthalate, polyacrylonitrile, polybutadiene, polystyrene, HIPS, ABS, MBS, epoxy resin or epoxy resin cross-linked acrylic resin; and / or the rubber is natural rubber, styrene-butadiene rubber, chloroprene rubber, butadiene rubber, isoprene rubber, nitrile rubber or thermoplastic TPU.

18. The polymer material according to claim 17, characterized in that: The polymer material is PP, the antioxidant comprises the phthalate-type benzofuranone compound described in any one of claims 1 to 3, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylbenzene) phosphite; and / or the added amount of the antioxidant is 0.01-0.15% of the weight of PP.

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