WO2022213904A1 - 分子内复合型受阻酚化合物、其制备方法及应用 - Google Patents

分子内复合型受阻酚化合物、其制备方法及应用 Download PDF

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WO2022213904A1
WO2022213904A1 PCT/CN2022/084886 CN2022084886W WO2022213904A1 WO 2022213904 A1 WO2022213904 A1 WO 2022213904A1 CN 2022084886 W CN2022084886 W CN 2022084886W WO 2022213904 A1 WO2022213904 A1 WO 2022213904A1
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antioxidant
monomer
hindered phenol
intramolecular
phenol compound
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French (fr)
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孙春光
林旭锋
范小鹏
李海平
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天津利安隆新材料股份有限公司
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Priority to KR1020237038456A priority Critical patent/KR20230167119A/ko
Priority to EP22783971.9A priority patent/EP4321502A1/en
Publication of WO2022213904A1 publication Critical patent/WO2022213904A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
    • C09K15/08—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen containing a phenol or quinone moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change

Definitions

  • the invention relates to the field of macromolecular material additives, in particular to an intramolecular composite hindered phenol compound, a preparation method and application thereof.
  • Symmetrical hindered phenol antioxidant 1010 the starting material of sterically hindered phenol is only 2,6-di-tert-butylphenol (symmetrical type), the chemical name of antioxidant 1010 is: tetra[beta-(3,5-di-tert-butyl] 1-4-hydroxyphenyl)propionic acid] pentaerythritol ester, white crystalline powder, melting point 110-125 °C, stable chemical properties, can be widely used in general plastics, engineering plastics, synthetic rubber, fibers, hot melt adhesives, resins, Oil, ink, paint and other industries.
  • Asymmetric hindered phenol antioxidants 1790 and 245 the starting material of sterically hindered phenol is only 2-methyl-6-tert-butylphenol (asymmetric type), and the side steric hindrance in the molecular structure is reduced, which makes the antioxidant The efficiency is significantly increased, especially with the hydrogen bond association with auxiliary antioxidants such as thioesters, and the synergistic effect is more significant; at the same time, the antioxidants are self-generated and resistant to yellowing, with excellent thermal oxidation stability and discoloration resistance. .
  • the above-mentioned asymmetric hindered phenol antioxidants 1790 and 245 lack the scope of application universality like the symmetric hindered phenol antioxidant 1010.
  • the hindered phenolic antioxidants in the prior art generally have the problems of poor resistance to yellowing, poor anti-oxidation efficiency, and poor coloring resistance to NOx.
  • the main purpose of the present invention is to provide an intramolecular composite hindered phenol compound, its preparation method and application, so as to solve the common problems of the hindered phenolic antioxidants in the prior art, such as poor yellowing resistance, poor antioxidant efficiency, Problems such as poor colorability against NOx.
  • an intramolecular composite hindered phenol compound which has a structure shown in formula I:
  • n 1-3
  • m+n 4.
  • n 1, and n is 3; or, m is 2, and n is 2; or, m is 3, and n is 1; preferably, m is 2, and n is 2.
  • a method for preparing an intramolecular composite hindered phenol compound comprises the following steps: subjecting pentaerythritol and a first monomer to a first transesterification reaction to obtain an intermediate substitution product; The substitution product and the second monomer are subjected to a second transesterification reaction to obtain an intramolecular composite hindered phenol compound; or, the pentaerythritol and the monomer mixture are subjected to a third transesterification reaction to obtain an intramolecular composite hindered phenol compound; the monomer mixture Including a first monomer and a second monomer; wherein, the first monomer and the second monomer are different, and are respectively selected from methyl 3-methyl-5-tert-butyl-4-hydroxyphenylpropionate or 3 , 5-di-tert-butyl-4-hydroxyphenylpropionate methyl ester; the number of substituents of the first monomer in the intermediate substitution product correspond
  • the first transesterification reaction step, the second transesterification reaction step and the third transesterification reaction step are all carried out under the action of a transesterification catalyst; preferably, the transesterification catalyst is selected from alkyl tin oxide, lithium amide, methanol One or more of sodium, lithium methoxide, aluminum alkoxide, zinc organic acid; more preferably, the alkyl tin oxide catalyst is selected from one or more of monobutyl tin oxide, dioctyl tin oxide .
  • the first monomer is 3-methyl-5-tert-butyl-4-hydroxyphenylpropionic acid methyl ester
  • the second monomer is 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid methyl ester
  • the preparation method includes the following steps: mixing pentaerythritol, a first monomer, and a transesterification catalyst under an inert gas, and performing a first transesterification reaction to obtain a pre-reaction system containing an intermediate substitution product; A second monomer is added to the system, and a second transesterification reaction is carried out to obtain an intramolecular complex hindered phenol compound.
  • a polymer material antioxidant which comprises one or more of the above-mentioned intramolecular complex hindered phenol compounds.
  • the polymer material antioxidants also include phosphite antioxidants and/or thioester antioxidants; preferably, the phosphite antioxidants are tris(2,4-di-tertiary phosphite) Butylbenzene) ester, bis(2,4-di-tert-butylbenzene) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, triisodecyl phosphite, Pentaerythritol diisodecyl diphosphite, tetraphenyl dipropylene glycol diphosphite, diphenyl monoisodecyl phosphite, triphenyl phosphite, monophenyl diisodecyl phosphite, tris(nonylbenzene phosphite) one or
  • a polymer material which includes a polymer material body and an antioxidant, wherein the antioxidant is the above-mentioned polymer material antioxidant.
  • the polymer material body is resin or rubber; preferably the resin is polyolefin, polyurethane, polyether, polyketone, polystyrene, polycarbonate, polyacrylate, polymethacrylate, polyacetal, halogen-containing Polymer, polyamide, polyoxymethylene, polyphenylene oxide, polyoxalyl terephthalate, polysuccinate terephthalate, polyacrylonitrile, polybutadiene, polystyrene, HIPS, ABS, MBS, epoxy or epoxy-crosslinked acrylic; preferably the rubber is natural rubber, styrene-butadiene rubber, neoprene, cis-butadiene, isoprene, nitrile or thermoplastic TPU.
  • the resin is polyolefin, polyurethane, polyether, polyketone, polystyrene, polycarbonate, polyacrylate, polymethacrylate, polyacetal, halogen-containing Polymer, polyamide, polyoxymethylene
  • the polymer material body is thermoplastic TPU, and the antioxidant is added in an amount of 0.01-3% by weight; or, the macromolecular material is PP, and the antioxidant is added in an amount of 0.01-1% by weight; preferably Typically, when the polymer material is PP, the antioxidant includes the above-mentioned intramolecular composite hindered phenolic compound and the antioxidant DSTDP, more preferably the weight ratio of the two is 1:5 to 5:1.
  • the intramolecular complex hindered phenol compound provided by the present invention is m[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]-n[ ⁇ -(3-methyl-5-tert-butyl) yl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, which has good self-yellowing resistance, and has the advantages of high antioxidant efficiency, good compatibility with the matrix, low melting point, and wide application range, especially It is used in the field of plastic processing, showing NOx-resistant coloring, and has good application performance.
  • Fig. 1 shows the infrared spectrum of the intramolecular complex hindered phenol compound prepared according to Example 1 of the present invention
  • Fig. 2 shows the hydrogen nuclear magnetic spectrum of the intramolecular complex hindered phenol compound prepared according to Example 1 of the present invention
  • Fig. 3 shows the carbon nuclear magnetic spectrum of the intramolecular complex hindered phenol compound prepared according to Example 1 of the present invention.
  • FIG. 4 shows the mass spectrum of the intramolecular complex hindered phenol compound prepared according to Example 1 of the present invention.
  • Fig. 5 shows the infrared spectrum of the intramolecular complex hindered phenol compound prepared according to Example 3 of the present invention
  • Figure 6 shows the hydrogen nuclear magnetic spectrum of the intramolecular complex hindered phenol compound prepared according to Example 3 of the present invention
  • Fig. 7 shows the carbon nuclear magnetic spectrum of the intramolecular complex hindered phenol compound prepared according to Example 3 of the present invention.
  • FIG. 8 shows the mass spectrum of the intramolecular complex hindered phenol compound prepared according to Example 3 of the present invention.
  • Fig. 9 shows the infrared spectrum of the intramolecular complex hindered phenol compound prepared according to Example 4 of the present invention.
  • Figure 10 shows the hydrogen nuclear magnetic spectrum of the intramolecular complex hindered phenol compound prepared according to Example 4 of the present invention
  • Figure 11 shows the carbon nuclear magnetic spectrum of the intramolecular complex hindered phenol compound prepared according to Example 4 of the present invention.
  • the hindered phenolic antioxidants in the prior art generally have problems such as poor yellowing resistance, poor oxidation resistance, and poor NOx colorability.
  • the present invention provides an intramolecular composite hindered phenol compound, which has the structure shown in formula I:
  • n 1-3
  • m+n 4.
  • the intramolecular complex hindered phenol compound provided by the present invention is m[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]-n[ ⁇ -(3-methyl-5-tert-butyl) yl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, which has good self-yellowing resistance, and has the advantages of high antioxidant efficiency, good compatibility with the matrix, low melting point, and wide application range, especially It is used in the field of plastic processing, showing NOx-resistant coloring, and has good application performance.
  • the above hindered phenol compound of the present invention forms a new symmetrical-asymmetrical composite structure in the molecule.
  • the steric hindrance effect of the bulky tert-butyl group has a protective effect on the hydroxyl group, which can prevent the oxidative loss of antioxidants.
  • the phenolic hydroxyl group in the molecular structure of asymmetric hindered phenolic antioxidants has one tert-butyl group and one methyl group at the ortho position, which reduces the steric hindrance effect of the phenolic hydroxyl group, making it easier to form intermolecular hydrogen bonds with other materials, improving the Synergistic stabilization effect; it also makes the meta-position of the phenolic hydroxyl group more prone to nitro substitution reaction, and the formation of stable m-nitro compounds is generally white, which overcomes the disadvantages of completely symmetrical hindered phenol para-nitro oxidation into easily colored products; that is, asymmetric hindered Phenolic antioxidants have their own anti-yellowing ability.
  • the hindered phenol compound of the present invention as an intramolecular symmetric-asymmetric hindered phenol composite antioxidant, has both the advantages of the above-mentioned symmetric hindered phenol antioxidant and asymmetric hindered phenol antioxidant.
  • the hindered phenolic compound of the present invention has a remarkable property, which can greatly reduce the melting point of the product (especially compared with the symmetrical hindered phenolic antioxidant 1010 in the prior art), making the process more operable. , adding more easily.
  • one of the above-mentioned intramolecular composite hindered phenolic compounds can be used alone as a polymer antioxidant, or at least two of them can be mixed in any ratio and used as a polymer antioxidant.
  • n is 3, corresponding to the following compound 1; or, m is 2, n is 2, corresponding to the following compound 2; or, m is 3, n is 1, corresponding to the following compound 3.
  • m is 2 and n is 2, that is, compound 2 above.
  • a method for preparing the above-mentioned intramolecular composite hindered phenol compound which comprises the following steps: subjecting pentaerythritol and a first monomer to a first transesterification reaction to obtain an intermediate substitution product; The intermediate substitution product and the second monomer are subjected to a second transesterification reaction to obtain an intramolecular composite hindered phenol compound; or, the pentaerythritol and the monomer mixture are subjected to a third transesterification reaction to obtain an intramolecular composite hindered phenol compound; the monomer The mixture includes a first monomer and a second monomer; wherein the first monomer and the second monomer are different and are respectively selected from methyl 3-methyl-5-tert-butyl-4-hydroxyphenylpropionate or 3,5-di-tert-butyl-4-hydroxyphenylpropionate methyl ester; the number of substituents of the first monomer in the
  • the other is to combine pentaerythritol and methyl 3-methyl-5-tert-butyl-4-hydroxyphenylpropionate and methyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate in the raw material preparation stage According to the ratio of target m and n, a mixed monomer is prepared, and the mixed monomer is directly used for transesterification reaction with pentaerythritol to form the target product intramolecular complex hindered phenol compound in one step.
  • the prepared intramolecular complex hindered phenol compound is m[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]-n[ ⁇ -(3-methyl-5-tert-butyl) -4-hydroxyphenyl)propionic acid] pentaerythritol ester, which has good self-yellowing resistance, and has the advantages of high antioxidant efficiency, good compatibility with the matrix, low melting point, and wide application range, especially Used in the field of plastic processing, it shows NOx-resistant coloring and has good application performance.
  • the first transesterification reaction step, the second transesterification reaction step and the third transesterification reaction step are all performed under the action of a transesterification catalyst.
  • the transesterification catalyst is selected from one or more of alkyl tin oxide, lithium amide, sodium methoxide, lithium methoxide, aluminum alkoxide, and organic acid zinc.
  • the reaction conditions are milder.
  • the alkyl tin oxide catalyst is selected from one or more of monobutyl tin oxide and dioctyl tin oxide.
  • the first monomer is methyl 3-methyl-5-tert-butyl-4-hydroxyphenylpropionate
  • the second monomer is 3,5-di-tert-butyl- Methyl 4-hydroxyphenylpropionate.
  • the above preparation method includes the following steps: mixing pentaerythritol, a first monomer, and a transesterification catalyst under an inert gas, and performing a first transesterification reaction to obtain a pre-reaction system containing an intermediate substitution product; add a second monomer into the pre-reaction system to carry out a second transesterification reaction to obtain an intramolecular composite hindered phenol compound.
  • the first transesterification reaction specifically includes the following steps: mixing pentaerythritol, the first monomer, and the transesterification catalyst under an inert gas, and then raising the temperature to 120-180° C. to carry out a heat preservation reaction; using an inert gas to purge the pre-reaction system , in order to discharge methanol; continue to heat up to 180 ⁇ 185 °C to carry out the heat preservation reaction, obtain the pre-reaction system.
  • the second transesterification reaction specifically includes the following steps: cooling the pre-reaction system to 80-150 °C, then adding the second monomer to it, and heating the temperature to 180-185 °C to carry out the heat preservation reaction, and the reaction pressure is 500-760 mm Hg column to obtain an intramolecular complex hindered phenol compound.
  • Controlling the reaction temperature of each step within the above range is beneficial to further improve the reaction efficiency.
  • the reaction is carried out in the presence of an inert gas, and the by-product methanol is taken out by the inert gas in the middle of the reaction, which is beneficial to promote the forward progress of the reaction.
  • the specific inert gas can be nitrogen, argon or the like.
  • the crude product of the above-mentioned intramolecular complex hindered phenol compound is obtained.
  • the crude product can be purified after the reaction, preferably by the following method: vacuum distillation is carried out under a high vacuum of 0.5 mm Hg, and the excess second monomer is recovered. Then, the reaction solution was cooled to 115°C, and toluene was added to dissolve in nitrogen flow atmosphere, and then fully washed with 5% oxalic acid solution, and then washed twice with water, the toluene phase was concentrated, and vacuum-dried to obtain the pure product of the target product.
  • the weight ratio of the transesterification catalyst to pentaerythritol is (0.03-0.2): 1; preferably, When the first monomer is methyl 3-methyl-5-tert-butyl-4-hydroxyphenylpropionate, the molar ratio of the first monomer to pentaerythritol is [n ⁇ (n+0.2)]:1, The molar ratio of the second monomer to pentaerythritol is [m ⁇ (m+1)]:1; when the first monomer is methyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, the first The molar ratio of the monomer to pentaerythritol is [m ⁇ (m+0.2)]: 1, and the molar ratio of the second monomer to pentaerythritol is [n ⁇ (n+1)]
  • an application of one or more of the above-mentioned intramolecular composite hindered phenol compounds as an antioxidant for polymer materials is provided.
  • the intramolecular complex hindered phenol compound is m[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]-n[ ⁇ -(3-methyl-5-tert- Butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, which has good self-yellowing resistance, high antioxidant efficiency, good compatibility with the matrix, low melting point, and wide application range.
  • one of the above-mentioned intramolecular composite hindered phenolic compounds can be used alone as a polymer antioxidant, or at least two of them can be mixed in any ratio and used as a polymer antioxidant.
  • the intramolecular composite hindered phenol compound of the present invention is used in combination with a phosphite type antioxidant and a thioester type antioxidant, and the antioxidant effect is better.
  • phosphite antioxidant refers to an auxiliary antioxidant having a phosphite or diphosphite structure, such as tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) , bis(2,4-di-tert-butylbenzene) pentaerythritol diphosphite (antioxidant 626), bis(2,4-dicumylphenyl) pentaerythritol-diphosphite (antioxidant 686), Triisodecyl phosphite (antioxidant PL-81), pentaerythritol diisodecyl diphosphite (antioxidant PL-90), tetraphenyldipropylene glycol diphosphite (antioxidant THOP), phosphorous acid Diphenyl monoisodecyl (antioxidant DPDP), triphenyl pho
  • thioester antioxidants refer to auxiliary antioxidants containing thioether groups, such as pentaerythritol tetrakis (3-dodecyl thiopropionate) (antioxidant 412S), thiodipropionic acid Distearyl alcohol ester (antioxidant DSTDP), didodecyl thiodipropionate (antioxidant DLTDP), ditetradecyl thiodipropionate (antioxidant DMTDP), thiodipropylene Ditridecyl acid ester (antioxidant DTDTP).
  • auxiliary antioxidants containing thioether groups such as pentaerythritol tetrakis (3-dodecyl thiopropionate) (antioxidant 412S), thiodipropionic acid Distearyl alcohol ester (antioxidant DSTDP), didodecyl thiodipropionate (antioxidant DLTDP),
  • the intramolecular composite hindered phenol compound of the present invention can also be used in combination with auxiliary agents such as ultraviolet absorbers, hindered amine light stabilizers, flame retardants, and nucleating agents.
  • auxiliary agents such as ultraviolet absorbers, hindered amine light stabilizers, flame retardants, and nucleating agents.
  • the type of the ultraviolet absorber is not particularly limited, and can be a conventional type in the art, such as benzophenones, benzotriazoles, triazines, benzoates, and the like.
  • a polymer material which includes a polymer material body and an antioxidant.
  • the antioxidant of the present invention can be used in polymer materials, such as resins or rubbers; for example, resins include but are not limited to polyolefins, polyurethanes, polyethers, polyketones, polystyrenes, Carbonate, polyacrylate, polymethacrylate, polyacetal, halogenated polymers, polyamide, polyoxymethylene, polyphenylene ether, polyethylene terephthalate, polysuccinic acid terephthalate Ester, polyacrylonitrile, polybutadiene, polystyrene, HIPS, ABS, MBS, epoxy or epoxy-crosslinked acrylic resin; such as rubber including but not limited to natural rubber, styrene butadiene rubber, neoprene , butadiene rubber, isoprene rubber, nitrile rubber or thermoplastic TPU.
  • resins include but are not limited to polyolefins, polyurethan
  • the body of the polymer material is TPU, and the added amount of the antioxidant is 0.01 to 3% of the weight of the TPU. More preferably, the above-mentioned intramolecular composite hindered phenol compound is used as the TPU antioxidant, and there is a stronger relationship between the TPU and the TPU. Good compatibility, can play a more sufficient role; alternatively, the polymer material is PP, and the amount of antioxidant added is 0.01 to 1% of the weight of PP, more preferably, intramolecular composite hindered phenol compounds and antioxidants are used. DSTDP is compounded as an antioxidant for PP, which has a more significant effect. Preferably, the weight ratio of the intramolecular complex hindered phenol compound to the antioxidant DSTDP is 1:5 to 5:1, more preferably 1:3.
  • the tin catalyst was heated to 165°C, stirred and incubated for 3 hours, blown away the methanol that escaped, heated to 180 ⁇ 185°C for 2 hours and basically reacted completely; then cooled to 120°C, then added 35.1 g (120 mmol) of Methyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, stirred and heated to 180-185 degrees and reacted for 8 hours, blowing nitrogen to drive off the escaping methanol. Next, the excess methyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate was recovered by vacuum distillation under high vacuum of 0.5 mmHg.
  • reaction solution was cooled to 115 degrees, and 400 ml of toluene was added to dissolve it in a nitrogen atmosphere. Then, it was fully washed with 200 ml of 5% oxalic acid solution, and then washed twice with water (200 ml each time). The toluene phase was concentrated and vacuumed.
  • the infrared spectrum is shown in Figure 1
  • the H NMR spectrum is shown in Figure 2
  • the C NMR spectrum is shown in Figure 3
  • the high-resolution mass spectrum is shown in Figure 4.
  • the tin catalyst was heated to 165°C, stirred and incubated for 3 hours, blowing nitrogen to drive off the escaped methanol, heated to 180-185°C for 2 hours and the reaction was basically complete; then cooled to 120°C, and then added 80mmol of 3,5- Methyl di-tert-butyl-4-hydroxyphenylpropionate, turn on the vacuum, keep the reaction pressure at 700 mmHg, stir and heat up to 180-185° C. to react for 2 hours. Then the reaction solution was cooled to room temperature and recrystallized with a mixed solvent of toluene and methanol to obtain 32 g of product.
  • the main product was confirmed to be bis[beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid by hydrogen NMR spectroscopy. ]-bis[ ⁇ -(3-methyl-5-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (compound 2), the product yield was 73%; the melting point was 48-50°C.
  • reaction solution was cooled to room temperature, and recrystallized with a mixed solvent of toluene and methanol to obtain 26 g of product.
  • the main product was confirmed by hydrogen NMR to be tris[beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid. ]-[ ⁇ -(3-methyl-5-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (compound 1), the melting point is 39-40°C, and the product yield is 57%.
  • the infrared spectrum is shown in Fig. 5, the hydrogen nuclear magnetic spectrum is shown in Fig. 6, the carbon nuclear magnetic spectrum is shown in Fig. 7, and the high-resolution mass spectrum is shown in Fig. 8.
  • the tin catalyst was heated to 165°C, stirred and incubated for 2 hours, blown away the methanol that escaped, heated to 180 ⁇ 185°C for 1 hour and basically reacted completely; then cooled to 120°C, then added 30 grams (120mmol) of Methyl 3-methyl-5-tert-butyl-4-hydroxyphenylpropionate (referred to as methyl 345), turn on the vacuum, keep the reaction pressure at 700 mmHg, stir and heat up to 180-185 degrees and react for 3 hours. Then the reaction solution was cooled to room temperature and recrystallized with a mixed solvent of toluene and methanol to obtain 25 g of product.
  • methyl 345 Methyl 3-methyl-5-tert-butyl-4-hydroxyphenylpropionate
  • the infrared spectrum is shown in Figure 9
  • the hydrogen nuclear magnetic spectrum is shown in Figure 10
  • the carbon nuclear magnetic spectrum is shown in Figure 11
  • the high-resolution mass spectrum is shown in Figure 12.
  • the sample of compound 2 synthesized in Example 1, the compound 1 synthesized in Example 3, the compound 3 synthesized in Example 4, and the commonly used antioxidant 1010 in the market were all added at a mass fraction of 2% to prepare a polyurethane elastomer ( TPU) pellets, respectively prepared test pieces a1 (corresponding to compound 2), a2 (corresponding to compound 1), a3 (corresponding to compound 3), b (corresponding to antioxidant 1010) by an elastomer injection machine; as a comparison, without adding The TPU pellets of the antioxidant are prepared by the elastomer injection machine to prepare the test piece c;
  • TPU polyurethane elastomer
  • the sample of compound 2 synthesized in Example 1, the compound 1 synthesized in Example 3, the compound 3 synthesized in Example 4, the commonly used antioxidant Irganox 1010 in the market, and the thiopropionate DSTDP are all in the form of mass fractions
  • Antioxidant formula Dosage 5% brittle time/hour No added antioxidants - 5 Irganox 1010 0.05% 155 Compound 2 0.05% 180 Compound 1 0.05% 167 Compound 3 0.05% 170 DSTDP 0.15% 50 Irganox 1010/DSTDP 0.05%/0.15% 640 Compound 2/DSTDP 0.05%/0.15% 1300 Compound 1/DSTDP 0.05%/0.15% 950 Compound 3/DSTDP 0.05%/0.15% 1020

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Abstract

本发明提供了一种分子内复合型受阻酚化合物、其制备方法及应用。该分子内复合型受阻酚化合物，其具有式I所示结构，其中，m为1～3，n为1～3，且m+n为4。本发明提供的分子内复合型受阻酚化合物具有良好的自身耐黄变性特性，且兼具了抗氧化效率高、与基体相容性好、熔点低、应用范围广等优势，尤其是用于塑料加工领域显示了耐NOx的着色性，具有良好的应用性能。

Description

分子内复合型受阻酚化合物、其制备方法及应用
本申请是以CN申请号为202110377984.5，申请日为2021年04月08日的中国申请为基础，并主张其优先权，该CN申请的公开内容再次作为整体引入本申请中。
技术领域
本发明涉及高分子材料助剂领域，具体而言，涉及一种分子内复合型受阻酚化合物、其制备方法及应用。
背景技术
高分子材料在制造、贮存、加工和使用过程中，会因为受到氧化而引起塑料等高分子材料及其制品性能的下降或损失，导致高分子材料的老化。添加抗氧剂可以使高分子材料具备必要的抗氧能力。
自1937年世界上第一个具有受阻酚结构的抗氧剂BHT问世以来，受阻酚类抗氧剂的开发和研究倍受关注。目前世界上受阻酚抗氧剂大多数是以2,6-二叔丁基苯酚(对称型)或2-甲基-6-叔丁基苯酚(非对称型)为基础原料合成的，并且总是以单一位阻酚为原料合成相应的受阻酚抗氧剂。对称型受阻酚抗氧剂1010，起始位阻酚原料只有2,6-二叔丁基苯酚(对称型)，抗氧剂1010化学名为：四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯，为白色结晶粉末，熔点110-125℃，化学性状稳定，可广泛应用于通用塑料，工程塑料，合成橡胶，纤维，热熔胶，树脂，油品，墨水，涂料等行业中。然而，尽管产销价格低廉、综合性能突出，实际应用中还是发现了抗氧剂自身不耐黄变、抗氧化效率不够高、与基体的相容性不够理想等缺点。非对称型受阻酚抗氧剂1790和245，起始位阻酚原料只有2-甲基-6-叔丁基苯酚(非对称型)，分子结构中一边位阻有所减小，使抗氧效率显著增高，尤其与硫代酯等辅助抗氧剂之间存在氢键缔合，协同效果更为显著；同时，抗氧剂自生耐黄变，具有优异的抗热氧化稳定性能和耐变色性。然而，上述非对称型受阻酚抗氧剂1790和245缺乏像对称型受阻酚抗氧剂1010的应用普适性范围等。
总之，现有技术中的受阻酚类抗氧剂普遍存在自身耐黄变性能差、抗氧化效率差、耐NOx的着色性差等方面的问题。
发明内容
本发明的主要目的在于提供一种分子内复合型受阻酚化合物、其制备方法及应用，以解决现有技术中的受阻酚类抗氧剂普遍存在自身耐黄变性能差、抗氧化效率差、耐NOx的着色性差等方面的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种分子内复合型受阻酚化合物，其具有式I所示结构：
Figure PCTCN2022084886-appb-000001
其中，m为1～3，n为1～3，且m+n为4。
进一步地，m为1，n为3；或者，m为2，n为2；或者，m为3，n为1；优选地，m为2，n为2。
根据本发明的另一方面，还提供了一种分子内复合型受阻酚化合物的制备方法，其包括以下步骤：将季戊四醇和第一单体进行第一酯交换反应，得到中间取代产物；将中间取代产物和第二单体进行第二酯交换反应，得到分子内复合型受阻酚化合物；或者，将季戊四醇和单体混合物进行第三酯交换反应，得到分子内复合型受阻酚化合物；单体混合物包括第一单体和第二单体；其中，第一单体和第二单体不同，且分别选自3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯或3,5-二叔丁基-4-羟基苯基丙酸甲酯；中间取代产物中第一单体的取代基数目与式I中的m或n相对应；单体混合物中第一单体和第二单体的摩尔比与式I中的m和n的比例相对应。
进一步地，第一酯交换反应步骤、第二酯交换反应步骤及第三酯交换反应步骤均在酯交换催化剂的作用下进行；优选地，酯交换催化剂选自烷基氧化锡、氨基锂、甲醇钠、甲醇锂、烷氧基铝、有机酸锌中的一种或多种；更优选地，烷基氧化锡催化剂选自单丁基氧化锡、二辛基氧化锡中的一种或多种。
进一步地，第一单体为3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯，第二单体为3,5-二叔丁基-4-羟基苯基丙酸甲酯；优选地，制备方法包括以下步骤：将季戊四醇、第一单体、酯交换催化剂在惰性气体下混合，并进行第一酯交换反应，得到含有中间取代产物的预反应体系；向预反应体系中加入第二单体，进行第二酯交换反应，得到分子内复合型受阻酚化合物。
根据本发明的又一方面，还提供了一种高分子材料抗氧剂，其包括上述分子内复合型受阻酚化合物中的一种或多种。
进一步地，高分子材料抗氧剂还包括亚磷酸酯类抗氧剂和/或硫代酯类抗氧剂；优选地，亚磷酸酯类抗氧剂为亚磷酸三(2,4-二叔丁基苯)酯、双(2,4-二叔丁基苯)季戊四醇二亚磷酸酯、双(2,4-二枯基苯基)季戊四醇-二亚磷酸酯、亚磷酸三异癸酯，二亚磷酸季戊四醇二异癸酯、四苯基二丙二醇二亚磷酸酯、亚磷酸二苯一异癸酯、亚磷酸三苯酯、亚磷酸一苯二异 癸酯、亚磷酸三(壬基苯基)酯中的一种或多种；优选地，硫代酯类抗氧剂为季戊四醇四(3-十二基硫代丙酸酯)、硫代二丙酸双十八醇酯、硫代二丙酸双十二醇酯、硫代二丙酸双十四醇酯、硫代二丙酸双十三醇酯中的一种或多种。
根据本发明的再一方面，还提供了一种高分子材料，其包括高分子材料本体和抗氧剂，其中抗氧剂为上述高分子材料抗氧剂。
进一步地，高分子材料本体为树脂或橡胶；优选树脂为聚烯烃、聚氨酯、聚醚、聚酮、聚苯乙烯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚缩醛、含卤聚合物、聚酰胺、聚甲醛、聚苯醚、聚对苯二甲酸乙二酸酯、聚对苯二甲酸丁二酸酯、聚丙烯腈、聚丁二烯、聚苯乙烯、HIPS、ABS、MBS、环氧树脂或环氧树脂交联的丙烯酸树脂；优选橡胶为天然橡胶、丁苯橡胶、氯丁橡胶、顺丁橡胶、异戊橡胶、丁腈橡胶或热塑性TPU。
进一步地，高分子材料本体为热塑性TPU，抗氧剂的添加量为其重量的0.01～3％；或者，高分子材料为PP，抗氧剂的添加量为其重量的0.01～1％；优选地，当高分子材料为PP时，抗氧剂包括上述分子内复合型受阻酚化合物与抗氧剂DSTDP，更优选二者的重量比为1:5～5:1。
本发明提供的分子内复合型受阻酚化合物为m[β-(3，5-二叔丁基-4-羟基苯基)丙酸]-n[β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸]季戊四醇酯，其具有良好的自身耐黄变性特性，且兼具了抗氧化效率高、与基体相容性好、熔点低、应用范围广等优势，尤其是用于塑料加工领域显示了耐NOx的着色性，具有良好的应用性能。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1示出了根据本发明实施例1制备的分子内复合型受阻酚化合物的红外图谱；
图2示出了根据本发明实施例1制备的分子内复合型受阻酚化合物的核磁氢谱；
图3示出了根据本发明实施例1制备的分子内复合型受阻酚化合物的核磁碳谱；以及
图4示出了根据本发明实施例1制备的分子内复合型受阻酚化合物的质谱图。
图5示出了根据本发明实施例3制备的分子内复合型受阻酚化合物的红外图谱；
图6示出了根据本发明实施例3制备的分子内复合型受阻酚化合物的核磁氢谱；
图7示出了根据本发明实施例3制备的分子内复合型受阻酚化合物的核磁碳谱；以及
图8示出了根据本发明实施例3制备的分子内复合型受阻酚化合物的质谱图。
图9示出了根据本发明实施例4制备的分子内复合型受阻酚化合物的红外图谱；
图10示出了根据本发明实施例4制备的分子内复合型受阻酚化合物的核磁氢谱；
图11示出了根据本发明实施例4制备的分子内复合型受阻酚化合物的核磁碳谱；以及
图12示出了根据本发明实施例4制备的分子内复合型受阻酚化合物的质谱图。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
正如背景技术部分所描述的，现有技术中的受阻酚类抗氧剂普遍存在自身耐黄变性能差、抗氧化效率差、耐NOx的着色性差等方面的问题。
为了解决上述问题，本发明提供了一种分子内复合型受阻酚化合物，其具有式I所示结构：
Figure PCTCN2022084886-appb-000002
其中，m为1～3，n为1～3，且m+n为4。
本发明提供的分子内复合型受阻酚化合物为m[β-(3，5-二叔丁基-4-羟基苯基)丙酸]-n[β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸]季戊四醇酯，其具有良好的自身耐黄变性特性，且兼具了抗氧化效率高、与基体相容性好、熔点低、应用范围广等优势，尤其是用于塑料加工领域显示了耐NOx的着色性，具有良好的应用性能。
不同于传统的受阻酚，本发明上述受阻酚化合物在分子内形成了对称型-非对称型复合新结构。对称型受阻酚抗氧剂分子结构中的酚羟基邻位上具有两个特丁基，提高了苯氧自由基共轭体系的电子云密度，赋予良好的稳定性，呈现较高的抗氧化效率，同时，庞大的特丁基基团的空间位阻效应对羟基具有保护作用，可防止抗氧剂的氧化损失。非对称受阻酚抗氧剂分子结构中的酚羟基邻位上具有特丁基和甲基各一个，减小了酚羟基的空间位阻效应，使其更易与其它物料形成分子间氢键，提高协同稳定效果；还使得酚羟基的间位更容易发生硝基取代反应，形成稳定的间硝基化合物一般是白色，克服完全对称受阻酚对位硝基氧化成易着色产物弊端；即非对称受阻酚抗氧剂具有自身抗黄变的能力。而本发明上述受阻酚化合物作为分子内对称型-非对称型受阻酚复合类抗氧剂，兼具了上述对称型受阻酚抗氧剂和非对称受阻酚抗氧剂的优点。另外，本发明的受阻酚化合物还有一个显著性能——可大幅度降低产品的熔点(尤其相比于现有技术中的对称型受阻酚抗氧剂1010)，使得加工过程可操作性更强，添加更方便。
实际应用过程中，可以单独使用一种上述分子内复合型受阻酚化合物作为高分子材料抗氧剂使用，也可以将其中的至少两种以任意比例混合后作为高分子材料抗氧剂使用。
在一种优选的实施方式中，m为1，n为3，对应以下化合物1；或者，m为2，n为2，对应以下化合物2；或者，m为3，n为1，对应以下化合物3。
化合物1、
Figure PCTCN2022084886-appb-000003
化合物2、
Figure PCTCN2022084886-appb-000004
化合物3、
Figure PCTCN2022084886-appb-000005
出于进一步提高耐黄变性性、抗氧化效率、与基体相容性、耐NOx的着色性等方面的综合性能的目的，更优选地，m为2，n为2，即上述化合物2。
根据本发明的另一方面，还提供了一种上述分子内复合型受阻酚化合物的制备方法，其包括以下步骤：将季戊四醇和第一单体进行第一酯交换反应，得到中间取代产物；将中间取代产物和第二单体进行第二酯交换反应，得到分子内复合型受阻酚化合物；或者，将季戊四醇和单体混合物进行第三酯交换反应，得到分子内复合型受阻酚化合物；单体混合物包括第一单体和第二单体；其中，第一单体和第二单体不同，且分别选自3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯或3,5-二叔丁基-4-羟基苯基丙酸甲酯；中间取代产物中第一单体的取代基数目与式I中的m或n相对应；单体混合物中第一单体和所述第二单体的摩尔比与式I中的m和n的比例相对应。
采用该制备方法，一种是先将季戊四醇和3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯(或3,5-二叔丁基-4-羟基苯基丙酸甲酯)先进行酯交换反应，使季戊四醇中1至3个(具体根据第一单体的不同参照m或n的数值即可)羟基发生反应，生成中间取代产物；然后加入3,5-二叔 丁基-4-羟基苯基丙酸甲酯(或3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯)进一步进行酯交换反应，取代季戊四醇中剩余的羟基，即可形成目标产物分子内复合型受阻酚化合物。另一种是在原料配制阶段将季戊四醇和3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯和3,5-二叔丁基-4-羟基苯基丙酸甲酯按照目标m和n的比例配制成混合单体，利用该混合单体直接与季戊四醇进行酯交换反应，一步形成目标产物分子内复合型受阻酚化合物。
以上通过反应原料的比例进行先后两次酯交换反应或者利用混合单体进行一次酯交换反应的方式，都可以控制最终分子内复合型受阻酚化合物中的m和n值，但不可避免地会有微量产物组分中两种单体取代个数与目标m和n值不符，这是本领域技术人员都应理解的，后续可以通过分离的手段进行提纯，且即使不提纯，以混合物的形式作为高分子抗氧剂使用，也不影响使用效果。
使用该方法，步骤简单，反应效率较高，合成方便。制备得到的分子内复合型受阻酚化合物为m[β-(3，5-二叔丁基-4-羟基苯基)丙酸]-n[β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸]季戊四醇酯，其具有良好的自身耐黄变性特性，且兼具了抗氧化效率高、与基体相容性好、熔点低、应用范围广等优势，尤其是用于塑料加工领域显示了耐NOx的着色性，具有良好的应用性能。
为了进一步提高酯交换反应的效率，在一种优选的实施方式中，第一酯交换反应步骤、第二酯交换反应步骤及第三酯交换反应步骤均在酯交换催化剂的作用下进行。优选地，酯交换催化剂选自有烷基氧化锡、氨基锂、甲醇钠、甲醇锂、烷氧基铝、有机酸锌中的一种或多种。使用以上几类酯交换催化剂，除了具有较高的催化活性，能够进一步提高反应效率以外，其反应条件更为温和。更优选地，烷基氧化锡催化剂选自单丁基氧化锡、二辛基氧化锡中的一种或多种。
在一种优选的实施方式中，上述第一单体为3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯，第二单体为3,5-二叔丁基-4-羟基苯基丙酸甲酯。这样，反应过程可以按照以下路线进行：
Figure PCTCN2022084886-appb-000006
为了进一步改善反应安全性和稳定性，在一种优选的实施方式中，上述制备方法包括以下步骤：将季戊四醇、第一单体、酯交换催化剂在惰性气体下混合，并进行第一酯交换反应，得到含有中间取代产物的预反应体系；向预反应体系中加入第二单体，进行第二酯交换反应，得到分子内复合型受阻酚化合物。
更优选地，第一酯交换反应具体包括以下步骤：将季戊四醇、第一单体、酯交换催化剂在惰性气体下混合，然后升温至120～180℃进行保温反应；采用惰性气体吹扫预反应体系，以排出甲醇；继续升温至180～185℃进行保温反应，得到预反应体系。优选地，第二酯交换反应具体包括以下步骤：将预反应体系降温至80～150℃，然后向其中加入第二单体，并升温至180～185℃进行保温反应，反应压力500～760毫米汞柱，得到分子内复合型受阻酚化合物。
将各步骤反应温度控制在上述范围内，有利于进一步提高反应效率。同时，在惰性气体存在下反应，并在反应中途利用惰性气体将副产物甲醇带出，有利于促进反应正向进行。具体的惰性气体可以为氮气、氩气等。
经两步酯交换反应后，得到上述分子内复合型受阻酚化合物的粗品。在实际合成过程中，可以在反应结束后对粗品进行提纯，优选采用以下方法进行提纯：0.5毫米汞柱高真空下进行减压蒸馏，回收过量的第二单体。然后将反应液冷却到115℃，氮气流氛围下，加入甲苯溶解，接着用5％草酸溶液充分洗涤，再用水洗2次，甲苯相进行浓缩，并真空抽干得到目标产物纯品。
为了进一步促进反应正向进行，同时尽量避免过多第一单体取代多余羟基，在一种优选的实施方式中，酯交换催化剂与季戊四醇的重量比为(0.03～0.2):1；优选地，当第一单体为3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯时，第一单体与季戊四醇的摩尔比为[n～(n+0.2)]:1，第二单体与季戊四醇的摩尔比为[m～(m+1)]:1；当第一单体为3,5-二叔丁基-4-羟基苯基丙酸甲酯时，第一单体与季戊四醇的摩尔比为[m～(m+0.2)]:1，第二单体与季戊四醇的摩尔比为[n～(n+1)]:1；其中m和n具有与前文所述相同定义。
根据本发明的另一方面，提供了一种上述分子内复合型受阻酚化合物的一种或多种混合后作为高分子材料抗氧剂的应用。如前文所述，分子内复合型受阻酚化合物为m[β-(3，5-二叔丁基-4-羟基苯基)丙酸]-n[β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸]季戊四醇酯，其具有良好的自身耐黄变性特性，且兼具了抗氧化效率高、与基体相容性好、熔点低、应用范围广等优势，尤其是用于塑料加工领域显示了耐NOx的着色性，具有良好的应用性能。实际应用过程中，可以单独使用一种上述分子内复合型受阻酚化合物作为高分子材料抗氧剂使用，也可以将其中的至少两种以任意比例混合后作为高分子材料抗氧剂使用。
更优选地，在具体实施例中，本发明分子内复合型受阻酚化合物与亚磷酸酯类抗氧剂、硫代酯类抗氧剂组合使用，抗氧化效果更佳。
上述亚磷酸酯类抗氧剂是指具有亚磷酸酯或二亚磷酸酯结构的辅助抗氧剂，例如可以为亚磷酸三(2,4-二叔丁基苯)酯(抗氧剂168)、双(2,4-二叔丁基苯)季戊四醇二亚磷酸酯(抗氧剂626)、双(2,4-二枯基苯基)季戊四醇-二亚磷酸酯(抗氧剂686)、亚磷酸三异癸酯(抗 氧剂PL-81)，二亚磷酸季戊四醇二异癸酯(抗氧剂PL-90)、四苯基二丙二醇二亚磷酸酯(抗氧剂THOP)、亚磷酸二苯一异癸酯(抗氧剂DPDP)、亚磷酸三苯酯(抗氧剂TPPi)、亚磷酸一苯二异癸酯(抗氧剂PDDP)、亚磷酸三(壬基苯基)酯(抗氧剂TNPP)，最优选为亚磷酸二苯一异癸酯。但是，本发明不受上述化合物的任何限制。
上述硫代酯类抗氧剂是指含硫醚基团的辅助抗氧剂，例如可以为季戊四醇四(3-十二基硫代丙酸酯)(抗氧剂412S)、硫代二丙酸双十八醇酯(抗氧剂DSTDP)、硫代二丙酸双十二醇酯(抗氧剂DLTDP)、硫代二丙酸双十四醇酯(抗氧剂DMTDP)、硫代二丙酸双十三醇酯(抗氧剂DTDTP)。但是，本发明不受上述化合物的任何限制。在具体实施例中，本发明分子内复合型受阻酚化合物还可以与紫外线吸收剂、受阻胺光稳定剂、阻燃剂、成核剂等助剂联合使用。所述紫外线吸收剂的类型不做特别限定，可以为本领域常规的类型，如二苯甲酮类，苯并三氮唑类，三嗪类，苯甲酸酯类等。
根据本发明的另一方面，还提供了一种高分子材料，其包括高分子材料本体和抗氧剂。在实际应用过程中，本发明的抗氧剂可用于高分子材料中，例如用于树脂或橡胶中；比如，树脂包括但不限于聚烯烃、聚氨酯、聚醚、聚酮、聚苯乙烯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚缩醛、含卤聚合物、聚酰胺、聚甲醛、聚苯醚、聚对苯二甲酸乙二酸酯、聚对苯二甲酸丁二酸酯、聚丙烯腈、聚丁二烯、聚苯乙烯、HIPS、ABS、MBS、环氧树脂或环氧树脂交联的丙烯酸树脂；比如橡胶包括但不限于天然橡胶、丁苯橡胶、氯丁橡胶、顺丁橡胶、异戊橡胶、丁腈橡胶或热塑性TPU。优选将上述抗氧化剂用于作为热塑性TPU、聚丙烯PP等高分子材料的抗氧助剂。
根据高分子材料本体类型的不同，本领域技术人员可以选择具体的抗氧剂加入量。优选地，高分子材料本体为TPU，抗氧剂的添加量为TPU重量的0.01～3％，更优选地，采用上述分子内复合型受阻酚化合物作为TPU抗氧剂，与TPU之间具有更好的相容性，能够更充分地发挥作用；或者，高分子材料为PP，抗氧剂的添加量为PP重量的0.01～1％，更优选采用分子内复合型受阻酚化合物和抗氧剂DSTDP进行复配以作为PP的抗氧剂，具有更显著的效果。优选分子内复合型受阻酚化合物与抗氧剂DSTDP的重量比为1:5～5:1，更优选为1:3。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例1：
Figure PCTCN2022084886-appb-000007
氮气流氛围下向反应瓶中加入5.45克(40mmol)的季戊四醇、20克(80mmol)的3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯和0.7克二辛基氧化锡催化剂，升温到165℃，搅拌保温反应3小时，吹氮气赶走逸出的甲醇，升温到180～185℃反应2小时基本反应完全；接着降温到120度，再加入35.1克(120mmol)的3,5-二叔丁基-4-羟基苯基丙酸甲酯，搅拌升温到180～185度反应8小时，吹氮气赶走逸出的甲醇。接着，0.5毫米汞柱高真空下进行减压蒸馏回收过量的3，5-二叔丁基-4-羟基苯基丙酸甲酯。然后将反应液冷却到115度，氮气流氛围下，加入400毫升甲苯溶解，接着用200毫升5％草酸溶液充分洗涤，再用水洗2次(每次200毫升)，甲苯相进行浓缩，并真空抽干得到42克产品，确认主产物是二[β-(3，5-二叔丁基-4-羟基苯基)丙酸]-二[β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸]季戊四醇酯(化合物2)，产品收率为96％；熔点48～50℃。化合物2表征数据如下：
核磁氢谱 1H NMR(400MHz,CDCl 3)δ＝6.98(s,4H),6.93(d,J＝1.8Hz,2H),6.81(d,J＝1.6Hz,2H),5.08(s,2H),4.68(s,2H),3.99(s,4H),3.97(s,4H),2.85-2.79(m,8H),2.60-2.56(m,8H),2.19(s,6H),1.43(s,36H),1.39(s,18H)。
核磁碳谱 13C NMR(101MHz,CDCl 3)δ172.66，172.64,152.27,151.20,136.07，136.05,131.27,130.73,128.13,124.82，124.80,123.51,62.34,41.74,36.11,34.46，34.44,30.82,30.43，30.41,29.80,16.02。
高分辨质谱HRMS(EI-TOF，M+K +):1131.6536。
红外光谱如图1所示，核磁氢谱如图2所示，核磁碳谱如图3所示，高分辨质谱如图4所示。
实施例2：
氮气流氛围下向反应瓶中加入5.45克(40mmol)的季戊四醇、20克(80mmol)的3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯和0.2克单丁基氧化锡催化剂，升温到165℃，搅拌保温反应3小时，吹氮气赶走逸出的甲醇，升温到180～185℃反应2小时基本反应完全；接着降温到120℃，再加入80mmol的3,5-二叔丁基-4-羟基苯基丙酸甲酯，开启真空，保持反应压力700毫米汞柱，搅拌升温到180～185℃反应2小时。然后将反应液冷却到室温，用甲苯和甲醇混合溶剂重结晶得32克产品，核磁氢谱确认主产物是二[β-(3，5-二叔丁基-4-羟基苯基)丙酸]-二[β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸]季戊四醇酯(化合物2)，产品收率为73％；熔点48～50℃。
实施例3：
Figure PCTCN2022084886-appb-000008
氮气流氛围下向反应瓶中加入5.45克(40mmol)的季戊四醇、10克(40mmol)的3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯(简称345甲酯)和0.2克单丁基氧化锡催化剂，升温到165℃，搅拌保温反应2小时，吹氮气赶走逸出的甲醇，升温到180～185℃反应1小时基本反应完全；接着降温到120℃，再加入120mmol的3，5-二叔丁基-4-羟基苯基丙酸甲酯(简称35甲酯)，开启真空，保持反应压力700毫米汞柱，搅拌升温到180～185℃反应3小时。然后将反应液冷却到室温，用甲苯和甲醇混合溶剂重结晶得26克产品，核磁氢谱确认主产物是三[β-(3，5-二叔丁基-4-羟基苯基)丙酸]-[β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸]季戊四醇酯(化合物1)，熔点39～40℃，产品收率为57％。监控反应TLC展开剂乙酸乙酯/正己烷＝1：6；原料和各产物的Rf值：345甲酯为0.7，35甲酯为0.6，化合物1为0.5。化合物1表征数据如下：
核磁氢谱 1H NMR(400MHz,CDCl 3)δ＝6.98(s,6H),6.94(d,J＝1.8Hz,1H),6.81(d,J＝1.6Hz,1H),5.08(s,3H),4.67(s,1H),4.03(d,J＝6.9Hz,8H),2.83(dd,J＝15.7,7.2Hz,8H),2.60(dd,J＝10.3,6.0Hz,8H),2.19(s,3H),1.43(s,54H),1.39(s,9H)。
核磁碳谱 13C NMR(101MHz,CDCl 3)δ.172.67,152.27,151.19,136.05,136.06,131.27,130.73,128.13,124.80,124.81,123.51,62.32,41.83,36.14,34.44,34.45,30.82,30.42,30.83,29.76,29.77,16.01。
高分辨质谱HRMS(EI-TOF，M+K +):1173.7004。
红外光谱如图5所示，核磁氢谱如图6所示，核磁碳谱如图7所示，高分辨质谱如图8所示。
实施例4：
Figure PCTCN2022084886-appb-000009
氮气流氛围下向反应瓶中加入5.45克(40mmol)的季戊四醇、40mmol的3，5-二叔丁基-4-羟基苯基丙酸甲酯(简称35甲酯)和0.2克单丁基氧化锡催化剂，升温到165℃，搅拌保温反应2小时，吹氮气赶走逸出的甲醇，升温到180～185℃反应1小时基本反应完全；接着降温到120℃，再加入30克(120mmol)的3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯(简称345甲酯)，开启真空，保持反应压力700毫米汞柱，搅拌升温到180～185度反应3小时。然后将反应液冷却到室温，用甲苯和甲醇混合溶剂重结晶得25克产品，核磁氢谱确认主产物是[β-(3，5-二叔丁基-4-羟基苯基)丙酸]-三[β-(3-甲基-5-叔丁基-4-羟基苯基)丙酸]季戊四醇酯(化合物3)，熔点49-50℃，产品收率为60％。监控反应TLC展开剂乙酸乙酯/正己烷＝1：6；原料和各产物的Rf值：345甲酯为0.7，35甲酯为0.6，化合物3为0.3。化合物表征数据如下：
核磁氢谱 1H NMR(400MHz,CDCl 3)δ＝6.98(s,2H),6.93(d,J＝1.8Hz,3H),6.80(d,J＝1.6Hz,3H),5.08(s,1H),4.68(s,3H),3.93(d,J＝5.9Hz,8H),2.82(dd,J＝15.3,7.7Hz,8H),2.57(t,J＝7.7Hz,8H),2.19(s,9H),1.43(s,19H),1.39(s,28H)。
核磁碳谱 13C NMR(101MHz,CDCl 3)δ172.64，172.65,152.27,151.19,136.05，136.06,131.27,130.72,128.13,124.80，124.81,123.51,62.35,41.66,36.09,34.44，34.45,30.80,30.40，30.41,29.80,16.01。
高分辨质谱HRMS(EI-TOF，M+K +):1089.6063。
红外光谱如图9所示，核磁氢谱如图10所示，核磁碳谱如图11所示，高分辨质谱如图12所示。
应用性能表征：
TPU抗氧化性能：
将实施例1合成的化合物2的样品、实施例3合成的化合物1、实施例4合成的化合物3、市场通用的抗氧剂1010均按质量分数为2％的加入比例，制备聚氨酯弹性体(TPU)粒料，分别依次经弹性体注射机制备试片a1(对应化合物2)、a2(对应化合物1)、a3(对应化合物3)、b(对应抗氧剂1010)；作为对比，不添加抗氧剂的TPU粒料经弹性体注射机制备试片c；
所有试片在90℃恒温水浴中进行老化试验，然后测试各弹性体试片的机械性能。下表1是各试片老化试验前后的测试结果。从表中结果可见，添加化合物1、2、3样品的聚氨酯弹性体片，有更好的抗老化性能。
表1
Figure PCTCN2022084886-appb-000010
Figure PCTCN2022084886-appb-000011
PP抗氧化性能：
将实施例1合成的化合物2的样品、实施例3合成的化合物1、实施例4合成的化合物3、市场通用的抗氧剂Irganox 1010、以及硫代丙酸酯DSTDP，均按质量分数为表格中指定的的加入比例，应用于对聚丙烯PP(均聚物MI＝2)的稳定效果实验。物料混合均匀后，投入双螺杆挤出机挤出，挤出温度为210-230℃，经冷却、烘干、切粒、分筛后得到改性聚丙烯。
考察这些改性聚丙烯在160℃下吉尔烘箱中老化数据，结果如下表2所示(注意基本配方：PP中含有占比0.05％的硬脂酸钙)。
从表中结果可见，抗氧剂样品化合物2、化合物1、化合物3和1010作为主抗氧剂单独使用时，二者对聚丙烯的稳定性相当；当同样质量的主抗氧剂与辅助抗氧剂硫代丙酸酯复合使用的时候，有协同稳定效果，抗氧剂化合物2明显优于1010，而且比单独使用主抗氧剂比较有更好的抗老化性能。
表2
抗氧剂配方 用量 5％脆变时间/小时
无添加抗氧剂 - 5
Irganox 1010 0.05％ 155
化合物2 0.05％ 180
化合物1 0.05％ 167
化合物3 0.05％ 170
DSTDP 0.15％ 50
Irganox 1010/DSTDP 0.05％/0.15％ 640
化合物2/DSTDP 0.05％/0.15％ 1300
化合物1/DSTDP 0.05％/0.15％ 950
化合物3/DSTDP 0.05％/0.15％ 1020
自身耐黄变性能表征
作为汽车尾气和化学废气排放在大气中的NOx浓度持续提高，而NOx气体对聚合物制品的着色性问题日益突出，考察抗氧剂NOx的着色性能也很重要。考察比较化合物2、化合物1、化合物3的样品、市场通用的抗氧剂Irganox 1010作为粉末暴露于3％二氧化氮气体(NO 2)中，在室温下放置1.5小时观察发现抗氧剂Irganox 1010粉末已经完全变成黄色，而化合物2、化合物1、化合物3的粉末为类白色，几乎无变化，说明本发明提供的分子内复合型受阻酚化合物具有良好的耐黄变性能，更耐NOx的着色。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种分子内复合型受阻酚化合物，其特征在于，所述分子内复合型受阻酚化合物具有式I所示结构：
    Figure PCTCN2022084886-appb-100001
    其中，m为1～3，n为1～3，且m+n为4。
  2. 根据权利要求1所述的分子内复合型受阻酚化合物，其特征在于，m为1，n为3；或者，m为2，n为2；或者，m为3，n为1；
    优选地，m为2，n为2。
  3. 一种权利要求1或2所述的分子内复合型受阻酚化合物的制备方法，其特征在于，所述制备方法包括以下步骤：
    将季戊四醇和第一单体进行第一酯交换反应，得到中间取代产物；将所述中间取代产物和第二单体进行第二酯交换反应，得到所述分子内复合型受阻酚化合物；或者，
    将季戊四醇和单体混合物进行第三酯交换反应，得到所述分子内复合型受阻酚化合物；所述单体混合物包括第一单体和第二单体；
    其中，所述第一单体和所述第二单体不同，且分别选自3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯或3,5-二叔丁基-4-羟基苯基丙酸甲酯；所述中间取代产物中所述第一单体的取代基数目与式I中的m或n相对应；所述单体混合物中所述第一单体和所述第二单体的摩尔比与式I中的m和n的比例相对应。
  4. 根据权利要求3所述的分子内复合型受阻酚化合物的制备方法，其特征在于，所述第一酯交换反应步骤、所述第二酯交换反应步骤及所述第三酯交换反应步骤均在酯交换催化剂的作用下进行；
    优选地，所述酯交换催化剂选自烷基氧化锡、氨基锂、甲醇钠、甲醇锂、烷氧基铝、有机酸锌中的一种或多种；
    更优选地，所述烷基氧化锡选自单丁基氧化锡、二辛基氧化锡中的一种或多种。
  5. 根据权利要求4所述的分子内复合型受阻酚化合物的制备方法，其特征在于，所述第一单体为所述3-甲基-5-叔丁基-4-羟基苯基丙酸甲酯，所述第二单体为所述3,5-二叔丁基-4-羟基苯基丙酸甲酯；优选地，所述制备方法包括以下步骤：
    将所述季戊四醇、所述第一单体、所述酯交换催化剂在惰性气体下混合，并进行所述第一酯交换反应，得到含有所述中间取代产物的预反应体系；
    向预反应体系中加入所述第二单体，进行所述第二酯交换反应，得到所述分子内复合型受阻酚化合物。
  6. 一种高分子材料抗氧剂，其特征在于，包括权利要求1或2所述的分子内复合型受阻酚化合物中的一种或多种。
  7. 根据权利要求6所述的高分子材料抗氧剂，其特征在于，所述高分子材料抗氧剂还包括亚磷酸酯类抗氧剂和/或硫代酯类抗氧剂；优选地，所述亚磷酸酯类抗氧剂为亚磷酸三(2,4-二叔丁基苯)酯、双(2,4-二叔丁基苯)季戊四醇二亚磷酸酯、双(2,4-二枯基苯基)季戊四醇-二亚磷酸酯、亚磷酸三异癸酯，二亚磷酸季戊四醇二异癸酯、四苯基二丙二醇二亚磷酸酯、亚磷酸二苯一异癸酯、亚磷酸三苯酯、亚磷酸一苯二异癸酯、亚磷酸三(壬基苯基)酯中的一种或多种；优选地，所述硫代酯类抗氧剂为季戊四醇四(3-十二基硫代丙酸酯)、硫代二丙酸双十八醇酯、硫代二丙酸双十二醇酯、硫代二丙酸双十四醇酯、硫代二丙酸双十三醇酯中的一种或多种。
  8. 一种高分子材料，包括高分子材料本体和抗氧剂，其特征在于，所述抗氧剂为权利要求6或7所述的高分子材料抗氧剂。
  9. 根据权利要求8所述的高分子材料，其特征在于，所述高分子材料本体为树脂或橡胶；优选所述树脂为聚烯烃、聚氨酯、聚醚、聚酮、聚苯乙烯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚缩醛、含卤聚合物、聚酰胺、聚甲醛、聚苯醚、聚对苯二甲酸乙二酸酯、聚对苯二甲酸丁二酸酯、聚丙烯腈、聚丁二烯、聚苯乙烯、HIPS、ABS、MBS、环氧树脂或环氧树脂交联的丙烯酸树脂；优选所述橡胶为天然橡胶、丁苯橡胶、氯丁橡胶、顺丁橡胶、异戊橡胶、丁腈橡胶或热塑性TPU。
  10. 根据权利要求8所述的高分子材料，其特征在于，
    所述高分子材料本体为热塑性TPU，所述抗氧剂的添加量为其重量的0.01～3％；或者，
    所述高分子材料为PP，所述抗氧剂的添加量为其重量的0.01～1％；优选地，当所述高分子材料为PP时，所述抗氧剂包括权利要求1或2所述的分子内复合型受阻酚化合物与抗氧剂DSTDP，更优选二者的重量比为1:5～5:1。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5925349A (ja) * 1982-08-03 1984-02-09 Sumitomo Chem Co Ltd テトラキス〔メチレン−３−（３−メチル−５−ｔ−ブチル−４−ヒドロキシフエニル）プロピオネ−ト〕メタンおよびこれを含有してなる安定化ポリオレフイン樹脂組成物
US5892097A (en) * 1996-05-23 1999-04-06 Ciba Specialty Chemicals Corporation Process for the preparation of substituted hydroxyhydrocinnamate esters
CN101508644A (zh) * 2009-03-26 2009-08-19 北京极易化工有限公司 一种受阻酚类抗氧化剂的合成新方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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CN101215235B (zh) * 2007-12-27 2011-01-26 上海金海雅宝精细化工有限公司 一种受阻酚类抗氧剂的合成方法
CN106588663B (zh) * 2016-10-28 2018-08-17 南雄志一精细化工有限公司 一种受阻酚类抗氧剂及其制备方法
CN111320542B (zh) * 2018-12-17 2023-04-25 中国石油天然气股份有限公司 一种包含双受阻酚结构抗氧化剂及制备方法
CN110862317B (zh) * 2019-12-02 2022-04-22 山东省临沂市三丰化工有限公司 一种受阻酚类抗氧剂及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5925349A (ja) * 1982-08-03 1984-02-09 Sumitomo Chem Co Ltd テトラキス〔メチレン−３−（３−メチル−５−ｔ−ブチル−４−ヒドロキシフエニル）プロピオネ−ト〕メタンおよびこれを含有してなる安定化ポリオレフイン樹脂組成物
US5892097A (en) * 1996-05-23 1999-04-06 Ciba Specialty Chemicals Corporation Process for the preparation of substituted hydroxyhydrocinnamate esters
CN101508644A (zh) * 2009-03-26 2009-08-19 北京极易化工有限公司 一种受阻酚类抗氧化剂的合成新方法

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