Sustainable antioxidant composition, its use and polymer composition containing the same

Abstract

The present disclosure relates to an antioxidant composition comprising component (a) and component (b), a process for preparing an aqueous dispersion comprising the antioxidant composition, the use of the antioxidant composition as a chain terminator and / or stabilizer, and a polymer composition comprising the antioxidant composition.

Description

Technical Field

[0001] The present disclosure relates to an antioxidant composition, a process for preparing an aqueous dispersion containing the antioxidant composition, the use of the antioxidant composition as a chain terminator and / or stabilizer, and a polymer composition containing the antioxidant composition.

Background Art

[0002] Antioxidants can be used as chain terminators in free radical polymerization. Conventional antioxidants for free radical polymerization, especially for PVC polymerization, are either inefficient in terminating the chain or have issues related to EHS (such as BPA). Also, conventional chain terminators such as ATSC (acetone thiosemicarbazone) and DEHA (diethylhydroxylamine) have a very weak effect on thermally stabilizing polymers, especially PVC resins. Furthermore, these chain terminators need to be pre-dissolved in methanol or similar (toxic) organic solvents or alkaline water in free radical polymerization such as PVC production, and their usage is not simple.

Summary of the Invention

Problems to be Solved by the Invention

[0003] Therefore, in the art, there is still a need to provide an antioxidant composition that not only has excellent chain termination properties but also is excellent in thermally stabilizing polymers and can be immediately used in free radical polymerization.

[0004] An object of the present disclosure is to provide an antioxidant composition that not only has excellent chain termination properties but also is excellent in thermally stabilizing polymers and can be immediately used in free radical polymerization.

[0005] Another object of the present disclosure is to provide a process for preparing an aqueous dispersion containing the antioxidant composition.

[0006] A further object of the present disclosure is to provide the use of the antioxidant composition of the present disclosure as a chain terminator and / or stabilizer.

[0007] A further object of the present disclosure is to provide a polymer composition comprising an antioxidant composition.

Means for Solving the Problems

[0008] Surprisingly, it has been found that the above object can be achieved by the following embodiments. 1. An antioxidant composition, comprising: (a) Formula (I): [Chemical formula] (In the formula, R1 is selected from hydrogen or an aliphatic group having 1 to 6 carbon atoms; R2 is an organic group having 1 to 30 carbon atoms; R3, R4, and R5 are each independently selected from hydrogen or C1-C4-alkyl) a derivative of chromanol; and (b) Formula (II): [Chemical formula] (In the formula, R 21 is C1-C6-alkyl, R 22 is C1-C8-alkyl, m is an integer of 1, 2, or 3, provided that when m is 2 or 3, at most one of the two ortho positions to the hydroxyl group has R 22 ) a compound An antioxidant composition comprising. 2. The antioxidant composition according to item 1, wherein the composition further comprises a protective colloid and / or a surfactant. 3. R1 is selected from hydrogen or C1-C6-alkyl; Preferably, R1 is selected from hydrogen or C1-C4-alkyl; More preferably, R1 is hydrogen or C1-C3 alkyl; In the above alkyl (C1-C6-alkyl, C1-C4-alkyl and C1-C3-alkyl), one or more non-adjacent sulfur / oxygen atoms may be optionally inserted, and / or one or more non-adjacent carbon atoms of the above alkyl may be optionally replaced by -(CO)-O-, the antioxidant composition according to item 1 or 2. 4. R2 is selected from C1-C 30 -alkyl or C2-C 30 -alkenyl; more preferably, R2 is selected from C8-C 30 -alkyl or C8-C 30 -alkenyl, and in the above alkyl (C1-C 30 -alkyl and C8-C 30 -alkyl), one or more non-adjacent sulfur / oxygen atoms may be optionally inserted, and / or one or more non-adjacent carbon atoms of the above alkyl may be optionally replaced by -(CO)-O-, the antioxidant composition according to any one of items 1-3. 5. R3, R4, and R5 are each independently selected from hydrogen, methyl, or ethyl, the antioxidant composition according to any one of items 1-4. 6. Component (a) is α-, β-, γ-, δ-tocopherol or α-, β-, γ-, δ-tocotrienol or a mixture thereof, preferably vitamin E, more preferably, the compound of formula (I’-1):

Chemical formula

[0009] The following are the advantageous technical effects obtained by the antioxidant composition of the present disclosure, but are not limited thereto: (1) It shows excellent chain termination properties in free radical polymerization such as PVC polymerization and even shows a synergistic effect in chain termination; (2) It is excellent in thermally stabilizing polymers; (3) It not only improves the sustainability (EHS) of PVC polymerization (without using toxic / organic solvents), but also is easy to use (no need to pre-dissolve); (4) It has an excellent effect of preventing yellowing.

[0010] It should be understood that the summary part of the invention is not intended to limit the scope of the present disclosure. Other features of the present disclosure will be readily understood according to the following description.

Embodiments for Carrying out the Invention

[0011] In the following description, for the purpose of facilitating a sufficient understanding by those skilled in the art, the present disclosure will be further described with reference to embodiments. It should be understood that these embodiments are provided merely for a better understanding of the subject matter of the present disclosure and are not intended to limit the scope of protection, applicability, or embodiments described in a series of claims of the present invention. Those skilled in the art should understand that, without departing from the spirit of the present disclosure, various technical features can be omitted, substituted, or added to each embodiment based on actual needs. Furthermore, the technical features described in some embodiments can be combined with the technical features described in other embodiments.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which the present disclosure belongs.

[0013] The terms "comprise", "comprising", "include", "including" and their various modifications in the present disclosure can be understood as open-ended terms meaning "including but not limited to". On the other hand, the term "consisting of" and its various modifications exclude any component, step or procedure not specifically described. The term "one embodiment" can be understood as "at least one embodiment", and the term "another embodiment" can be understood as "at least one other embodiment". Other terms that may appear but are not mentioned here should not be interpreted or limited in a manner contrary to the concepts underlying the embodiments of the present disclosure unless explicitly stated.

[0014] Throughout this disclosure, the indefinite articles "a," "an," the definite article "the," and the expression "one or more" are used interchangeably, and are intended to include both plural and singular forms unless the singular form is explicitly specified or clearly indicated by the context. When only the singular form is intended, the term "one" is typically used. Also, the term "or" is generally intended to include the meaning of "and / or" unless the content clearly dictates otherwise. As used herein, the terms "preferred," "preferable," and "preferably" refer to embodiments of the disclosure that may provide certain advantages under certain circumstances. However, other embodiments may also be preferable under the same circumstances. Further, the description of one or more preferred embodiments is not intended to mean that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the disclosure.

[0015] All percentages, ppm, parts, and ratios are by weight unless otherwise specified. Also, the recitation of numerical ranges by endpoints includes all numbers within that range (e.g., 5 to 10 includes 5, 5.1, 5.2, 5.55, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10).

[0016] In connection with the present disclosure, any specific value (including a specific value recited as an endpoint in a range) referred to in connection with a feature can be re - combined to form new ranges.

[0017] As used herein, the term "C n ~C m -alkyl" or "alkyl" (and C n ~C mAlkoxy or alkoxy, alkylthio and alkylcarbonyl (similarly) has n to m, for example, 1 to 30 or 1 to 20 carbon atoms, preferably 1 to 16 or 1 to 12 or 1 to 8 or 1 to 6, 1 to 4 or 8 to 30 or 8 to 20 or 1 to 18 carbon atoms, a branched or unbranched saturated hydrocarbon group, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl and their isomers. C1-C4-alkyl means, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0018] "C n ~C m The term "-alkenyl" or "alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon group having n to m carbon atoms, for example, 2 to 30 or 2 to 20 carbon atoms, preferably 2 to 16 or 2 to 12 or 2 to 8 or 2 to 6 or 2 to 4 carbon atoms and at least 1 (for example, 1, 2 or 3) double bond at any position. Examples thereof include ethenyl, 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.

[0019] "C n ~C mThe term "-alkoxy" or "alkoxy" refers to a linear or branched alkyl group (as described above) having from n to m carbon atoms, for example from 1 to 30, from 1 to 20 carbon atoms, preferably from 1 to 16 or from 1 to 12 or from 1 to 8 or from 1 to 6 or from 1 to 4 carbon atoms, bonded via an oxygen on any bond within the alkyl group. Examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy.

[0020] As used herein, "C3-C m The term "cycloalkyl" or "cycloalkyl" refers to a monocyclic ring of 3 to m members, for example 3 to 10 members (or 3 to 8 members), preferably 4 to 10 members (4 to 8 members), for example 4 to 7 members (for example, 4-, 5-, 6- or 7-membered) saturated alicyclic group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.

[0021] The term "aryl" as used herein refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group. Aryl can contain from 6 to 10 carbon atoms, such as phenyl or naphthyl, in particular phenyl (also referred to as C6H5 as a substituent).

[0022] The term "aryloxy" refers to an aryl group as defined above, for example C6-C 10 -aryloxy, bonded to the remainder of the molecule via an oxygen atom.

[0023] The term "polymer" or "polymers" as used herein includes both homopolymers, i.e., polymers prepared from a single species of reactive compound, and copolymers, i.e., polymers prepared by reacting at least two polymer-forming reactive monomer compounds.

[0024] Antioxidant composition In a first aspect, the present disclosure is an antioxidant composition comprising: (a) a compound of formula (I):

Chemical formula

Chemical formula

[0025] In one embodiment, the aliphatic group having 1 to 6 carbon atoms described for R1 in the compound of formula (I) can have 1, 2, 3, 4, 5, or 6 carbon atoms, for example, 1 to 4, 1 to 3, or 1 to 2 carbon atoms. In one embodiment, the aliphatic group having 1 to 6 carbon atoms described for R1 can be selected from alkyl, and one or more non-adjacent sulfur / oxygen atoms can be optionally inserted into the above alkyl, and / or one or more non-adjacent carbon atoms of the above alkyl can be optionally replaced by -(CO)-O-.

[0026] In the compound of formula (I), R1 can be selected from hydrogen or C1-C6-alkyl, and in the above-mentioned C1-C6-alkyl, one or more non-adjacent sulfur / oxygen atoms may be optionally inserted, and / or one or more non-adjacent carbon atoms of the above-mentioned alkyl may be optionally replaced by -(CO)-O-.

[0027] R1 of the compound of formula (I) can be selected from hydrogen or C1-C4-alkyl (for example, methyl, ethyl, propyl or butyl), and in the above-mentioned C1-C4-alkyl, one or more non-adjacent sulfur / oxygen atoms may be optionally inserted, and / or one or more non-adjacent carbon atoms of the above-mentioned alkyl may be optionally replaced by -(CO)-O-.

[0028] In one embodiment, the organic group having 1 to 30 carbon atoms described for R2 of the compound of formula (I) can have 2 to 30 (for example, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 and 30), 6 to 30, 8 to 30, 8 to 22, 10 to 22 carbon atoms. In one embodiment, R2 is a hydrocarbyl. In one embodiment, R2 is a straight-chain or branched hydrocarbyl.

[0029] In one embodiment, R2 is selected from C1-C 30 -alkyl or C2-C 30 -alkenyl; more preferably, R2 is selected from C8-C 30 -alkyl or C8-C 30 -alkenyl. In one embodiment, R2 is selected from C8-C 22 -alkyl or C8-C 22 -alkenyl. In one embodiment, R2 is C 10 ~C 22 -alkyl or C 10 ~C 22-Alkenyl. In one embodiment, the alkenyl described for R2 can have 1 to 3 double bonds, for example, 1, 2, or 3 double bonds. The above-mentioned alkyl (C1-C 30 -Alkyl and C8-C 30 -Alkyl) may optionally have one or more non-adjacent sulfur / oxygen atoms inserted therein, and / or one or more non-adjacent carbon atoms of the above-mentioned alkyl may optionally be replaced by -(CO)-O-.

[0030] In the compound of formula (I), R3, R4, and R5 are each independently selected from hydrogen or C1-C4-alkyl. In a preferred embodiment, R3, R4, and R5 are each independently selected from hydrogen, methyl, or ethyl, preferably from hydrogen or methyl.

[0031] In one embodiment, the variable elements of the compound of formula (I) have the following meanings: R1 is selected from hydrogen or C1-C6-alkyl; R2 is selected from C1-C 30 -Alkyl or C2-C 30 -Alkenyl; R3, R4, and R5 are each independently selected from hydrogen or C1-C4-alkyl; The above-mentioned alkyl (C1-C6-alkyl and C1-C 30 -Alkyl) may optionally have one or more non-adjacent sulfur / oxygen atoms inserted therein, and / or one or more non-adjacent carbon atoms of the above-mentioned alkyl may optionally be replaced by -(CO)-O-.

[0032] In one embodiment, the variable elements of the compound of formula (I) have the following meanings: R1 is selected from hydrogen or C1-C3-alkyl; R2 is selected from C8-C 30 -Alkyl or C8-C 30 -Alkenyl; R3, R4, and R5 are each independently selected from hydrogen, methyl, or ethyl; The above-mentioned alkyl (C1-C3-alkyl and C8-C 30 -alkyl) may optionally have one or more non-adjacent sulfur / oxygen atoms inserted therein, and / or one or more non-adjacent carbon atoms of the above-mentioned alkyl may optionally be replaced by -(CO)-O-.

[0033] In one embodiment, the variable elements of the compound of formula (I) have the following meanings: R1 is selected from hydrogen or C1-C2-alkyl; R2 is C8-C 22 -alkyl or C8-C 22 -alkenyl; R3, R4, and R5 are each independently selected from hydrogen or methyl; The above-mentioned alkyl (C8-C 22 -alkyl) may optionally have one or more non-adjacent sulfur / oxygen atoms inserted therein, and / or one or more non-adjacent carbon atoms of the above-mentioned alkyl may optionally be replaced by -(CO)-O-.

[0034] In one embodiment, at least one of R1 and R5 (i.e., one or two) is hydrogen. In one embodiment, at least one of R1 and R5 (i.e., one or two) is methyl. In one embodiment, both R1 and R5 are methyl.

[0035] In one embodiment, the compound of formula (I) is of formula (I’):

Chemical Formula

[0036] In one embodiment, R1 and R5 in formula (I’) are C1-alkyl (i.e., methyl).

[0037] The compound of formula (I’) has three asymmetric carbon atoms at the 2, 4’ and 8’ positions in its chemical structure. All combinations of R and S configurations of one asymmetric carbon atom are included, including mixtures of enantiomers and diastereomers, such as racemic mixtures. The compound of formula (I’) is, for example, α-tocopherol, i.e., the one where R1 is C1-alkyl, R5 is C1-alkyl, and has 2R, 4’R and 8’R configurations, β-tocopherol, i.e., the one where R1 is C1-alkyl, R5 is hydrogen, and has 2R, 4’R and 8’R configurations, γ-tocopherol, i.e., the one where R1 is hydrogen, R5 is C1-alkyl, and has 2R, 4’R and 8’R configurations, or δ-tocopherol, i.e., the one where R1 is hydrogen, R5 is hydrogen, and has 2R, 4’R and 8’R configurations. Mixtures of the compounds of formula (I’) are also suitable. For example, natural vitamin E or industrially synthesized vitamin E contains the compounds of formula (I’). Preferably, at least one of R1 and R5 is C1-alkyl. In particular, R1 and R5 are C1-alkyl.

[0038] In one embodiment, the compound (component (a)) of formula (I) is selected from tocopherols, tocotrienols and mixtures thereof. Examples of tocopherols include α-, β-, γ- and δ-tocopherols. Examples of tocotrienols include α-, β-, γ- and δ-tocotrienols.

[0039] In one embodiment, component (a) includes α-, β-, γ-, δ-tocopherols or α-, β-, γ-, δ-tocotrienols or mixtures thereof.

[0040] In one embodiment, the compound of formula (I) (component (a)) is vitamin E. Vitamin E includes naturally derived vitamin E and synthetically derived vitamin E. In one embodiment, vitamin E is a synthesized mixture of stereoisomers.

[0041] In one embodiment, the compound of formula (I) (component (a)) is of formula (I'-1):

Chemical formula

[0042] The compound of formula (I'-1) has three asymmetric carbon atoms at the 2, 4', and 8' positions in its chemical structure. All combinations of R and S configurations of one asymmetric carbon atom are included, including all mixtures of enantiomers and diastereomers, such as racemic mixtures. In one embodiment, component (a) is a racemic mixture of stereoisomers of formula (I'-1).

[0043] The amount of component (a) can range from 2 to 60% by weight, for example, 2% by weight, 4% by weight, 5% by weight, 6% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 50% by weight or 60% by weight, preferably in the range of 5 to 50% by weight or in the range of 6 to 40% by weight or in the range of 8 to 30% by weight, based on the total weight of the antioxidant composition.

[0044] In one embodiment, the variable elements of the compound of formula (II) have the following meanings: R 21 is C1-C4-alkyl; R 22 is C4-C8 alkyl, preferably tertiary C4-C8-alkyl; m is an integer of 1 or 2, preferably 1, provided that when m is 2, at most one of the two ortho positions to the hydroxyl group has R 22 having it.

[0045] In one embodiment, the variable elements of the compound of formula (II) have the following meanings: R 21 is C1-C2-alkyl; R 22 is tertiary C4-C6-alkyl; m is an integer of 1 or 2, preferably 1, provided that when m is 2, at most one of the two ortho positions to the hydroxyl group has R 22 therein.

[0046] In the compound of formula (II), when m is 2 or 3, R 22 may be the same or different.

[0047] In one embodiment, one of the two ortho positions to the hydroxyl group has R 22 therein, i.e., the other ortho position does not have R 22 therein.

[0048] In one embodiment, the compound of formula (II) is selected from 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole.

[0049] In one embodiment, component (b) contains 3-tert-butyl-4-hydroxyanisole. In one embodiment, component (b) contains 2-tert-butyl-4-hydroxyanisole. In one embodiment, component (b) contains 3-tert-butyl-4-hydroxyanisole and / or 2-tert-butyl-4-hydroxyanisole.

[0050] In one embodiment, component (b) comprises or consists of 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole. The ratio of 3-tert-butyl-4-hydroxyanisole to 2-tert-butyl-4-hydroxyanisole can be in the range of 100:1 to 1:20 (for example, 100:1, 80:1, 50:1, 20:1, 10:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:10, 1:20) or in the range of 80:1 to 1:10 or in the range of 50:1 to 1:1 or in the range of 50:1 to 2:1.

[0051] In one embodiment, component (a) comprises or is vitamin E, and / or component (b) comprises or consists of 3-tert-butyl-4-hydroxyanisole and optionally 2-tert-butyl-4-hydroxyanisole. More preferably, component (a) is vitamin E and component (b) consists of 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole.

[0052] In one embodiment, component (a) is a compound of formula (I'-1) and component (b) consists of 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole.

[0053] The amount of component (b) can be in the range of 2 to 60% by weight, for example, 2% by weight, 4% by weight, 5% by weight, 6% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 50% by weight or 60% by weight, preferably in the range of 5 to 50% by weight or in the range of 6 to 40% by weight or in the range of 8 to 30% by weight, based on the total weight of the antioxidant composition.

[0054] The weight ratio of component (a) to component (b) in the antioxidant composition of the present disclosure is 10:1 to 1:10 (for example, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10), preferably 8:1 to 1:8, more preferably 5:1 to 1:5 or 1:3 to 3:1, for example 1:1.5 to 1:3 or 3:1 to 1.5:1.

[0055] Hindered phenol In one embodiment, the antioxidant composition of the present disclosure further comprises a hindered phenol, that is, a sterically hindered phenol different from the compound of formula (I) and the compound of formula (II).

[0056] Examples of the hindered phenol include phenols having one or more phenolic hydroxyl groups on the aromatic ring, preferably those having substituents, preferably alkyl groups, at the ortho position, most preferably at the ortho and para positions, with respect to the phenolic hydroxyl group.

[0057] It should be understood that the above description is not intended to limit the scope of the hindered phenols suitable for the present disclosure. In the present disclosure, the sterically hindered phenol is not limited as long as it has antioxidant properties.

[0058] Examples of suitable hindered phenols include alkylphenols such as o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol or 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-oxydiphenol, 3,4-methylenedioxydiphenol (sesamol), 3,4-dimethylphenol, hydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, pyrocatechol (1,2-dihydroxybenzene), 2-(1'-methylcyclohex-1'-yl)-4,6-dimethylphenol, 2- or 4-(1'-phenyleth-1'-yl)phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tris-tert-butylphenol, 2,6-di-tert-butylphenol, nonylphenol [11066-49-2], octylphenol [140-66-9], 2,6-dimethylphenol, bisphenol A, bisphenol F, bisphenol B, bisphenol C, bisphenol S, 3,3',5,5'-tetrabromobisphenol A, Koresin® from BASF AG, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylpyrocatechol, 2-hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl-m-cresol, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5,-tris-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl isocyanurate, 1,3,5-tris-(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate or pentaerythritol tetrakis[β-(3,5,-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 6-isobutyl-2,4-dinitrophenol, 6-sec-butyl-2,4-dinitrophenol, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, octadecyl 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionate, hexadecyl 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionate, octyl 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionate, 3-thia-1,5-pentanediol bis[(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3’-tert-butyl-4’-hydroxy-5’-methylphenyl)propionate], 1,9-nonanediol bis[(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionate], 1,7-heptanediamine bis[3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionamide], 1,1-methanediamine bis[3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionamide], 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionohydrazide, 3-(3’,5'-dimethyl-4'-hydroxyphenyl)propionic acid hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis[3-(1'-methylcyclohex-1'-yl)-5-methyl-2-hydroxyphen-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)sulfide, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)sulfide, 1,1-bis(3,4-dimethyl-2-hydroxyphen-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen-1-yl)butane, 1,3,5-tris[1'-(3'',5''-di-tert-butyl-4''-hydroxyphen-1''-yl)-meth-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl)butane, aminophenol, for example, para-aminophenol, 3-diethylaminophenol, nitrosophenol, for example, para-nitrosophenol, p-nitros-o-cresol, alkoxyphenol, for example, 2-methoxyphenol (guaiacol, pyrocatechol monomethyl ether), 4-methoxyphenol (hydroquinone monomethyl ether), 2-ethoxyphenol, 4-ethoxyphenol, 2-isopropoxyphenol, 4-butoxyphenol, mono- or di-tert-butyl-4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-Dimethoxy-4-hydroxybenzyl alcohol (syringyl alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1-(4-hydroxy-3-methoxyphenyl)ethanone (acetovanillin), eugenol, dihydroeugenol, isoeugenol, tocopherol, α-tocopherol hydroquinone, 4-methylpyrocatechol, 3-methylpyrocatechol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2,5-di-tert-amylhydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), 6-hydroxy-2,5,7,8-tetramethylchromane-2-carboxylic acid (Trolox (registered trademark)), p-cresol, and butylated dicyclopentadiene, and derivatives thereof are included.,

[0059] Corresponding sterically hindered phenol products include, for example, those having the trade name of Irganox® (BASF), such as pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (e.g., Irganox® 1010), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)trione (e.g., Irganox® 3114), thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate] (e.g., Irganox® 1035), 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9-alkyl ester (e.g., Irganox® 1135), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., Irganox® 1076), ester of polyglycol ether having a phenol derivative at the end (e.g., Irganox® 2000), 4,6-bis(octylthiomethyl)-o-cresol (e.g., Irganox® 1520); 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C 13 ~C 15 -alkyl ester (e.g., Anox® 1315), butylated product of p-cresol and dicyclopentadiene (Wingstay L) are available.

[0060] In one embodiment, the hindered phenol comprises or consists of octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate and the butylated product of p-cresol and dicyclopentadiene (Wingstay L), preferably in a ratio of 10:1 to 1:10 or 5:1 to 1:5 or 1:3 to 3:1 or 2:1 to 1:2 or 1:1.

[0061] The amount of the hindered phenol can range from 0 to 40 wt% or from 2 to 40 wt% based on the total weight of the antioxidant composition, for example, 2 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt% or from 0 to 30 wt% or from 2 to 30 wt% or from 0 to 25 wt% or from 4 to 25 wt%.

[0062] Thio synergist In one embodiment, the antioxidant composition of the present disclosure further includes a thio synergist. The thio synergist can include thioether and / or thioester.

[0063] The thioether used in accordance with the present disclosure includes compounds containing at least one thioether group, i.e., a sulfur atom substituted with two identical or different organic substituents. Each organic substituent can contain 1 to 20 or 1 to 18 or 1 to 12 carbon atoms. It should be understood that the above description is not intended to limit the scope of the thioether of the present disclosure. In the present disclosure, the thioether is not limited.

[0064] Suitable thioethers are of formula (III): R 31 -S-R 32 (III) (wherein, R 31 and R 32 are each independently of the other, C1-C 18 -alkyl, C2-C 18 -alkyl in which one or more oxygen atoms and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups are inserted, C2-C 18 -alkenyl, C6-C 12 -aryl, C5-C 12- It can be a cycloalkyl or a 5- or 6-membered heterocycle containing oxygen, nitrogen and / or sulfur, and the above groups are optionally substituted with hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic ring, heteroatom and / or heterocycle), and has a structure.

[0065] Here R 31 and R 32 can each independently be selected from the group consisting of the following groups: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxolan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl; 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxoundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxoundecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxoundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl; vinyl, 1-propenyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl; phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl; cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl or a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl; and furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.

[0066] In some embodiments, the thioether is selected from the group consisting of 2-methyl-1-propenyl tert-dodecyl thioether, cyclohexylidene methyl n-dodecyl thioether, 3-cyclohexene-(1)-ylidene methyl-n-octadecyl thioether, 3-cyclohexene-(1)-ylidene methyl-n-dodecyl thioether, 3-cyclohexene-(1)-ylidene methyl n-octyl thioether, 3-cyclohexene-(1)-ylidene methyl cyclohexyl thioether, 3-methyl-(3)-cyclohexene-(1)-ylidene methyl n-dodecyl thioether, 3-cyclohexene-(1)-ylidene methyl p-tolyl thioether, 3-cyclohexene-(1)-ylidene methyl benzyl thioether, preferably 3-cyclohexene-(1)-ylidene methyl n-dodecyl thioether and 1-hexenyl-n-dodecyl thioether.

[0067] In other embodiments, the thioether has the formula (IV):

Chemical formula

[0068] Here R 33 and R 35 can each independently be selected from the group consisting of the following groups: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, n-decyl, n-dodecyl, n-tetradecyl, n-heptadecyl, n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxolan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl;, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxau ndecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxau ndecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxau ndecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl; Phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl; and Cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl or a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

[0069] Here, R 34 can be selected from the group consisting of the following groups: Methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,1-dimethyl-1,2-ethylene or 1,2-dimethyl-1,2-ethylene, 1,6-hexylene, 1,8-octylene, 1,10-decylene, 1,12-dodecylene and 1,20-eicosylene, and cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene and cyclododecylene.

[0070] In some preferred embodiments, R 33 is optionally substituted C6-C 12-Aryl or C1-C 18 -Alkyl, preferably optionally substituted C1-C 18 -Alkyl, particularly preferably unsubstituted C1-C 18 -Alkyl; R 5 is optionally substituted C1-C 18 -Alkyl, preferably unsubstituted C1-C 18 -Alkyl; and / or R 4 is methylene, 1,2-ethylene or 1,2-propylene, preferably 1,2-ethylene.

[0071] In some embodiments, compounds having the structure of formula (V):

Chemical formula

[0072] In a preferred embodiment, the thioether is at least one selected from the group consisting of thiodipropionic acid esters such as dimethyl 3,3'-thiodipropionate, didodecyl 3,3'-thiodipropionate (DLTDP) (e.g., Irganox® PS800 from BASF), dilauryl thiodipropionate (DLTDP), ditridecyl 3,3'-thiodipropionate (DTDTP) (e.g., Songnox® DTDTP from Songwon International AG), dioctadecyl 3,3'-thiodipropionate (DSTDP), dimyristyl thiodipropionate (DMTDP), and 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diyl bis[3-(dodecylthio)propionate] (e.g., Seenox 412S).

[0073] Examples of thioesters include dilauryl thiodipropionate, dimyristyl thiodipropionate, or distearyl thiodipropionate.

[0074] In one embodiment, the thio synergist comprises or consists of dilauryl thiodipropionate (DLTDP).

[0075] The amount of the thio synergist can be in the range of 0 to 30 wt% or 2 to 30 wt%, for example, 2 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or in the range of 0 to 25 wt% or 2 to 25 wt% or 0 to 20 wt% or 4 to 20 wt%, based on the total weight of the antioxidant composition.

[0076] In one embodiment, the antioxidant composition comprises component (a), component (b), a hindered phenol different from the compound of formula (I) and the compound of formula (II), and a thio synergist.

[0077] The ratio of the total of component (a) and component (b) to the total of the hindered phenol and the thio synergist can be in the range of 10:1 to 1:100 (for example, 10:1, 8:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:10, 1:20, 1:50, 1:80 or 1:100), preferably in the range of 5:1 to 1:80 or in the range of 2:1 to 1:50. The ratio of the hindered phenol to the thio synergist can be in the range of 10:1 to 1:10 (for example, 8:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:8 or 1:10), preferably in the range of 5:1 to 1:5 or in the range of 3:1 to 1:3.

[0078] Protective colloid and / or surfactant In one embodiment, the antioxidant composition further comprises a protective colloid and / or a surfactant.

[0079] Examples of suitable protective colloids are polyvinyl alcohol, starch derivatives and cellulose derivatives or vinylpyrrolidone copolymers. A more detailed description of other suitable protective colloids is given in Houben-Weyl, Methoden der Organischen Chemie, Volume XIV / 1, Makromolekulare Stoffe [(macromolecular substances)], Georg-Thieme-Verlag, Stuttgart 1961, pp. 411-420.

[0080] The surfactant can be selected from nonionic, anionic and / or cationic surfactants, preferably nonionic surfactants.

[0081] Suitable nonionic surfactants (b) include the following: - alkoxylated C8-C 22 alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and geraniol ethoxylates: the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. Block copolymers or random copolymers may be present. These usually contain at least one alkylene oxide in an amount of 2 to 50 mol, preferably 3 to 20 mol, per mole of alcohol. The preferred alkylene oxide is ethylene oxide. The alcohol preferably has 10 to 18 carbon atoms. - alkylphenol alkoxylates, in particular, C6-C 14 - alkylphenol ethoxylates containing an alkyl chain and 5 to 30 mol of alkylene oxide per mole. - C8-C 22 -, preferably C 10 ~C 18 - alkyl polyglucosides containing an alkyl chain and usually 1 to 20, preferably 1.1 to 5, glucoside units. - N-alkyl glucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

[0082] Suitable anionic surfactants are, for example, as follows: - Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18 carbon atoms, in particular C9C 11 - alcohol sulfate, C 12 C 14 - alcohol sulfate, C 12 ~C 18 - alcohol sulfate, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow alcohol sulfate. - Sulfated alkoxylated C8-C 22 - alcohol (alkyl ether sulfate): Compounds of this type are prepared, for example, by first alkoxylating a C8-C 22 -, preferably C 10 ~C 18 - alcohol, such as a fatty alcohol, and then sulfating the alkoxylate. Ethylene oxide is preferably used for alkoxylation. - Linear C8-C 20 - alkylbenzene sulfonate (LAS), preferably linear C9-C 13 - alkylbenzene sulfonate and - alkyltoluene sulfonate. - Alkane sulfonates, in particular C8-C 24 -, preferably C 10 ~C 18 - alkane sulfonate. - Soaps, for example, Na and K salts of C8-C 24 - carboxylic acids.

[0083] Anionic surfactants are preferably added to the detergent in the form of salts. Suitable salts in this regard are, for example, alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium salts, di(hydroxyethyl)ammonium salts and tri(hydroxyethyl)ammonium salts.

[0084] Suitable cationic surfactants include the following: - C7-C 25 - alkylamines; - N,N-dimethyl-N-(hydroxy-C7-C 25 - alkyl)ammonium salts; - mono- and di-(C7-C 25 - alkyl)dimethylammonium compounds quaternized with an alkylating agent; - ester quats, in particular, esterified quaternary mono-, di- and trialkanolamines esterified with C8-C 22 - carboxylic acids; - imidazoline quats, in particular, of formula (VI) or (VII):

Chemical formula

[0085] The amount of the protective colloid and / or surfactant can be in the range of 0.2 to 12% by weight, for example, 0.2% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.8% by weight, 1% by weight, 2% by weight, 4% by weight, 6% by weight, 8% by weight, 10% by weight or 12% by weight, or in the range of 0.4 to 10% by weight or in the range of 0.6 to 8% by weight, based on the total weight of the antioxidant composition.

[0086] In one embodiment, the antioxidant composition of the present disclosure is in the form of an aqueous dispersion. In one embodiment, the average particle size (D50) of the aqueous dispersion is 10 μm or less, or 5 μm or less, or 2 μm or less. The dispersion can be a suspension or an emulsion.

[0087] The term "particle size" refers to the diameter of the particles formed by the solid component, or the diameter of the oil droplets formed by the liquid component dispersed in the continuous phase. Typical particle size / droplet diameter parameters include D10, D50, and D90. The term "median particle size" or "average particle size" refers to the D50 value at which 50% by volume of the particles / droplets have a diameter less than or equal to the D50 value. The average particle size is measured using a Malvern Mastersizer 2000 spectrometer by diluting 1.0 ml of the sample with 40 ml of deionized water and recorded in microns as the median particle size (D50).

[0088] In one embodiment, the antioxidant composition contains component (a) at 2 to 60% by weight; component (b) at 2 to 60% by weight; hindered phenol at 0 to 40% by weight or 2 to 40% by weight; thio synergist at 0 to 30% by weight or 2 to 30% by weight; protective colloid and / or surfactant at 0.2 to 12% by weight; and water as the remainder up to 100% by weight, each based on the total weight of the antioxidant composition.

[0089] In one embodiment, the antioxidant composition comprises 5 to 50% by weight of component (a); 5 to 50% by weight of component (b); 0 to 30% by weight or 2 to 30% by weight of a hindered phenol; 0 to 25% by weight or 2 to 25% by weight of a thio synergist; 0.4 to 10% by weight of a protective colloid and / or a surfactant; and water as the balance up to 100% by weight, each based on the total weight of the antioxidant composition.

[0090] In one embodiment, the antioxidant composition comprises 6 to 40% by weight of component (a); 6 to 40% by weight of component (b); 0 to 30% by weight or 2 to 30% by weight of a hindered phenol; 0 to 20% by weight or 2 to 20% by weight of a thio synergist; 0.6 to 8% by weight of a protective colloid and / or a surfactant; and water as the balance up to 100% by weight, each based on the total weight of the antioxidant composition.

[0091] In one embodiment, the antioxidant composition comprises 8 to 30% by weight of component (a); 8 to 30% by weight of component (b); 0 to 30% by weight or 2 to 30% by weight of a hindered phenol; 0 to 20% by weight or 2 to 20% by weight of a thio synergist; 0.6 to 8% by weight of a protective colloid and / or a surfactant; and water as the balance up to 100% by weight, each based on the total weight of the antioxidant composition.

[0092] The antioxidant composition of the present disclosure can further contain other additives such as epoxidized vegetable oil. The epoxidized vegetable oil is present in an amount of 20% by weight or less, preferably in the range of 0 to 15% by weight, more preferably in the range of 0 to 10% by weight, based on the weight of the antioxidant composition. An example of the epoxidized vegetable oil is epoxidized soybean oil.

[0093] According to the present disclosure, the antioxidant composition substantially does not contain an organic solvent, particularly methanol. "Substantially does not contain an organic solvent" means that the content of the organic solvent is 5% by weight or less, preferably 2% by weight or less, or 1% by weight or less, or 0.5% by weight or less, or 0.2% by weight or less, or 0.1% by weight or less, or 0.05% by weight or less, based on the weight of the antioxidant composition.

[0094] According to the present disclosure, the pH value of the antioxidant composition is 7.5 or less or 7.3 or less. The pH value can be measured at room temperature using, for example, a Metrohm 744 pH meter.

[0095] Preparation Process, Use, and Polymer Composition In a further aspect, the present disclosure provides a process for preparing an aqueous dispersion (or an antioxidant composition in the form of an aqueous dispersion) containing the antioxidant composition of the present disclosure, the process comprising homogenizing component (a), component (b), an optional hindered phenol, and an optional thio synergist, and a protective colloid and / or a surfactant in water.

[0096] Those skilled in the art can understand that when the antioxidant composition of the present disclosure is in the form of an aqueous dispersion, the "process for preparing an aqueous dispersion containing the antioxidant composition of the present disclosure" means the "process for preparing an antioxidant composition in the form of an aqueous dispersion".

[0097] In one embodiment, when component (a), component (b), the hindered phenol or the thio synergist is solid, this solid component is melted by heating before homogenization, and the homogenization is carried out in water in the presence of a protective colloid and / or a surfactant.

[0098] In one embodiment, the protective colloid and / or the surfactant is dissolved in water before homogenization. When both the protective colloid and the surfactant are used, both the protective colloid and the surfactant are dissolved in water before homogenization.

[0099] In one embodiment, the homogenization is carried out at a high temperature, preferably at a temperature exceeding the melting points of component (a), component (b), the hindered phenol (if present) and the thio synergist (if present).

[0100] In a further aspect, the present disclosure provides the use of the antioxidant composition of the present disclosure as a chain terminator and / or a stabilizer.

[0101] Generally, the antioxidant composition of the present disclosure can be used as a chain terminator and / or a stabilizer in free radical polymerization.

[0102] Examples of free radical polymerization include suspension polymerization, microsuspension polymerization, emulsion polymerization and the like. In free radical polymerization, a free radical polymerization initiator such as an organic peroxide or an azo compound can be used.

[0103] The monomers for free radical polymerization contain free radical polymerizable groups. The free radical polymerizable groups can be selected from allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamide, methacrylamide or ethynyl. Generally, examples of the monomers include vinyl monomers, conjugated diene monomers, acrylic monomers, methacrylic monomers, acrylonitrile and mixtures thereof, particularly vinyl chloride, styrene, acrylonitrile, butadiene and (meth)acrylate.

[0104] The total input amount of component (a) and component (b) into the free radical polymerization system can be in the range of 20 to 4000 ppm (for example, 20 ppm, 30 ppm, 35 ppm, 40 ppm, 50 ppm, 80 ppm, 100 ppm, 200 ppm, 500 ppm, 800 ppm, 1000 ppm, 1500 ppm, 2000 ppm, 3000 ppm or 4000 ppm), preferably in the range of 30 to 2000 ppm or in the range of 40 to 1000 ppm or in the range of 45 to 800 ppm, based on the weight of the monomers added to the polymerization system.

[0105] In a further aspect, the present disclosure provides a polymer composition comprising the antioxidant composition of the present disclosure. The polymer can be derived from the monomers described above, and in particular, can be selected from polyvinyl chloride, acrylonitrile-butadiene-styrene (ABS), methyl methacrylate-butadiene-styrene (MBS), nitrile butadiene rubber or styrene butadiene rubber, etc.

[0106] The total amount of component (a) and component (b) in the polymer composition can be in the range of 20 to 4000 ppm (for example, 20 ppm, 30 ppm, 35 ppm, 40 ppm, 50 ppm, 80 ppm, 100 ppm, 200 ppm, 500 ppm, 800 ppm, 1000 ppm, 1500 ppm, 2000 ppm, 3000 ppm or 4000 ppm), preferably in the range of 30 to 2000 ppm or in the range of 40 to 1000 ppm or in the range of 45 to 800 ppm, based on the total weight of the polymer composition.

Examples

[0107] Materials Component (a): Vitamin E (Irganox E 201) from BASF. This is a phenolic antioxidant and is 2,5,7,8-tetramethyl-2-[4,8,12-trimethyltridecyl]chroman-6-ol as shown below:

Chemical formula

[0108] Irganox E 201 consists of 100% D,L-α-tocopherol.

[0109] Component (b): BHA (butylated hydroxy-anisole) from DANISCO; containing 90% 3-tert-butyl-4-hydroxyanisole, total of 98% of 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole. Protective colloid: Inovol PA8 from Ineos, degree of hydrolysis: 86 - 90 mol% (TM / SA / 6), viscosity (mPa·s) of 4% aqueous solution: 5 - 6 (TM / SA / 7). Hindered phenol: Irganox 1076: octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate from BASF; Wingstay L: butylated product of p-cresol and dicyclopentadiene. Thio synergist: Irganox PS 800 FL = DLTDP = dilauryl 3,3'-thiodipropionate. Commercial product P: A mixture of 33.3% Irganox 1076, 33.3% DLTDP and 33.3% Wingstay L.

[0110] Test methods - Pressure drop: Reading of the pressure gauge - Hydrochloric acid elimination test: This test is based on a device that measures the time until the conductivity of an aqueous HCl solution reaches 200 microsiemens / cm by heating the PVC resin to 180°C, then recovering HCl in water (i.e., obtaining an aqueous HCl solution) and testing the conductivity of the aqueous HCl solution. - Whiteness: The whiteness was inspected with a Datacolor SF 600X (spectrophotometer). Before the inspection, the polymer sample was filled in a petri dish and the surface of the polymer sample was scraped off. - D50: 1.0 ml of the sample was diluted with 40 ml of deionized water, and the particle size of the solid antioxidant and the droplet size of the liquid antioxidant in the aqueous suspoemulsion of the antioxidant were measured using a Malvern Mastersizer 2000 spectroscopic device and recorded in micron units as the median particle size (D50).

[0111] Example 1: Preparation of Sample 1 1) 2.67 Kg of BHA was added to a container and heated to 85°C. Then, 1.33 Kg of vitamin E was added, and the mixture was stirred at 25 RPM until completely melted. 2) While stirring, 3 Kg of a 20% aqueous solution of Poval 8 - 88 (polyvinyl alcohol) was added to the container. Then, the speed of the stirrer was increased to 75 RPM, and the homogenizer was started at 3000 RPM. 3) After 5 minutes, the homogenization speed was further increased to 6000 RPM to start emulsification. 4) After 1 hour, the average particle size (D50) was examined to confirm whether it had become 2 μm or less. If not, homogenization was continued, and when the average particle size (D50) became 2 μm or less, homogenization was stopped. 5) After adding 3 Kg (30 wt%) of deionized water, the mixture was stirred well at 75 RPM to obtain Sample 1.

[0112] Example 2: Preparation of Sample 2 1) 1.33 Kg of BHA was added to a container and heated to 85°C. Then, 2.67 Kg of vitamin E was added, and the mixture was stirred at 25 RPM until completely melted. 2) While stirring, 3 Kg (30 wt%) of a 20% aqueous solution of polyvinyl alcohol was added to the container. Then, the speed of the stirrer was increased to 75 RPM, and the homogenizer was started at 3000 RPM. 3) The homogenization speed was further increased to 6000 RPM to start emulsification. 4) After 1 hour, the average particle size was examined to confirm whether it had become 2 μm or less. If not, homogenization was continued, and when the average particle size (D50) became 2 μm or less, homogenization was stopped. 5) After adding 3 Kg (30% by weight) of deionized water, Sample 2 was obtained by sufficiently stirring the mixture at 75 RPM.

[0113] Example 3: Preparation of Sample 3 1) Irganox 1076 (10 parts by weight), DLTDP (10 parts by weight), Wingstay L (10 parts by weight) and BHA (5 parts by weight) were added to a container, heated to 85 °C, and then stirred at 75 RPM until completely melted. 2) The temperature was cooled to 65 °C, vitamin E (5 parts by weight) was added, and the mixture was sufficiently stirred at 75 RPM. 3) A 20% aqueous solution of polyvinyl alcohol (25 parts by weight) was added, and the homogenizer was started at 3000 RPM. 4) The homogenization rate was increased to 6000 RPM to initiate emulsification. 5) After 1 hour, the average particle size was examined to confirm whether it had become 2 μm or less. If not, homogenization was continued, and homogenization was stopped when the average particle size (D50) became 2 μm or less. 6) After adding deionized water (35 parts by weight), Sample 3 was obtained by stirring the mixture at 75 RPM.

[0114] Examples 4 and 5 and Comparative Examples 1 and 2: PVC polymerization using Samples 1 and 2, vitamin E, and BHA respectively This experiment was carried out based on a K67 grade PVC resin polymerized at 57 °C. The detailed preparation of polyvinyl chloride is as follows: (1) 666 g of deionized water, 0.250 g of cumyl peroxypivalate (50% by weight in water and methanol), 0.222 g of di(2-ethylhexyl) peroxydicarbonate (50% by weight in water and methanol), and 0.8 g of polyvinyl alcohol were mixed in a 2 L polymerization reactor; (2) After evacuating the reactor, 444 g of vinyl chloride monomer was added with stirring, and when the temperature was raised to 57 °C, the internal pressure of the reactor during polymerization became 9 bar; (3) When the internal pressure of the reactor dropped to 8 bar (conversion rate of monomer about 85%), Sample 1, Sample 2, vitamin E or BHA was added at the input amounts shown in Table 1 below. The input amounts of the active substances in Table 1 are based on the first-added vinyl chloride, i.e., 444 g. The input amounts of the active substances in Examples 4 and 5 relate to the total of vitamin E and BHA. (4) The temperature was maintained and the pressure drop was observed for 1.5 hours and summarized in Table 1. A smaller pressure drop indicates a higher efficiency of chain termination (because less further polymerization occurs). (5) After removing the residual monomer from the obtained polymer slurry, the polymer slurry was dried to obtain a polyvinyl chloride resin.

[0115] The whiteness (initial) of the PVC resin and the whiteness of the PVC resin after heating at 160 °C for 10 minutes were inspected and summarized in Table 1.

[0116]

Table 1

[0117] From the results of the pressure drop in Table 1, it is shown that the chain termination effects of Sample 1 and Sample 2 of the present invention are not only superior to that of vitamin E alone, but also superior to that of BHA alone. Further, it is also shown that components (a) and (b) exhibit a synergistic effect in terms of chain termination.

[0118] Furthermore, as can be seen from the whiteness (initial), when Samples 1 and 2 of the present invention were used, the whiteness was much higher than when vitamin E was used alone. The whiteness of the polymer of Example 5 (vitamin E:BHA = 2:1) after heating at 160 °C for 10 minutes was 93, which was higher than those of vitamin E alone and BHA alone. Therefore, a strong synergistic effect was shown in terms of preventing yellowing. Furthermore, in Example 4 (vitamin E:BHA = 1:2) as well, the whiteness (after 10 minutes at 160 °C), that is, 91, was much higher than the mathematically predicted whiteness, that is, 1 / 3 × 87 (Comparative Example 1, VE alone) + 2 / 3 × 91 (Comparative Example 2, BHA alone) = 89.6, indicating a relative synergistic effect.

[0119] The PVC resins obtained from Examples 4 and 5 showed that in the dehydrochlorination test, the time until the conductivity of the HCl aqueous solution reached 200 microsiemens / cm was 45 minutes and 46 minutes, respectively. The longer this time, the slower the rate of HCl release from the PVC resin, which means less decomposition of the PVC resin.

[0120] Examples 6 and Comparative Example 3: PVC polymerization using Sample 3 and a commercial product P, respectively This experiment was carried out based on a K67 grade PVC resin polymerized at 57 °C. The detailed preparation of polyvinyl chloride is as follows: (1) 666 g of deionized water, 0.250 g of cumyl peroxypivalate (50 wt% in water and methanol), 0.222 g of di(2-ethylhexyl) peroxydicarbonate (50 wt% in water and methanol), and 0.8 g of polyvinyl alcohol were mixed in a 2 L polymerization reactor; (2) After evacuating the reactor, 444 g of vinyl chloride monomer was added with stirring, and when the temperature was raised to 57 °C, the internal pressure of the reactor during polymerization reached 9 bar; (3) When the internal pressure of the reactor dropped to 8 bar (the conversion rate of the monomer was about 85%), Sample 3 or the commercial product P was added in the amounts shown in Table 2 below. The amounts in Table 2 are based on 444 g of vinyl chloride added initially. The amount of active substances in Example 6 relates to the total of vitamin E, BHA, Irganox 1076, DLTDP, and Wingstay L. The amount of active substances in Comparative Example 3 relates to the total of Irganox 1076, DLTDP, and Wingstay L. (4) The temperature was maintained and the pressure drop was observed for 1.5 hours and summarized in Table 2. A smaller pressure drop indicates a higher efficiency of terminating the chain (because less further polymerization occurs). (5) After removing the residual monomer from the obtained polymer slurry, the polymer slurry was dried to obtain a polyvinyl chloride resin.

[0121] The whiteness of the PVC resin (initial) and the whiteness of the PVC resin after heating at 160 °C for 10 minutes were inspected and summarized in Table 2. The results of the dehydrochlorination test were also summarized in Table 2.

[0122]

Table 2

[0123] The total of vitamin E and BHA in Example 6 was 50 ppm, and excellent chain termination property was also shown in this example (the pressure drop was only 0.65), which was significantly superior to Comparative Example 3 (without vitamin E and BHA). Furthermore, from the results of the dehydrochlorination test, it was shown that the active components of Sample 3 exerted a synergistic effect on the thermal stabilization of the polymer.

Claims

1. An antioxidant composition, (a) Equation (I): 【Chemistry 1】 (In the formula, R １ It is selected from hydrogen or an aliphatic group having 1 to 6 carbon atoms; R ２ This is an organic group having 1 to 30 carbon atoms; R ３ , R ４ , R ５ These are, independently of each other, hydrogen or C １ ~C ４ Chromanol derivatives (selected from alkyl groups); and (b) Formula (II): 【Chemistry 2】 (In the formula, R ２１ is C １ to C ６ -alkyl; R ２２ C １ ~C ８ -It is alkyl, m is an integer of 1, 2, or 3, except when m is 2 or 3, where R is one of the two ortho positions of the hydroxyl group. ２２ (There can be at most one) An antioxidant composition containing the compound.

2. The antioxidant composition according to claim 1, further comprising a protective colloid and / or a surfactant.

3. R １ is hydrogen or C １ ~C ６ - Selected from alkyl groups; Preferably, R １ is hydrogen or C １ ~C ４ - Selected from alkyl groups; More specifically, R １ is hydrogen or C １ ~C ３ - Alkyl; The alkyl (C １ ~C ６ - Alkyl, C １ ~C ４ - Alkyl and C １ ~C ３ The antioxidant composition according to claim 1, wherein one or more non-adjacent sulfur / oxygen atoms may be optionally inserted into the alkyl group, and / or one or more non-adjacent carbon atoms of the alkyl group may be optionally replaced with -(CO)-O-.

4. R ２ C １ ~C ３０ - Alkyl or C ２ ~C ３０ - Selected from alkenyls; more preferably R ２ C ８ ~C ３０ - Alkyl or C ８ ~C ３０ - Selected from alkenyls, the alkyl (C １ ~C ３０ - Alkyl and C ８ ~C ３０ The antioxidant composition according to claim 1, wherein one or more non-adjacent sulfur / oxygen atoms may be optionally inserted into the alkyl group, and / or one or more non-adjacent carbon atoms of the alkyl group may be optionally replaced with -(CO)-O-.

5. R ３ , R ４ , R ５ The antioxidant composition according to claim 1, wherein each of the elements is independently selected from hydrogen, methyl, or ethyl.

6. Component (a) is α-,β-,γ-,δ-tocopherol or α-,β-,γ-,δ-tocotrienol or a mixture thereof, preferably vitamin E, more preferably formula (I'-1): 【Transformation 3】 The antioxidant composition according to claim 1, comprising the compound.

7. R ２１ C １ ~C ４ - Alkyl; R ２２ C ４ ~C ８ Alkyl, preferably tertiary C ４ ~C ８ - Alkyl; m is an integer of 1 or 2, preferably 1, however, when m is 2, R is one of the two ortho positions of the hydroxyl group. ２２ The antioxidant composition according to claim 1, wherein it has at most one of the following properties.

8. The antioxidant composition according to claim 1, wherein component (b) comprises 3-tert-butyl-4-hydroxyanisole and / or 2-tert-butyl-4-hydroxyanisole, preferably comprising 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole in a ratio of 100:1 to 1:20 or 80:1 to 1:

10.

9. The antioxidant composition according to claim 1, wherein the weight ratio of component (a) to component (b) is 5:1 to 1:5, preferably 3:1 to 1:3, and more preferably 1:2 to 2:

1.

10. The antioxidant composition according to claim 1, further comprising a hindered phenol, a thio synergist, or a combination thereof, different from the compound of formula (I) and the compound of formula (II).

11. The antioxidant composition according to claim 1, wherein the composition is in the form of an aqueous dispersion, and the average particle size (D50) of the aqueous dispersion is 10 μm or less, preferably 5 μm or less, and more preferably 2 μm or less.

12. The antioxidant composition according to claim 2, Component (a) in an amount of 2 to 60% by weight or 5 to 50% by weight; Component (b) in an amount of 2 to 60% by weight or 5 to 50% by weight; Hindered phenol in an amount of 0-40% by weight or 2-40% by weight; A thio synergistic agent in an amount of 0-30% by weight or 2-30% by weight; Protective colloid and / or surfactant in an amount of 0.2 to 12% by weight or 0.4 to 10% by weight; With water, which is the remainder up to 100% by weight; An antioxidant composition comprising the above, each based on the total weight of the antioxidant composition.

13. The antioxidant composition according to claim 1, wherein the composition substantially does not contain an organic solvent.

14. A process for preparing an aqueous dispersion comprising an antioxidant composition according to any one of claims 1 to 13, the process comprising homogenizing component (a) and component (b), an optional hindered phenol, an optional thio synergist, and a protective colloid and / or surfactant in water at a high temperature.

15. The process according to claim 14, wherein if component (a), component (b), hindered phenol, or thio synergist is solid, the solid component is melted by heating before the homogenization is carried out, and the homogenization is carried out in water in the presence of the protective colloid and / or surfactant.

16. The process according to claim 14, wherein the homogenization is carried out at a temperature above the melting points of component (a), component (b), and optionally hindered phenol and optionally thio synergist.

17. Use of the antioxidant composition according to any one of claims 1 to 13 as a chain stopper and / or stabilizer.

18. A polymer composition comprising the antioxidant composition according to any one of claims 1 to 13.

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