Hindered phenol functional group-containing polyhedral oligomeric silsesquioxane as well as preparation method and application thereof

Abstract

The invention provides a hindered phenol functional group-containing polyhedral oligomeric silsesquioxane as well as a preparation method and application thereof. The hindered phenol functional group-containing polyhedral oligomeric silsesquioxane has one or more structures in the following formulas I-III: # imgabs 0 # imgabs 1 #, r1 and R2 are independently selected from hydrogen, alkyl, alkoxy, hydroxyalkyl, cycloalkyl, cycloalkyl alkyl, aryl, aralkyl, heterocyclic group, heterocyclic alkyl, carboxyl, ester group, acylamino, amino, amido, halogen, nitro, cyano, oxycarbonyl and aminocarbonyl; r3 and R4 are independently selected from alkylene groups having 0 to 20 carbons. The hindered phenol functional group-containing polyhedral oligomeric silsesquioxane is a novel antioxidant which is stable in structure, long in time, efficient and environment-friendly under the condition of low addition amount.

Description

Technical Field

[0001] The present invention belongs to the field of cage-shaped polyhedral oligomeric silsesquioxanes, and particularly relates to a cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups, a preparation method thereof, and an application thereof. Background Art

[0002] Currently, most hindered phenol antioxidants have problems such as low molecular weight, strong volatility, poor extraction resistance, and easy diffusion and migration from the polymer to the outside, resulting in the loss of their use effectiveness.

[0003] CN111040471B discloses that first, amino-functionalized silica nanoparticles are prepared, and then a hindered phenol antioxidant with a carboxyl group is grafted onto the surface of the silica nanoparticles through an amide bond by a chemical reaction to obtain an inorganic particle-supported hindered phenol antioxidant. This can reduce the migration and volatilization of the hindered phenol antioxidant and improve its extraction resistance, thereby enhancing the long-term anti-aging ability of the antioxidant. However, in this technology, the inorganic carrier, amino-functionalized silica nanoparticles, has a large size, an unclear structure, and a small number of effective functional groups, resulting in a low grafting rate of the hindered phenol antioxidant and an insufficiently obvious protective effect of the antioxidant.

[0004] CN 102206432B discloses that using an antioxidant as a solvent, a hindered phenol antioxidant molecule is chemically grafted onto nano-silica by a transesterification method under the action of a catalyst without a solvent, and the grafting amount is 2 wt% to 10 wt%. The prepared nano-silica with surface-grafted antioxidant molecules has good dispersibility in the polymer and can improve the mechanical properties and photo-oxidative aging resistance of the polymer material. In this technology, using the antioxidant as a solvent requires a large amount of antioxidant for the reaction, and a large amount of unreacted antioxidant needs to be removed during the subsequent solvent washing process, resulting in a low utilization rate of the antioxidant. The prepared nano-silica particles with surface-grafted hindered phenol antioxidant molecules have a large particle size, a low grafting rate of the hindered phenol antioxidant, and a large addition amount (3 wt% to 5 wt%), and the anti-aging protection effect on the polymer is not obvious enough.

[0005] A. Niemczyk et al. prepared alkyl-grafted cage-like polyhedral oligomeric silsesquioxanes (POSS), octakis({n-octyl}dimethylsilyloxy)silsesquioxane (POSS8) and octakis({n-octadecyl}dimethylsilyloxy)silsesquioxane (POSS18), which can be used as ultraviolet light stabilizers and / or antioxidants for polypropylene (PP). This is due to the good compatibility between the alkyl-modified POSS and PP. The uniformly dispersed modified POSS can fill the free volume of the material, limit the diffusion of oxygen, and may also inhibit the formation of oxidation products such as ketones and carboxylic acids, thereby improving the aging resistance of PP. However, the antioxidant performance and extraction resistance of the alkyl-grafted cage-like polyhedral oligomeric silsesquioxanes obtained by this technology need to be improved.

[0006] Therefore, further research on antioxidants is still needed in this field. Summary of the Invention

[0007] The main object of the present invention is to provide a cage-like polyhedral oligomeric silsesquioxane containing a hindered phenol functional group, its preparation method and application, so as to overcome the problem that the hindered phenol antioxidants are prone to diffuse and migrate from the polymer to the outside and lose their effectiveness when used as antioxidants.

[0008] To achieve the above object, the present invention provides a cage-like polyhedral oligomeric silsesquioxane containing a hindered phenol functional group, having one or more structures of the following formulas I to III:

[0009]

[0010]

[0011] Among them, R 1 and R 2 are independently selected from: hydrogen, alkyl, alkoxy, hydroxyalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclic group, heterocyclic group alkyl, carboxyl, ester group, amide group, amino, amine group, halogen, nitro, cyano, oxycarbonyl, aminocarbonyl;

[0012] R 3 and R 4 are independently selected from alkylene groups having 0-20 carbons.

[0013] The cage-like polyhedral oligomeric silsesquioxane containing a hindered phenol functional group according to the present invention, wherein, R 1 and R 2 each have 0-18 carbons, and R 3 and R 4 each have 0-6 carbons.

[0014] The cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups of the present invention, wherein, R 1 and R 2 at least one of them is a branched - chain alkyl group of C 3 -C 8 .

[0015] The cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups of the present invention, wherein, R 1 is H or methyl, R 2 is a branched - chain alkyl group of C 3 -C 8 ; and / or, R 3 is -CH 2 -CH 2 (-), R 4 is -CH 2 -CH 2 -CH 2 .

[0016] In order to achieve the above - mentioned purpose, the present invention also provides a preparation method of the above - mentioned cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups, which comprises the following steps:

[0017] Step 1, reacting a cage - type polyhedral oligomeric silsesquioxane containing halogen atoms with a hindered phenol compound containing a carboxylate group;

[0018] Step 2, post - treating the reaction mixture to obtain a cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups;

[0019] Among them, the cage - type polyhedral oligomeric silsesquioxane containing halogen atoms has one or more of the following structures of formula IV - VI, and the hindered phenol compound containing a carboxylate group has the following structure of formula VII:

[0020]

[0021]

[0022] R 1 and R 2 are independently selected from: hydrogen, alkyl, alkoxy, hydroxyalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclic group, heterocyclic group alkyl, carboxyl, ester group, amide group, amino, amine group, halogen, nitro, cyano, oxycarbonyl, aminocarbonyl;

[0023] R 3 and R 4 are independently selected from alkylene groups having 0 - 20 carbons;

[0024] X is selected from halogen elements;

[0025] M is selected from hydrogen element or metal elements.

[0026] The preparation method of the cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups, wherein the molar ratio of the cage - type polyhedral oligomeric silsesquioxane containing halogen atoms to the hindered phenol compound containing carboxylate is 1:(1 - 18).

[0027] The preparation method of the cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups, wherein the catalyst is selected from one of sodium iodide, potassium iodide, and potassium carbonate.

[0028] The preparation method of the cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups, wherein a catalyst is further added to the reaction in step 1, and the molar ratio of the catalyst to the cage - type polyhedral oligomeric silsesquioxane containing halogen atoms is (0 - 8):1.

[0029] The preparation method of the cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups, wherein the reaction temperature is 0℃ - 120℃, and the reaction time is 1 - 72 h.

[0030] In order to achieve the above - mentioned purpose, the present invention further provides the application of the above - mentioned cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups as an antioxidant.

[0031] The beneficial effects of the present invention:

[0032] The present invention provides a cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups, that is, a cage - type polyhedral oligomeric silsesquioxane containing T 8 、T 10 and T 12 cage - like structures or their mixtures, and the hindered phenol functional groups are connected to the organic substitution arms through ester bonds to form a high - molecular - weight antioxidant with a relative molecular mass of about 2000 - 6000 and a stable structure, solving the problem of easy migration and loss of small - molecular - weight hindered phenol compounds, being able to effectively improve the thermal - oxidative aging resistance of polymers, significantly extending the oxidation induction time of polymers, and having good dispersion, non - toxicity, low exudation, and strong stability in polymers. It is a new type of antioxidant that can achieve stable structure, long - term, high - efficiency, and environmentally friendly properties at low addition amounts. Description of the Drawings

[0033] Figure 1 It is the matrix - assisted laser desorption / ionization time - of - flight mass spectrum of the product of Example 3;

[0034] Figure 2 It is the matrix - assisted laser desorption / ionization time - of - flight mass spectrum of the product of Example 5. Detailed Embodiments

[0035] The technical solution of the present invention will be described in detail below. The following embodiments are implemented on the premise of the technical solution of the present invention, and the detailed implementation process is given. However, the protection scope of the present invention is not limited to the following embodiments. For the structures or experimental methods without specific conditions in the following embodiments, they are usually in accordance with conventional conditions.

[0036] The present invention provides a cage-shaped polyhedral oligomeric silsesquioxane containing a hindered phenol functional group, having one or more of the structures in the following formulas I to III:

[0037]

[0038]

[0039] Wherein, R 1 and R 2 are independently selected from: hydrogen, alkyl, alkoxy, hydroxyalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclic group, heterocyclic group alkyl, carboxyl, ester group, amide group, amino group, amine group, halogen, nitro, cyano, oxycarbonyl, aminocarbonyl;

[0040] R 3 and R 4 are independently selected from alkylene groups having 0-20 carbons.

[0041] The cage-shaped polyhedral oligomeric silsesquioxane containing a hindered phenol functional group of the present invention can be a pure substance, that is, having any one of the structures in formulas I to III; it can also be a mixture, having any two of the structures in formulas I to III or having all three structures in formulas I to III.

[0042] The cage-shaped polyhedral oligomeric silsesquioxane containing a hindered phenol functional group of the present invention can be used as an antioxidant for antioxidant protection during the polymerization, granulation, storage, processing, molding and use of polymer materials such as polymer materials. Further, the above polymer materials are plastics, for example, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethacrylate PMMA, ethylene-vinyl acetate copolymer PVA, polyamide (PA), polytetrafluoroethylene (TFE), etc.

[0043] Among the hindered phenol antioxidants immobilized on traditional inorganic carriers, the inorganic carriers are large in size and unclear in structure, and there are generally problems such as low grafting rate and insufficient protection effect. Different from traditional inorganic immobilization, the cage-shaped polyhedral oligomeric silsesquioxane used in the present invention has a clear chemical structure and a smaller size. Its Si-O-Si cage framework is small in size, with a diameter between several nanometers; at the same time, it has more abundant modifiable functional groups, enabling a higher grafting amount. The hindered phenol functional group content of the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups prepared in the present invention is high and the size is small, which can achieve long-term and efficient protection at low addition amounts, effectively improving the thermal oxidation resistance of polymers.

[0044] In addition, when preparing high molecular weight antioxidants containing hindered phenol functional groups in the prior art, if the direct synthesis method is used, the synthesis process is complex, the design is difficult, the reaction controllability is low, and a large amount of toxic solvents need to be used; if the polymer grafting method is used, a reactive polymer with good compatibility with the matrix needs to be selected, and the effective antioxidant loading will be significantly reduced after grafting, affecting its antioxidant ability. The preparation method of the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups provided by the present invention can realize a one-step reaction of the cage-shaped polyhedral oligomeric silsesquioxane and the hindered phenol compound by using group reaction, and then obtain the product after washing and drying. The preparation process is simple, the energy consumption is low, the operation is simple, and the product yield is high.

[0045] The cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups provided by the present invention can be a pure substance or a mixture, that is, a cage-shaped polyhedral oligomeric silsesquioxane of a T 8 、T 10 or T 12 cage structure, or a cage-shaped polyhedral oligomeric silsesquioxane mixture containing one or more of the cage structures of T 8 、T 10 and T 12 . The hindered phenol functional groups are connected to the organic substitution arms through ester bonds to form a high molecular weight antioxidant with a relative molecular weight of about 2000-6000 and a stable structure, solving the problem that small molecular weight hindered phenol compounds are easy to migrate and lose. The product of the present invention can effectively improve the thermal oxidation resistance of polymers, significantly extend the oxidation induction time of polymers, and the additive is well dispersed, non-toxic, not easy to exude, and stable in polymers. It is a new type of antioxidant that can achieve stable structure, long-term, high-efficiency, and environmentally friendly at low addition amounts.

[0046] In the present invention, R 1 and R 2 are the same or different. In one embodiment, R 1 and R 2 each have 0-18 carbons. In another embodiment, R 1 and R 2 are independently selected from C1 -C 18 alkyl group.

[0047] In one embodiment, at least one of R 1 and R 2 is a branched-chain alkyl group of C 3 -C 8 , such as isopropyl, tert-butyl, tert-pentyl, tert-hexyl, tert-octyl. In another embodiment, R 1 is H or methyl, and R 2 is a branched-chain alkyl group of C 3 -C 8 . In yet another embodiment, R 1 and R 2 are independently selected from branched-chain alkyl groups of C 3 -C 8 ; for example, both R 1 and R 2 are tert-butyl. At this time, the cage-type polyhedral oligomeric silsesquioxane containing a hindered phenol functional group of the present invention has the following structure:

[0048]

[0049]

[0050] In one embodiment, R 3 and R 4 of the present invention have 0-6 carbons respectively, that is, R 3 and R 4 are independently selected from alkylene groups of C 0 -C 6 . When R 3 or R 4 has 0 carbons, it indicates that R 3 or R 4 does not exist, and the carbonyl group is directly connected to the phenyl group or the silicon is directly connected to the oxygen. In another example, R 3 is an alkylene group -CH 2 -CH 2 - of C 2 , and R 4 is an alkylene group -CH 3 -CH 2 -CH 2 -CH 2 - of C 3 . In yet another example, R 0 is C 4 , that is, the carbonyl group is directly connected to the phenyl group, and R 3 is an alkylene group -CH 2 -CH 2 -CH 2 - of C

[0051] When R 1 and R 2 are both tert-butyl groups, R 3 is C 0 , that is, the carbonyl group is directly connected to the phenyl group, and R 4 is an alkylene group of C 3 -CH 2 -CH 2 -CH 2 -, the cage-type polyhedral oligomeric silsesquioxane containing a hindered phenol functional group of the present invention has the following structure:

[0052]

[0053] When R 1 and R 2 are both tert-butyl groups, R 3 is an alkylene group of C 2 -CH 2 -CH 2 -, and R 4 is an alkylene group of C 3 -CH 2 -CH 2 -CH 2 -, the cage-type polyhedral oligomeric silsesquioxane containing a hindered phenol functional group of the present invention has the following structure:

[0054]

[0055] The present invention also provides a preparation method of the above-mentioned cage-type polyhedral oligomeric silsesquioxane containing a hindered phenol functional group, which includes the following steps:

[0056] Step 1, reacting a cage-type polyhedral oligomeric silsesquioxane containing a halogen atom with a hindered phenol compound containing a carboxylate group;

[0057] Step 2, post-treating the reaction mixture to obtain a cage-type polyhedral oligomeric silsesquioxane containing a hindered phenol functional group;

[0058] Among them, the cage-type polyhedral oligomeric silsesquioxane containing a halogen atom has one or more of the following structures of Formula IV to VI, and the hindered phenol compound containing a carboxylate group has the following Formula VII structure:

[0059]

[0060]

[0061] R 1 and R 2Independently selected from: hydrogen, alkyl, alkoxy, hydroxyalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclic group, heterocyclic group alkyl, carboxyl, ester group, amide group, amino group, amine group, halogen, nitro, cyano, oxycarbonyl, aminocarbonyl;

[0062] R 3 and R 4 Independently selected from alkylene groups having 0 - 20 carbons;

[0063] X is selected from halogen elements;

[0064] M is selected from hydrogen element or metal element.

[0065] In one embodiment, a halogen - atom - containing cage - type polyhedral oligomeric silsesquioxane, a carboxylic - acid - root - containing hindered phenolic compound and a solvent are mixed and reacted. After the reaction, the mixture is post - treated to obtain a cage - type polyhedral oligomeric silsesquioxane containing a hindered phenol functional group, that is, the compounds represented by the structures of Formulas I - III. In another embodiment, after a halogen - atom - containing cage - type polyhedral oligomeric silsesquioxane, a carboxylic - acid - root - containing hindered phenolic compound and a solvent are mixed, a catalyst is further added and the reaction is carried out.

[0066] For the preferred structures of R 1 、R 2 、R 3 、R 4 , they have been described in detail above and will not be elaborated here. M is selected from hydrogen element or metal element, preferably selected from alkali metal elements such as sodium and potassium.

[0067] In one embodiment, the solvent is selected from one or more of common solvents such as N,N - dimethylformamide, dichloromethane, water, acetonitrile, tetrahydrofuran, acetone, ethanol, ethyl acetate, dimethyl sulfoxide, etc. In the mixed solution of the halogen - atom - containing cage - type polyhedral oligomeric silsesquioxane and the carboxylic - acid - root - containing hindered phenolic compound and the solvent, the molar concentration of the halogen - atom - containing cage - type polyhedral oligomeric silsesquioxane in the solvent is 0.01 - 1.0 mo1 / L, preferably 0.02 - 0.2 mol / L.

[0068] In one embodiment, the molar ratio of the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane to the carboxylate group-containing hindered phenolic compound is 1:(1 - 18). Specifically, if the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane is selected from formula (IV) and the carboxylate group-containing hindered phenolic compound is selected from formula (VII), the molar ratio of the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane to the carboxylate group-containing hindered phenolic compound is 1:(8 - 12), preferably 1:(8.4 - 9.6); if the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane is selected from formula (V) and the carboxylate group-containing hindered phenolic compound is selected from formula (VII), the molar ratio of the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane to the carboxylate group-containing hindered phenolic compound is 1:(10 - 15), preferably 1:(10.4 - 12.6); if the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane is selected from formula (VI) and the carboxylate group-containing hindered phenolic compound is selected from formula (VII), the molar ratio of the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane to the carboxylate group-containing hindered phenolic compound is 1:(12 - 18), preferably 1:(12.4 - 14.6).

[0069] In one embodiment, the catalyst of the present invention is selected from iodine-containing inorganic salts such as sodium iodide and potassium iodide, and potassium carbonate, etc. In another embodiment, the catalyst of the present invention is potassium iodide. The molar ratio of the catalyst to the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane is (0 - 8):1, preferably (0 - 4):1. When this molar ratio is 0, it means that the reaction can proceed without adding a catalyst.

[0070] In one embodiment, the reaction temperature of the present invention is 0°C - 120°C, the reaction time is 1 - 72 h, preferably reacting at 60 - 80°C for 4 - 7 h.

[0071] In one embodiment, the post-treatment includes cooling the reaction system to room temperature, adding it to an aqueous solution to precipitate the product, centrifuging, suction filtering, washing, rotary evaporation, and drying to obtain the product. A methanol solution can be used for washing to dissolve the product and filter out insoluble substances. The drying can be vacuum drying, with a temperature of 20 - 50°C and a vacuum degree of -0.1 to -0.05 MPa.

[0072] In a specific embodiment, the post-treatment includes: after cooling the reaction system to room temperature, pouring the reaction system into deionized water to precipitate a solid, filtering to obtain the solid, washing it with deionized water, then dissolving the obtained solid crude product in methanol, adsorbing residual moisture with saturated anhydrous magnesium sulfate, filtering out insoluble substances, then performing rotary evaporation on the filtrate, collecting the solid, and drying it in a vacuum oven at 50°C for 24 h to obtain the target product, a cage-type polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups.

[0073] The present invention utilizes the smaller size of several nanometers of cage-like polyhedral oligomeric silsesquioxane (POSS), more abundant modifiable functional groups, and a substituent structure suitable for customization, and prepares a cage-like polyhedral oligomeric silsesquioxane containing hindered phenol functional groups through a chemical reaction with low energy consumption, simple operation, and high product yield. As a new antioxidant that can achieve long-term and efficient protection at low addition amounts, it can effectively improve the thermal oxidation aging resistance of polymers, significantly extend the oxidation induction time of polymers, and it is well-dispersed in polymers, not easily exuded, has high stability, and strong extraction resistance.

[0074] The technical solution of the present invention will be further described in detail through specific embodiments below.

[0075] Source of raw materials or equipment:

[0076] Raw materials:

[0077] Cage-like polyhedral oligomeric silsesquioxane containing chlorine atoms: Prepared by itself according to the method shown in the public literature (Journal of Organometallic Chemistry, 1995, 489(1): 185-194.). The synthesis steps are as follows: First, 450 mL of methanol and 22.5 mL of concentrated hydrochloric acid are magnetically stirred evenly in a 1 L three-necked round-bottom flask, and then 19.9 g (0.1 mol) of 3-chloropropyltrimethoxysilane monomer is added. The mixture is stirred at room temperature for at least 5 weeks (840 h). After the reaction is completed, the solid product is filtered and washed with methanol, and a white powder product is obtained after drying, with a yield of 35%.

[0078] Cage-like polyhedral oligomeric silsesquioxane containing iodine atoms: 36 g of sodium iodide (0.24 mol) and 10.36 g of cage-like polyhedral oligomeric silsesquioxane containing chlorine atoms (0.1 mol) are dissolved in 330 ml of anhydrous acetone, magnetically stirred, and refluxed at an oil bath temperature of 65 °C for 72 h. After the reaction is completed, the acetone solvent is removed by rotary evaporation, and the crude product is washed with water and ethyl acetate respectively, and a white powder is obtained after filtration and vacuum drying at 70 °C, with a yield of 90.5%.

[0079] 3-Chloropropyltrimethoxysilane: Beijing Innochem Chemical Reagent Co., Ltd., molecular weight 198.72 g / mol, purity 98%.

[0080] 3,5-Di-tert-butyl-4-hydroxybenzoic acid: Aladdin Reagent Co., Ltd. (Aladdin), molecular weight 250.3 g / mol, purity 98%.

[0081] 3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid: Aladdin Reagent Co., Ltd. (Aladdin), molecular weight 278.4 g / mol, purity 98%.

[0082] Sodium 3,5-di-tert-butyl-4-hydroxybenzoate: At room temperature, 30 mmol of sodium hydroxide was added to a tetrahydrofuran solution containing 30 mmol of 3,5-di-tert-butyl-4-hydroxybenzoic acid. The reaction mixture was stirred magnetically for 3 h, and then the solvent was removed by rotary evaporation to obtain a white solid product with a yield of 98.1%.

[0083] Potassium 3,5-di-tert-butyl-4-hydroxybenzoate: At room temperature, 30 mmol of potassium hydroxide was added to a tetrahydrofuran solution containing 30 mmol of 3,5-di-tert-butyl-4-hydroxybenzoic acid. The reaction mixture was stirred magnetically for 3 h, and then the solvent was removed by rotary evaporation to obtain a white solid product with a yield of 90.1%.

[0084] Sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate: At room temperature, 30 mmol of sodium hydroxide was added to a tetrahydrofuran solution containing 30 mmol of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid. The reaction mixture was stirred magnetically for 3 h, and then the solvent was removed by rotary evaporation to obtain a white solid product with a yield of 95.7%.

[0085] Potassium 3,5-di-tert-butyl-4-hydroxyphenylpropionate: At room temperature, 30 mmol of potassium hydroxide was added to a tetrahydrofuran solution containing 30 mmol of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid. The reaction mixture was stirred magnetically for 3 h, and then the solvent was removed by rotary evaporation to obtain a white solid product with a yield of 93.2%.

[0086] 3-(3-tert-Butyl-4-hydroxy-5-methylphenyl)propanoic acid: Molecular weight 236.3 g / mol, purity 95%.

[0087] Sodium 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate: At room temperature, 30 mmol of sodium hydroxide was added to a tetrahydrofuran solution containing 30 mmol of 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid. The reaction mixture was stirred magnetically for 3 h, and then the solvent was removed by rotary evaporation to obtain a white solid product with a yield of 94.1%.

[0088] 3-(3-(2H-Benzotriazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propanoic acid: Shanghai Macklin Biochemical Co., Ltd., molecular weight 339.39 g / mol, purity 97%.

[0089] Sodium 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionate: At room temperature, 30 mmol of sodium hydroxide was added to a methanol solution containing 30 mmol of 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionic acid. The reaction mixture was stirred magnetically for 5 h, and then the solvent was removed by rotary evaporation to obtain a white solid product with a yield of 92.0%.

[0090] 3-(3,4,5-Trihydroxyphenyl)propionic acid: Aurora Fine Chemicals LLC (USA), molecular weight 198.175 g / mol, purity 98%.

[0091] 3-(4-Hydroxy-3,5-dimethoxyphenyl)propionic acid: Accela ChemBioScience (Shanghai) Co., Ltd., molecular weight 226.23 g / mol, purity 97%.

[0092] Sodium hydroxide: Beijing Tongguang Fine Chemical Co., analytical pure.

[0093] Potassium hydroxide: Beijing Tongguang Fine Chemical Co., analytical pure.

[0094] Potassium iodide: Macklin, analytical pure, content ≥ 99.0%.

[0095] Concentrated hydrochloric acid: Sinopharm Chemical Reagent Co., Ltd. Beijing, content 36.0 - 38.0%.

[0096] Methanol: Concord Technology Co., Ltd., extra pure grade, purity ≥ 99.7%.

[0097] Tetrahydrofuran: Concord, analytical pure, purity ≥ 99.5%.

[0098] Anhydrous N,N-dimethylformamide: Beijing Innochem Science & Technology Co., Ltd., water ≤ 50 ppm, purity 99.9%.

[0099] Deionized water: Self-made by the Institute of Chemistry, Chinese Academy of Sciences.

[0100] Polypropylene: Inner Mongolia Huhehaote Petrochemical Co., Ltd., grade T30S, melt index (230 °C) 3.2 g / 10 min.

[0101] Antioxidant 1010: Ciba Specialty Chemicals Inc., purity 99%, molecular weight 1173.7 g / mol.

[0102] Antioxidant 168: Ciba Specialty Chemicals Inc., purity 99%, molecular weight 646.9 g / mol.

[0103] Equipment: Vacuum oven, HAAKE MiniLabⅡ rheometer, molding press, differential scanning calorimeter (Diamond DSC)

[0104] Neither the vacuum oven nor the film press is a dedicated equipment.

[0105] Differential scanning calorimeter: Diamond model differential scanning calorimeter of Perkin-Elmer Company, USA, and it is used for the oxidation induction time test.

[0106] HAAKE MiniLabⅡ rheometer: HAAKE MiniLabⅡ rheometer of ThermoFisher Scientific Company, Germany, and its extrusion unit is used for melt blending.

[0107] Evaluation and analysis methods:

[0108] Oxidation induction time test: The test is carried out using Diamond DSC of Perkin-Elmer Company, USA. The test is carried out according to the method shown in ISO11357-6. The test sample is a thin film sample with a thickness of 600μm and a mass of about 11±1mg. Three samples are randomly taken for each sample for testing. The specific test conditions are as follows: The sample is placed in the DSC container, heated from 50℃ to the test temperature at a rate of 20℃ / min under a nitrogen atmosphere, held at a constant temperature for 3min, then the atmosphere is switched to an oxygen atmosphere with an oxygen flow rate of 50ml / min, and held at a constant temperature at the test temperature until an exothermic peak appears due to oxidation of the sample, and the experiment is stopped. The extrapolated onset time of the oxidation exotherm is calculated using the software on DSC Diamond. The time from the switch from the nitrogen atmosphere to the oxygen atmosphere to the extrapolated onset time of the oxidation exotherm is the oxidation induction time of the sample, and this is used to measure the thermal oxidation stability of the material.

[0109] Solvent extraction resistance experiment: The extraction resistance performance of the compound dispersed in the polymer matrix is evaluated by monitoring the change of the oxidation induction period of the PP sample after Soxhlet extraction for different times. The Soxhlet extraction device containing the PP sample is immersed in an oil bath at 50℃ for heating and maintaining the temperature, and dichloromethane is used as the Soxhlet extraction solvent. After an appropriate extraction time, the PP sample is taken out and dried in an air circulation oven at 80℃ for about 10 minutes to remove the residual solvent, and then the oxidation induction time test is carried out.

[0110] In the present invention, except for the content clearly stated, any matters or things not mentioned shall directly apply to those known in the art without any changes. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby shall be regarded as part of the original disclosure or original record of the present invention, and shall not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider that the combination is obviously unreasonable.

[0111] All features disclosed in the present invention can be combined arbitrarily, and these combinations shall be understood as the content disclosed or recorded in the present invention, unless those skilled in the art consider that the combination is obviously unreasonable.

[0112] In the present invention, the alkylene group refers to a free divalent atomic group formed by removing two hydrogen atoms from the same or different two carbons of an alkane. For example, the alkylene group of C 2 can be -CH 2 -CH 2 - or -CH(CH 3 )-, and the alkylene group of C 3 is -CH 2 -CH 2 -CH 2 - or -CH(CH 3 )-CH 2 - or -CH 2 -CH(CH 3 ).

[0113] In the present invention, the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane is selected from Formulas IV to VI, which respectively represent the cage structures of cage-type polyhedral oligomeric silsesquioxane T 8 , T 10 , T 12 . However, since some carboxylate-containing hindered phenol compounds can catalyze the rearrangement of the cage structure of individual halogen atom-containing cage-type polyhedral oligomeric silsesquioxanes during the reaction; therefore, when the catalytic rearrangement activity of the carboxylate-containing hindered phenol compound is greater than the cage structure stability of the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane, regardless of which structure ((IV) to (VI)) the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane is selected from T 8 , T 10 , T 12 , the resulting mixture of cage-type polyhedral oligomeric silsesquioxanes containing hindered phenol functional groups contains T 8 , T 10 , T 12Multiple cage structures; when the cage structure stability of the halogen - containing cage - type polyhedral oligomeric silsesquioxane is greater than the catalytic rearrangement activity of the carboxylate - containing hindered phenolic compound, the obtained cage - type polyhedral oligomeric silsesquioxane containing hindered phenol functional groups has the same structure as the cage - type polyhedral oligomeric silsesquioxane with halogen atoms selected before the reaction.

[0114] Example 1

[0115] In this embodiment, the halogen - containing cage - type polyhedral oligomeric silsesquioxane is selected from formula (IV), X is a chlorine atom, and R 4 is C 3 alkylene - CH 2 -CH 2 -CH 2 -; the carboxylate - containing hindered phenolic compound is selected from general formula (VII), which is sodium 3,5 - di - tert - butyl - 4 - hydroxybenzoate, M is sodium, and R 1 and R 2 are tert - butyl - C(CH 3 ) 3 , R 3 is C 0 .

[0116]

[0117] Add 2.08 g of the chlorine - containing cage - type polyhedral oligomeric silsesquioxane, 4.9 g of sodium 3,5 - di - tert - butyl - 4 - hydroxybenzoate, and 60 ml of anhydrous N,N - dimethylformamide into a 150 - mL three - necked flask. Then add 1 g of the catalyst potassium iodide. Under a nitrogen atmosphere, heat the reaction system to 80 °C, keep stirring for 5 h, and then cool it to room temperature naturally. Then pour the reaction system into 300 mL of deionized water. The product precipitates from the solution. Filter out the solid. Unreacted sodium 3,5 - di - tert - butyl - 4 - hydroxybenzoate, the catalyst, and the generated NaCl are removed in the solution. Wash the solid with deionized water. Dry the solid in a vacuum oven at a temperature of 40 °C and a vacuum degree of - 0.1 to - 0.05 MPa for 24 h to remove moisture. Then dissolve the obtained solid crude product in methanol by stirring at room temperature, filter out the insoluble unreacted chlorine - containing cage - type polyhedral oligomeric silsesquioxane, and then remove the methanol in the filtrate by rotary evaporation. Collect the solid and dry it in a vacuum oven at a temperature of 40 °C and a vacuum degree of - 0.1 to - 0.05 MPa for 24 h to obtain 4.7 g of the target product, the cage - type polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups (yield 85%).

[0118] Example 2

[0119] In this embodiment, the halogen - containing cage - type polyhedral oligomeric silsesquioxane is selected from formula (IV), X is a chlorine atom, and R 4 is C 3The alkylene -CH 2 -CH 2 -CH 2 -; The carboxylate - containing hindered phenolic compound is of the general formula (VII), which is potassium 3,5 - di - tert - butyl - 4 - hydroxybenzoate, M is potassium, R 1 and R 2 are tert - butyl - C(CH 3 ) 3 , R 3 is C 0 .

[0120]

[0121] 2.08 g of chlorine - atom - containing cage - type polyhedral oligomeric silsesquioxane, 5.2 g of potassium 3,5 - di - tert - butyl - 4 - hydroxybenzoate, and 60 ml of anhydrous N,N - dimethylformamide were added to a 150 - mL three - necked flask, and then 1 g of catalyst potassium iodide was added. Under a nitrogen atmosphere, the reaction system was heated to 80 °C, stirred for 6 h while maintaining the temperature, and then naturally cooled to room temperature. Then the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out. Unreacted potassium 3,5 - di - tert - butyl - 4 - hydroxybenzoate, the catalyst, and the generated KCl were all removed in the solution. The solid was washed with deionized water, and the solid was dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of - 0.1 to - 0.05 MPa for 24 h to remove moisture. Then the obtained solid crude product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted chlorine - atom - containing cage - type polyhedral oligomeric silsesquioxane was filtered out. Then the methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of - 0.1 to - 0.05 MPa for 24 h to obtain 4.9 g of the target product, the cage - type polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups (yield 89%).

[0122] Example 3

[0123] In this embodiment, the halogen - atom - containing cage - type polyhedral oligomeric silsesquioxane is selected from the formula (IV), X is a chlorine atom, R 4 is C 3 The alkylene -CH 2 -CH 2 -CH 2 -; The carboxylate - containing hindered phenolic compound is of the general formula (VII), which is potassium 3,5 - di - tert - butyl - 4 - hydroxyphenylpropionate, M is potassium, R 1 and R 2 are tert - butyl - C(CH 3 ) 3 , R 3 is C 2 The alkylene -CH 2 -CH 2-.

[0124]

[0125] 2.08 g of chlorine atom-containing cage-shaped polyhedral oligomeric silsesquioxane, 5.7 g of potassium 3,5-di-tert-butyl-4-hydroxyphenyl propionate, and 60 ml of anhydrous N,N-dimethylformamide were added to a 150 mL three-necked flask. Then, 1 g of catalyst potassium iodide was added. Under a nitrogen atmosphere, the reaction system was heated to 80 °C, stirred at a constant temperature for 7 h, and then naturally cooled to room temperature. Then, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out. Unreacted potassium 3,5-di-tert-butyl-4-hydroxyphenyl propionate, the catalyst, and the generated KCl were all removed in the solution. The solid was washed with deionized water, and the solid was dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of -0.1 to -0.05 MPa for 24 h to remove water. Then, the obtained solid crude product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted chlorine atom-containing cage-shaped polyhedral oligomeric silsesquioxane was filtered out. Then, the methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of -0.1 to -0.05 MPa for 24 h to obtain 4.9 g of the target product, a cage-shaped polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups (yield 83%).

[0126] Figure 1 It is the matrix-assisted laser desorption / ionization time-of-flight mass spectrum of the product of Example 3. It can be seen from this mass spectrum that the method of the present invention has indeed synthesized the target product.

[0127] Example 4

[0128] In this embodiment, the halogen atom-containing cage-shaped polyhedral oligomeric silsesquioxane is selected from formula (IV), X is a chlorine atom, and R 4 is an alkylene group -CH 3 -CH 2 -CH 2 -CH 2 -; the carboxylic acid root-containing hindered phenol compound is selected from the general formula (VII), which is sodium 3,5-di-tert-butyl-4-hydroxyphenyl propionate, M is sodium, and R 1 and R 2 are tert-butyl -C(CH 3 ) 3 , and R 3 is an alkylene group -CH 2 -CH 2 -CH 2 -.

[0129]

[0130] Add 2.08 g of a chlorine atom-containing cage-like polyhedral oligomeric silsesquioxane, 5.4 g of sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, and 60 ml of anhydrous N,N-dimethylformamide into a 150 mL three-necked flask. Then add 1 g of potassium iodide as a catalyst. Under a nitrogen atmosphere, heat the reaction system to 80 °C, stir for 6 h while maintaining the temperature, and then naturally cool to room temperature. Next, pour the reaction system into 300 mL of deionized water. The product precipitates from the solution. Filter out the solid. Unreacted sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, the catalyst, and the NaCl generated during the reaction are all removed in the solution. Wash the solid with deionized water. Dry the solid in a vacuum oven at 40 °C with a vacuum degree of -0.1 to -0.05 MPa for 24 h to remove moisture. Then dissolve the obtained solid crude product in methanol by stirring at room temperature, filter out the insoluble unreacted chlorine atom-containing cage-like polyhedral oligomeric silsesquioxane, and then remove the methanol in the filtrate by rotary evaporation. Collect the solid and dry it in a vacuum oven at 40 °C with a vacuum degree of -0.1 to -0.05 MPa for 24 h to obtain 5.4 g of the target product, a cage-like polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups (yield 91%).

[0131] Example 5

[0132] In this embodiment, the halogen atom-containing cage-like polyhedral oligomeric silsesquioxane is selected from formula (IV), X is an iodine atom, and R 4 is an alkylene group of C 3 -CH 2 -CH 2 -CH 2 -; the carboxylic acid root-containing hindered phenol compound is selected from the general formula (VII), which is 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, M is hydrogen, and R 1 and R 2 are tert-butyl -C(CH 3 ) 3 , and R 3 is an alkylene group of C 2 -CH 2 -CH 2 -.

[0133]

[0134] In a 150 mL three-necked flask, 3.55 g of a cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms, 5.1 g of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, and 60 mL of anhydrous N,N-dimethylformamide were added. Then, 4.5 g of potassium carbonate was added as an acid-binding agent. Under a nitrogen atmosphere, the reaction system was heated to 30 °C, stirred for 24 h while maintaining the temperature, and then naturally cooled to room temperature. Subsequently, the reaction system was poured into 300 mL of an aqueous sodium hydroxide solution, and the product precipitated from the solution. The solid was filtered out. Unreacted 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, the acid-binding agent, and the potassium iodide generated during the reaction were all removed from the solution. The solid was washed with deionized water, and then dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of -0.1 to -0.05 MPa for 24 h to remove moisture. The obtained crude solid product was then stirred and dissolved in methanol at room temperature, and the insoluble unreacted cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms was filtered out. Then, the methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of -0.1 to -0.05 MPa for 24 h to obtain 5.2 g of a pure product of the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups (yield 87%).

[0135] Figure 2 It is the matrix-assisted laser desorption / ionization time-of-flight mass spectrum of the product of Example 5. From this mass spectrum, it can be seen that the method of the present invention has indeed synthesized the target product.

[0136] Example 6

[0137] In this embodiment, the cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms is selected from formula (IV), X is a chlorine atom, and R 4 is an alkylene group of C 3 -CH 2 -CH 2 -CH 2 -; the hindered phenol compound containing a carboxylate group is selected from the general formula (VII), which is sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, M is sodium, and R 1 and R 2 are tert-butyl groups -C(CH 3 ) 3 , and R 3 is an alkylene group of C 2 -CH 2 -CH 2 -.

[0138]

[0139] In a 150 mL three-necked flask, 3.55 g of a cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms, 5.4 g of sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, and 60 mL of anhydrous N,N-dimethylformamide were added. No catalyst or acid-binding agent was added. Under a nitrogen atmosphere, the reaction system was heated to 50 °C, stirred for 10 h while maintaining the temperature, and then naturally cooled to room temperature. Then, the reaction system was poured into 300 mL of deionized water. The product precipitated from the solution, and the solid was filtered out. Unreacted sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate and sodium iodide generated by the reaction were removed in the solution. The solid was washed with deionized water and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to remove moisture. Then, the obtained crude solid product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms was filtered out. Then, the methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to obtain 5.4 g of a pure product of a cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups (yield 90%).

[0140] Example 7

[0141] In this embodiment, the cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms is selected from formula (IV), X is an iodine atom, and R 4 is an alkylene group of C 3 -CH 2 -CH 2 -CH 2 -; the hindered phenol compound containing a carboxylate group is selected from the general formula (VII), which is potassium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, M is potassium, and R 1 and R 2 are tert-butyl -C(CH 3 ) 3 , R 3 is an alkylene group of C 2 -CH 2 -CH 2 -.

[0142]

[0143] In a 150 mL three-necked flask, 3.55 g of a cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms, 5.7 g of potassium 3,5-di-tert-butyl-4-hydroxyphenyl propionate, and 60 mL of anhydrous N,N-dimethylformamide were added. No catalyst was added. Under a nitrogen atmosphere, the reaction system was heated to 60 °C, stirred for 5 h while maintaining the temperature, and then naturally cooled to room temperature. Then, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out. Unreacted potassium 3,5-di-tert-butyl-4-hydroxyphenyl propionate and the generated KCl were removed in the solution. The solid was washed with deionized water, and the solid was dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of -0.1 to -0.05 MPa for 24 h to remove moisture. Then, the obtained solid crude product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms was filtered out. Then, the methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of -0.1 to -0.05 MPa for 24 h to obtain 4.9 g of a pure product of a cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups (yield 83%).

[0144] Example 8

[0145] In this embodiment, the cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms is selected from formula (VI), X is a chlorine atom, and R 4 is an alkylene group of C 3 -CH 2 -CH 2 -CH 2 -; the hindered phenol compound containing a carboxylate group is selected from the general formula (VII), which is sodium 3,5-di-tert-butyl-4-hydroxybenzoate, M is sodium, and R 1 and R 2 are tert-butyl -C(CH 3 ) 3 , R 3 is an alkylene group of C 2 -CH 2 -CH 2 -.

[0146]

[0147] In a 150 mL three-necked flask, 2.08 g of a chlorine atom-containing cage-like polyhedral oligomeric silsesquioxane, 5.4 g of sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, and 50 mL of anhydrous N,N-dimethylformamide were added. Then, 1 g of the catalyst potassium iodide was added. Under a nitrogen atmosphere, the reaction system was heated to 80 °C, stirred for 6 h while maintaining the temperature, and then naturally cooled to room temperature. Subsequently, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out, and unreacted sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, the catalyst, and the NaCl generated during the reaction were all removed from the solution. The solid was washed with deionized water, and the solid was dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of -0.1 to -0.05 MPa for 24 h to remove moisture. Then, the obtained solid crude product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted chlorine atom-containing cage-like polyhedral oligomeric silsesquioxane was filtered out. The methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at a temperature of 40 °C and a vacuum degree of -0.1 to -0.05 MPa for 24 h to obtain 4.7 g of the target product, a cage-like polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups (yield 79%).

[0148] Example 9

[0149] In this embodiment, the halogen atom-containing cage-like polyhedral oligomeric silsesquioxane is selected from formula (VI), X is a chlorine atom, and R 4 is an alkylene group -CH 3 -CH 2 -CH 2 -CH 2 -; the hindered phenol compound containing a carboxylate group is selected from the general formula (VII), which is sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, M is sodium, and R 1 and R 2 are tert-butyl groups -C(CH 3 ) 3 , and R 3 is an alkylene group -CH 2 -CH 2 -CH 2 -.

[0150]

[0151] In a 150 mL three-necked flask, 3.55 g of a cage-like polyhedral oligomeric silsesquioxane containing iodine atoms, 5.4 g of sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, and 50 mL of anhydrous N,N-dimethylformamide were added. No catalyst or acid-binding agent was added. Under a nitrogen atmosphere, the reaction system was heated to 50 °C, stirred for 10 h while maintaining the temperature, and then naturally cooled to room temperature. Then, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out. Unreacted sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate and the sodium iodide generated by the reaction were removed in the solution. The solid was washed with deionized water and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to remove moisture. Then, the obtained solid crude product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted cage-like polyhedral oligomeric silsesquioxane containing iodine atoms was filtered out. The methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to obtain 4.5 g of the target product, a pure cage-like polyhedral oligomeric silsesquioxane containing hindered phenol functional groups (yield 75%).

[0152] Example 10

[0153] In this embodiment, the cage-like polyhedral oligomeric silsesquioxane containing halogen atoms is selected from formula (V), X is an iodine atom, and R 4 is an alkylene group -CH 3 -CH 2 -CH 2 -CH 2 -; the hindered phenol compound containing a carboxylate group is selected from the general formula (VII), which is sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, M is sodium, and R 1 and R 2 are tert-butyl groups -C(CH 3 ) 3 , and R 3 is an alkylene group -CH 2 -CH 2 -CH 2 -.

[0154]

[0155] In a 150 mL three-necked flask, 3.55 g of a cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms, 5.4 g of sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, and 50 mL of anhydrous N,N-dimethylformamide were added. No catalyst or acid-binding agent was added. Under a nitrogen atmosphere, the reaction system was heated to 60 °C, stirred for 6 h while maintaining the temperature, and then naturally cooled to room temperature. Then, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out. Unreacted sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate and the sodium iodide generated during the reaction were removed in the solution. The solid was washed with deionized water and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to remove moisture. Then, the obtained solid crude product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms was filtered out. The methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to obtain 5.3 g of the target product, a pure cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups (yield 88%).

[0156] Example 11

[0157] In this embodiment, the cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms is selected from formula (IV), X is a chlorine atom, and R 4 is an alkylene group of C 3 -CH 2 -CH 2 -CH 2 -; the hindered phenol compound containing a carboxylate group is selected from the general formula (VII), which is sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, M is sodium, and R 1 is a tert-butyl group -C(CH 3 ) 3 , R 2 is a methyl group -CH 3 , R 3 is an alkylene group of C 2 -CH 2 -CH 2 -.

[0158]

[0159] 2.08 g of a chlorine atom-containing cage-like polyhedral oligomeric silsesquioxane, 4.6 g of sodium 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and 60 mL of anhydrous N,N-dimethylformamide were added to a 150 mL three-necked flask. Then, 1 g of potassium iodide as a catalyst was added. Under a nitrogen atmosphere, the reaction system was heated to 80 °C, stirred for 5 h while maintaining the temperature, and then naturally cooled to room temperature. Subsequently, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out. Unreacted sodium 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, the catalyst, and the generated NaCl were removed in the solution. The solid was washed with deionized water and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to remove moisture. Then, the obtained solid crude product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted chlorine atom-containing cage-like polyhedral oligomeric silsesquioxane was filtered out. The methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to obtain 4.2 g of the target product, a cage-like polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups (yield 79%).

[0160] Example 12

[0161] In this embodiment, the halogen atom-containing cage-like polyhedral oligomeric silsesquioxane is selected from formula (IV), X is an iodine atom, and R 4 is an alkylene group -CH 3 -CH 2 -CH 2 -CH 2 -; the carboxylic acid root-containing hindered phenol compound is selected from the general formula (VII), which is 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, M is hydrogen, R 1 and R 2 are hydroxyl groups, and R 3 is an alkylene group -CH 2 -CH 2 -CH 2 -.

[0162]

[0163] In a 150 mL three-necked flask, 3.55 g of a cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms, 3.6 g of 3-(3,4,5-trihydroxyphenyl)propionic acid, and 60 mL of anhydrous N,N-dimethylformamide were added. Then, 6.0 g of potassium carbonate was added as an acid-binding agent. Under a nitrogen atmosphere, the reaction system was heated to 35 °C, stirred for 48 h while maintaining the temperature, and then naturally cooled to room temperature. Subsequently, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out, washed with deionized water, and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to remove moisture, obtaining 3.9 g of the target product, a pure cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups (yield 62%).

[0164] Example 13

[0165] In this embodiment, the cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms is selected from formula (IV), X is a chlorine atom, and R 4 is an alkylene group of C 3 -CH 2 -CH 2 -CH 2 -; the hindered phenol compound containing a carboxylate group is selected from the general formula (VII), which is sodium 3,5-di-tert-butyl-4-hydroxyphenylpropionate, M is sodium, and R 1 is tert-butyl -C(CH 3 ) 3 , R 2 is methyl -CH 3 , R 3 is an alkylene group of C 2 -CH 2 -CH 2 -.

[0166]

[0167] In a 150 mL three-necked flask, 2.08 g of a chlorine atom-containing cage-type polyhedral oligomeric silsesquioxane, 6.5 g of sodium 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionate, and 60 mL of anhydrous N,N-dimethylformamide were added. Then, 1 g of potassium iodide as a catalyst was added. Under a nitrogen atmosphere, the reaction system was heated to 100 °C, stirred for 5 h while maintaining the temperature, and then naturally cooled to room temperature. Subsequently, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out, and unreacted sodium 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionate, the catalyst, and the NaCl generated during the reaction were all removed in the solution. The solid was washed with deionized water and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to remove moisture. Then, the obtained solid crude product was stirred and dissolved in methanol at room temperature, and the insoluble unreacted chlorine atom-containing cage-type polyhedral oligomeric silsesquioxane was filtered out. The methanol in the filtrate was removed by rotary evaporation, and the solid was collected and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to obtain 4.8 g of the target product, a cage-type polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups (yield 70%).

[0168] Example 14

[0169] In this embodiment, the halogen atom-containing cage-type polyhedral oligomeric silsesquioxane is selected from formula (IV), X is an iodine atom, and R 4 is C 3 alkylene -CH 2 -CH 2 -CH 2 -; the carboxylic acid root-containing hindered phenol compound is selected from the general formula (VII), which is 3-(4-hydroxy-3,5-dimethoxyphenyl)propionic acid, M is hydrogen, R 1 and R 2 are methoxy groups, and R 3 is C 2 alkylene -CH 2 -CH 2 -.

[0170]

[0171] In a 150 mL three-necked flask, 3.55 g of a cage-shaped polyhedral oligomeric silsesquioxane containing iodine atoms, 4.1 g of 3-(4-hydroxy-3,5-dimethoxyphenyl)propionic acid, and 60 mL of anhydrous N,N-dimethylformamide were added. Then, 4.5 g of potassium carbonate was added as an acid-binding agent. Under a nitrogen atmosphere, the reaction system was heated to 35 °C, stirred at this temperature for 48 h, and then naturally cooled to room temperature. Subsequently, the reaction system was poured into 300 mL of deionized water, and the product precipitated from the solution. The solid was filtered out, washed with deionized water, and dried in a vacuum oven at 40 °C under a vacuum of -0.1 to -0.05 MPa for 24 h to remove moisture, obtaining 4.4 g of a pure cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups (yield 86%).

[0172] Example 15

[0173] Take polypropylene containing 0.35 wt% of the cage-shaped polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups prepared in Example 1 (the total amount of antioxidant and polypropylene is 100%, the same below) as the experimental group, polypropylene containing 0.38 wt% of the cage-shaped polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups prepared in Example 3 as the experimental group, polypropylene containing 0.38 wt% of the pure cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups prepared in Example 6 as the experimental group, and polypropylene containing 0.3 wt% of antioxidant 1010 as the control group; then take polypropylene containing 0.6 wt% of antioxidant 168 and 0.38 wt% of the cage-shaped polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups prepared in Example 3 as the experimental group, and take polypropylene containing 0.6 wt% of antioxidant 168 and 0.3 wt% of antioxidant 1010 as the control group. The concentration of hindered phenol functional groups in the above 6 groups of polypropylene samples is the same, all being 2.6 μmol / g PP. The sample composition information is shown in Table 1, the test results of oxidation induction time are shown in Table 2, and the test results of solvent extraction resistance experiment are shown in Table 3.

[0174] The extrusion unit of a HAAKE MiniLabⅡ rheometer from Thermo Fisher Scientific, Germany was used to melt-blend each group of samples. First, feeding was carried out at a rotation speed of 10 rpm for 1 min, then the rotation speed was increased to 50 rpm for blending for 5 min, and then the sample strips were extruded. Then, thin film samples were prepared by hot pressing for oxidation induction time testing. The hot pressing temperature was 210 °C, a hot pressing mold of 10 cm × 10 cm × 0.6 mm was used, the sample was preheated for 3 min without pressure to melt it, then hot pressed at 8 MPa for 4 min, and finally kept under pressure at 8 MPa and water-cooled at 20 °C for 1 min to prepare thin film samples with a thickness of about 600 μm.

[0175] Table 1 Specimen composition:

[0176]

[0177] Table 2 Oxidation induction period of PP specimens

[0178] Sample number <![CDATA[1 a > <![CDATA[2 a > <![CDATA[3 a > <![CDATA[4 a > <![CDATA[5 b > <![CDATA[6 b > <![CDATA[7 b > Oxidation induction period (min) 13.8 14.7 15.8 17.1 38.1 46.2 50.7

[0179] Note: a The DSC test temperature is 210 °C; b The DSC test temperature is 220 °C.

[0180] Table 3 Oxidation induction period of PP specimens after extraction with dichloromethane

[0181]

[0182]

[0183] Note: a The DSC test temperature is 210 °C.

[0184] As shown in Table 2, PP specimens 2, 3, and 4 have longer oxidation induction times than PP specimen 1. That is, the PP plastic containing the cage-shaped polyhedral oligomeric silsesquioxane with hindered phenol functional groups prepared by the synthesis method of the present invention has a longer oxidation induction time than the PP plastic added with the commercial antioxidant 1010. By comparing PP specimens 3 and 4 containing the products of Example 3 or Example 6, it can be found that the PP specimen containing the product of Example 6 has a longer oxidation induction time. The Si-O-Si cage framework size of the product of Example 6 is smaller and has better antioxidant effect. When each primary antioxidant is compounded with the commercial secondary antioxidant 168, the effect of the cage-shaped polyhedral oligomeric silsesquioxane with hindered phenol functional groups on prolonging the oxidation induction time of PP specimens is more significant. The oxidation induction times of PP specimens 6 and 7 are 33% and 21% higher than that of PP specimen 5. Therefore, on the basis of the same concentration of hindered phenol functional groups, the cage-shaped polyhedral oligomeric silsesquioxane with hindered phenol functional groups prepared by the synthesis method of the present invention has better antioxidant effect than the commercial antioxidant 1010 and can effectively improve the thermal oxidation aging resistance of polymers.

[0185] As shown in Table 3, adding the commercial antioxidant The retention rate of the oxidation induction time of the PP sample of 1010 was only 32% after 48 hours of dichloromethane extraction. For the PP samples added with the cage-like polyhedral oligomeric silsesquioxane mixture containing hindered phenol functional groups prepared by the synthesis method of the present invention, that is, the PP samples added with the products of Example 1, Example 3 and Example 6, the retention rates of the oxidation induction time were 66%, 72% and 65.2% respectively. The Si-O-Si cage-like skeleton size of the product of Example 3 was larger, and it had better solvent extraction resistance than the product of Example 6. It can be seen that the cage-like polyhedral oligomeric silsesquioxane containing hindered phenol functional groups prepared by the synthesis method of the present invention has good extraction resistance, and can improve the thermal oxygen stability of polymers for a long time and efficiently at low addition amounts, and can be used as an antioxidant for the preparation and processing of polymers.

[0186] It was experimentally confirmed that the cage-like polyhedral oligomeric silsesquioxanes containing hindered phenol functional groups with the structures of Formula I, II, and III of the present invention all had excellent antioxidant and extraction resistance effects.

[0187] Of course, the present invention can also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes and deformations should all fall within the protection scope of the claims of the present invention.

Claims

1. A cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups, characterized in that, it has one or more structures in the following formulas I to III: Wherein, R 1 and R 2 are independently selected from: hydrogen, alkyl, alkoxy, hydroxyalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclic group, heterocyclic group alkyl, carboxyl, ester group, amide group, amino group, amine group, halogen, nitro, cyano, oxycarbonyl, aminocarbonyl; R 3 and R 4 are independently selected from alkylene groups having 0 to 20 carbons.

2. The cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to claim 1, characterized in that, R 1 and R 2 each have from 0 to 18 carbons, R 3 and R 4 each have from 0 to 6 carbons.

3. The cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to claim 2, characterized in that, R 1 and R 2 at least one of which is a branched alkyl group of C 3 -C 8 ​ 4. The cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to claim 1, characterized in that, R 1 is H or methyl, R 2 is C 3 -C 8 branched alkyl; and / or, R 3 is -CH 2 -CH 2 -, R 4 is -CH 2 -CH 2 -CH 2 -.

5. A method for preparing the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to any one of claims 1-4, characterized in that, it includes the following steps: Step 1, reacting a cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms with a hindered phenol compound containing a carboxylate group; Step 2, post-treating the reaction mixture to obtain a cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups; wherein, the cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms has one or more structures in the following formulas IV to VI, and the hindered phenol compound containing a carboxylate group has the following formula VII structure: R 1 and R 2 are independently selected from: hydrogen, alkyl, alkoxy, hydroxyalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclic group, heterocyclic group alkyl, carboxyl, ester group, amide group, amino group, amine group, halogen, nitro group, cyano group, oxycarbonyl, aminocarbonyl; R 3 and R 4 are independently selected from alkylene groups having 0 to 20 carbons; X is selected from halogen elements; M is selected from hydrogen element or metal element.

6. The method for preparing the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to claim 5, characterized in that, the molar ratio of the cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms to the hindered phenol compound containing a carboxylate group is 1:(1-18).

7. The method for preparing the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to claim 5, characterized in that, a catalyst is further added to the reaction in Step 1, and the catalyst is selected from one of sodium iodide, potassium iodide, and potassium carbonate.

8. The method for preparing the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to claim 5, characterized in that, the molar ratio of the catalyst to the cage-shaped polyhedral oligomeric silsesquioxane containing halogen atoms is (0-8):

1.

9. The method for preparing the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to claim 5, characterized in that, the reaction temperature is 0°C - 120°C, and the reaction time is 1 - 72 h.

10. Use of the cage-shaped polyhedral oligomeric silsesquioxane containing hindered phenol functional groups according to any one of claims 1-4 as an antioxidant.

Images