Sustainable antioxidant composition, use thereof and polymer composition comprising 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 method for preparing an aqueous dispersion comprising the antioxidant composition, use of the antioxidant composition as a chain terminator and / or stabilizer, and a polymer composition comprising the antioxidant composition. Background Art

[0002] Antioxidants can be used as chain terminators in free radical polymerization. Conventional antioxidants used in free radical polymerization, especially PVC polymerization, are inefficient for chain termination or have EHS issues (like BPA). Moreover, traditional chain terminators such as ATSC (Acetone ThioSemiCarbazone) and DEHA (Diethylhydroxylamine) are very weak in thermal stabilization of polymers, especially PVC resins. In addition, these chain terminators are not easy to handle in free radical polymerization such as PVC production because they need to be pre-dissolved in methanol or similar (toxic) organic solvents or alkaline water.

[0003] Therefore, there is still a need in the art to provide an antioxidant composition which has excellent chain termination properties as well as excellent thermal stabilization of polymers and is also ready for use in free radical polymerization. Summary of the invention

[0004] One object of the present disclosure is to provide an antioxidant composition which has excellent chain termination properties as well as excellent thermal stabilization of polymers and is also ready for use in free radical polymerization.

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

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

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

[0008] It has been unexpectedly found that the above objects can be achieved by the following embodiments:

[0009] 1. An antioxidant composition comprising

[0010] (a) Derivatives of chromanol of formula (I)

[0011]

[0012] in

[0013] R1 is selected from hydrogen or an aliphatic group having 1 to 6 carbon atoms;

[0014] R2 is an organic group having 1 to 30 carbon atoms; and

[0015] R3, R4, R5 are independently selected from hydrogen or C1-C4-alkyl;

[0016] as well as

[0017] (b) Compounds of formula (II)

[0018]

[0019] in

[0020] R 21 is a C1-C6-alkyl group,

[0021] R 22 is C1-C8-alkyl, and

[0022] m is an integer of 1, 2 or 3, provided that if m is 2 or 3, at most one of the two ortho positions of the hydroxyl group carries R 22 .

[0023] 2. The antioxidant composition according to item 1, wherein the composition further comprises a protective colloid and / or a surfactant.

[0024] 3. The antioxidant composition according to item 1 or 2, wherein R1 is selected from hydrogen or C1-C6-alkyl;

[0025] Preferably, R1 is selected from hydrogen or C1-C4-alkyl;

[0026] More preferably, R1 is hydrogen or C1-C3-alkyl;

[0027] The above alkyl groups (C1-C6-alkyl, C1-C4-alkyl and C1-C3-alkyl) may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl groups may optionally be replaced by -(CO)-O-.

[0028] 4. The antioxidant composition according to any one of items 1 to 3, wherein 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, wherein the above alkyl (C1-C 30 -alkyl and C8-C 30-alkyl) may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl may optionally be replaced by -(CO)-O-.

[0029] 5. The antioxidant composition according to any one of items 1 to 4, wherein R3, R4, and R5 are independently selected from hydrogen, methyl or ethyl.

[0030] 6. The antioxidant composition according to any one of items 1 to 5, wherein component (a) comprises α-, β-, γ-, δ-tocopherol, or α-, β-, γ-, δ-tocotrienol, or a mixture thereof, preferably vitamin E, more preferably a compound of formula (I'-1):

[0031]

[0032] 7. The antioxidant composition according to any one of items 1 to 6, wherein

[0033] R 21 is C1-C4-alkyl;

[0034] R 22 is C4-C8-alkyl, preferably tertiary C4-C8-alkyl; and

[0035] m is an integer of 1 or 2, preferably 1, provided that if m is 2, at most one of the two ortho positions of the hydroxyl group carries R 22 .

[0036] 8. The antioxidant composition according to any one of items 1 to 7, wherein component (b) comprises 3-tert-butyl-4-hydroxyanisole and / or 2-tert-butyl-4-hydroxyanisole, preferably 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.

[0037] 9. The antioxidant composition according to any one of items 1 to 8, wherein the weight ratio of component (a) to component (b) is 5:1 to 1:5, preferably 3:1 to 1:3, more preferably 1:2 to 2:1.

[0038] 10. The antioxidant composition according to any one of items 1 to 9, wherein the composition further comprises a hindered phenol different from the compound of formula (I) and the compound of formula (II), a thiosynergist, or a combination thereof.

[0039] 11. The antioxidant composition according to any one of items 1 to 10, wherein the composition is in the form of an aqueous dispersion and the average particle size (D50) of the aqueous dispersion is not greater than 10 μm, preferably not greater than 5 μm, more preferably not greater than 2 μm.

[0040] 12. The antioxidant composition according to any one of items 2 to 11, wherein the composition comprises

[0041] 2 to 60 wt% or 5 to 50 wt% of component (a);

[0042] 2 to 60 wt% or 5 to 50 wt% of component (b);

[0043] 0 to 40 wt% or 2 to 40 wt% of hindered phenol;

[0044] 0 to 30 wt% or 2 to 30 wt% of a thiosynergist;

[0045] 0.2 to 12 wt% or 0.4 to 10 wt% of a protective colloid and / or a surfactant; and

[0046] Water: balance to 100wt%,

[0047] In each case based on the total weight of the antioxidant composition.

[0048] 13. The antioxidant composition according to any one of items 1 to 12, wherein the composition is substantially free of organic solvents.

[0049] 14. A method for preparing an aqueous dispersion comprising an antioxidant composition according to any one of items 1 to 13, comprising homogenizing component (a) and component (b), optionally hindered phenol, optionally thiosynergist, and protective colloid and / or surfactant in water at elevated temperature.

[0050] 15. The method according to item 14, wherein when component (a), component (b), hindered phenol or thiosynergist is in solid form, the solid components are heated to melt before the homogenization, and the homogenization is carried out in water in the presence of the protective colloid and / or surfactant.

[0051] 16. The method according to item 14 or 15, wherein the homogenization is carried out at a temperature above the melting point of component (a), component (b), and optionally hindered phenol and optionally thiosynergist.

[0052] 17. Use of the antioxidant composition according to any one of items 1 to 13 as a chain terminator and / or stabilizer.

[0053] 18. A polymer composition comprising the antioxidant composition according to any one of items 1 to 13.

[0054] The beneficial technical effects brought about by the antioxidant composition disclosed herein include but are not limited to:

[0055] (1) Excellent chain termination properties in free radical polymerization such as PVC polymerization, and even shows synergistic effects in chain termination;

[0056] (2) Excellent thermal stabilization of polymers;

[0057] (3) ease of operation (no pre-dissolution required) and improved sustainability (EHS) during PVC polymerization (no use of toxic / organic solvents);

[0058] (4) Excellent anti-yellowing effect.

[0059] It should be understood that the inventive content of the present invention is not intended to limit the scope of the present disclosure. According to the following description, other features of the present disclosure will become easily understood. DETAILED DESCRIPTION

[0060] In the following description, the present disclosure is further explained with reference to the embodiments to facilitate full understanding by those skilled in the art. It should be understood that these embodiments are provided only to better understand the subject matter of the present disclosure, rather than to impose any limitation on the scope of protection, applicability or embodiments as described in the present set of claims. It should be understood that, without departing from the spirit of the present disclosure, those skilled in the art may omit, replace or add various technical features to each embodiment based on actual needs. In addition, the technical features described in some embodiments may be combined with the technical features described in other embodiments.

[0061] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0062] In the present disclosure, it can be understood that the terms "comprise", "comprising", "include", "including" and their various variations are open terms, which mean "including but not limited to"; in contrast, the term "consisting of..." and its various variations exclude any unspecified components, steps or procedures; the term "embodiment" can be understood as "at least one embodiment"; the term "another embodiment" can be understood as "at least one other embodiment". Unless explicitly stated, other terms that may appear but are not mentioned here should not be interpreted or limited in a manner contrary to the concept on which the embodiments of the present disclosure are based.

[0063] Throughout this disclosure, the expressions "a / an", "the", and "one or more" are used interchangeably and are intended to include both the plural and singular, unless expressly specified or clearly indicated by the context as a separate singular. When a separate singular is intended, the term "one" is typically used. Unless the context clearly dictates otherwise, the term "or" is generally intended to include the meaning of "and / or". As used herein, "preferred", "preferable", and "preferably" refer to embodiments of the present disclosure that may confer certain advantages in certain circumstances. However, other embodiments may also be preferred under the same circumstances. In addition, the enumeration of one or more preferred embodiments does not mean that other embodiments are not available, and is not intended to exclude other embodiments from the scope of the present disclosure.

[0064] Unless otherwise indicated, all percentages, ppm, parts and ratios are by weight. And the enumeration of numerical ranges by endpoints includes all numerical values ​​contained in 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).

[0065] In the context of this disclosure, any specific values ​​mentioned for features (including specific values ​​mentioned as endpoints in ranges) can be recombined to form new ranges.

[0066] As used herein, the term "C n -C m -alkyl" or "alkyl" (and also C n -C mAlkoxy or alkoxy, alkylthio and alkylcarbonyl) refers to a branched or unbranched saturated hydrocarbon group having 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, 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 C1-C4-alkyl means methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 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 isomers thereof. For example, C1-C4-alkyl means methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0067] The term "C n -C m "-alkenyl" or "alkenyl" refers to a straight 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 one (e.g., one, two or three) double bond at any position. Examples 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.

[0068] The term "C n -C m "-Alkoxy" or "alkoxy" refers to a straight or branched alkyl group having n to m carbon atoms, for example, 1 to 30, 1 to 20 carbon atoms, preferably 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4 carbon atoms (as mentioned above) bonded through an oxygen atom at any bond in the alkyl group. Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy.

[0069] As used herein, the term "C3-C m"Cycloalkyl" or "cycloalkyl" refers to a monocyclic ring of a 3- to m-membered, for example, 3- to 10-membered (or 3- to 8-membered), preferably 4- to 10-membered (4- to 8-membered), such as 4- to 7-membered (e.g., 4-, 5-, 6- or 7-membered) saturated alicyclic group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.

[0070] As used herein, the term "aryl" refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group. The aryl group may contain 6 to 10 carbon atoms, such as phenyl or naphthyl, especially phenyl (also referred to as C6H5 as a substituent).

[0071] The term "aryloxy" refers to an aryl group as defined above which is bonded to the remainder of the molecule via an oxygen atom, for example a C6-C 10 -Aryloxy.

[0072] As used herein, the term "polymer" or "polymers" includes both homopolymers (ie, polymers prepared from a single reactive compound) and copolymers (ie, polymers prepared by the reaction of at least two polymer-forming reactive monomer compounds).

[0073] Antioxidant composition

[0074] In a first aspect, the present disclosure provides an antioxidant composition comprising

[0075] (a) Derivatives of chromanol of formula (I)

[0076]

[0077] in

[0078] R1 is selected from hydrogen or an aliphatic group having 1 to 6 carbon atoms;

[0079] R2 is an organic group having 1 to 30 carbon atoms; and

[0080] R3, R4, R5 are independently selected from hydrogen or C1-C4-alkyl;

[0081] as well as

[0082] (b) Compounds of formula (II)

[0083]

[0084] in

[0085] R 21 is a C1-C6-alkyl group,

[0086] R 22 is C1-C8-alkyl, and

[0087] m is an integer of 1, 2 or 3, provided that if m is 2 or 3, at most one of the two ortho positions of the hydroxyl group carries R 22 .

[0088] In an embodiment, the aliphatic group having 1 to 6 carbon atoms mentioned for R1 in the compound of formula (I) may have 1, 2, 3, 4, 5 or 6 carbon atoms, such as 1 to 4, 1 to 3, 1 to 2 carbon atoms. In an embodiment, the aliphatic group having 1 to 6 carbon atoms mentioned for R1 may be selected from alkyl, wherein the above alkyl may be optionally interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl may be optionally replaced by -(CO)-O-.

[0089] In the compounds of formula (I), R1 may be selected from hydrogen or C1-C6-alkyl,

[0090] The above C1-C6-alkyl group may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl group may optionally be replaced by -(CO)-O-.

[0091] In the compounds of formula (I), R1 can be selected from hydrogen or C1-C4-alkyl (e.g. methyl, ethyl, propyl or butyl), wherein the above C1-C4-alkyl can be optionally interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl can be optionally replaced by -(CO)-O-.

[0092] In an embodiment, the organic group with 1 to 30 carbon atoms mentioned for R2 in the compound of formula (I) can have 2 to 30 (e.g., 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 an embodiment, R2 is a hydrocarbon group. In an embodiment, R2 is a straight or branched hydrocarbon group.

[0093] In an embodiment, wherein 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 In an embodiment, R2 is selected from C8-C 22 -alkyl, or C8-C 22 In an embodiment, R2 is selected from C 10 -C 22 -alkyl, or C 10 -C 22-alkenyl. In an embodiment, the alkenyl mentioned for R2 may have 1 to 3 double bonds, for example 1, 2 or 3 double bonds. 30 -alkyl and C8-C 30 -alkyl) may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl may optionally be replaced by -(CO)-O-.

[0094] In the compounds of formula (I), R3, R4, R5 are independently selected from hydrogen or C1-C4-alkyl. In a preferred embodiment, R3, R4, R5 are independently selected from hydrogen, methyl or ethyl, preferably hydrogen or methyl.

[0095] In the embodiments, the variables in the compounds of formula (I) have the following meanings:

[0096] R1 is selected from hydrogen or C1-C6-alkyl;

[0097] R2 is selected from C1-C 30 -alkyl, or C2-C 30 -alkenyl; and

[0098] R3, R4, R5 are independently selected from hydrogen or C1-C4-alkyl;

[0099] Among them, the above alkyl groups (C1-C6-alkyl and C1-C 30 -alkyl) may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl may optionally be replaced by -(CO)-O-.

[0100] In the embodiments, the variables in the compounds of formula (I) have the following meanings:

[0101] R1 is selected from hydrogen or C1-C3-alkyl;

[0102] R2 is selected from C8-C 30 -alkyl, or C8-C 30 -alkenyl; and

[0103] R3, R4, R5 are independently selected from hydrogen, methyl or ethyl;

[0104] Among them, the above alkyl groups (C1-C3-alkyl and C8-C 30 -alkyl) may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl may optionally be replaced by -(CO)-O-.

[0105] In the embodiments, the variables in the compounds of formula (I) have the following meanings:

[0106] R1 is selected from hydrogen or C1-C2-alkyl;

[0107] R2 is selected from C8-C 22 -alkyl, or C8-C 22 -alkenyl; and

[0108] R3, R4, R5 are independently selected from hydrogen or methyl;

[0109] Among them, the above alkyl (C8-C 22 -alkyl) may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl may optionally be replaced by -(CO)-O-.

[0110] In an embodiment, at least one (i.e., one or both) of R1 and R5 is not hydrogen. In an embodiment, at least one (i.e., one or both) of R1 and R5 is methyl. In an embodiment, both R1 and R5 are methyl.

[0111] In embodiments, the compound of formula (I) includes a compound of formula (I'):

[0112]

[0113] in

[0114] R1 and R5 are independently H or C1-alkyl (ie, methyl).

[0115] In an embodiment, R1 and R5 in formula (I') are C1-alkyl (ie, methyl).

[0116] The compound of formula (I') has three asymmetric carbon atoms at position 2, 4' and 8' in its chemical structure. All combinations of R and S configurations at a single asymmetric carbon atom are covered, and also mixtures of enantiomers and diastereomers, such as racemic mixtures, are included. The compound of formula (I') is, for example, alpha-tocopherol (i.e. R1 is C1-alkyl, R5 is C1-alkyl and configuration 2R, 4'R and 8'R), beta-tocopherol (i.e. R1 is C1-alkyl, R5 is hydrogen and configuration 2R, 4'R and 8'R), gamma-tocopherol (i.e. R1 is hydrogen, R5 is C1-alkyl and configuration 2R, 4'R and 8'R), or delta-tocopherol (i.e. R1 is hydrogen, R5 is hydrogen and configuration 2R, 4'R and 8'R). The mixture of the compound of formula (I') is also suitable, for example, natural vitamin E or industrially synthesized vitamin E contain the compound of formula (I'). Preferably, at least one of R1 and R5 is a C1-alkyl group. In particular, R1 and R5 are C1-alkyl groups.

[0117] In an embodiment, the compound of formula (I) (component (a)) is selected from tocopherol, tocotrienol, and mixtures thereof. Tocopherol may include, for example, α-, β-, γ- and δ-tocopherol. Tocotrienol may include, for example, α-, β-, γ- and δ-tocotrienol.

[0118] In an embodiment, component (a) comprises α-, β-, γ-, δ-tocopherol, or α-, β-, γ-, δ-tocotrienol, or a mixture thereof.

[0119] In an embodiment, the compound of formula (I) (component (a)) is vitamin E. Vitamin E contains vitamin E from natural sources and vitamin E from synthetic sources. In an embodiment, vitamin E is synthetic and is a mixture of stereoisomers.

[0120] In an embodiment, the compound of formula (I) (component (a)) is a compound of formula (I'-1):

[0121]

[0122] The compound of formula (I'-1) contains three asymmetric carbon atoms at positions 2, 4' and 8' in its chemical structure. All combinations of R and S configurations at a single asymmetric carbon atom are contemplated, as well as mixtures of enantiomers and diastereomers, such as racemic mixtures. In an embodiment, component (a) is a racemic mixture of stereoisomers of formula (I'-1).

[0123] Based on the total weight of the antioxidant composition, the amount of component (a) can be in the range of 2 to 60 wt%, for example 2 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 50 wt%, or 60 wt%, preferably 5 to 50 wt%, or 6 to 40 wt%, or 8 to 30 wt%.

[0124] In the embodiments, the variables in the compounds of formula (II) have the following meanings:

[0125] R 21 is C1-C4-alkyl;

[0126] R 22 is C4-C8-alkyl, preferably tertiary C4-C8-alkyl; and

[0127] m is an integer of 1 or 2, preferably 1, provided that if m is 2, at most one of the two ortho positions of the hydroxyl group carries R 22 .

[0128] In the embodiments, the variables in the compounds of formula (II) have the following meanings:

[0129] R 21 is C1-C2-alkyl;

[0130] R 22 is a tertiary C4-C6-alkyl group; and

[0131] m is an integer of 1 or 2, preferably 1, provided that if m is 2, at most one of the two ortho positions of the hydroxyl group carries R 22 .

[0132] In the compound of formula (II), if m is 2 or 3, then R 22 Can be the same or different.

[0133] In an embodiment, one of the two ortho positions of the hydroxyl group carries R 22 , that is, the other adjacent position does not carry R 22 .

[0134] In an embodiment, the compound of formula (II) is selected from 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole.

[0135] In an embodiment, component (b) comprises 3-tert-butyl-4-hydroxyanisole. In an embodiment, component (b) comprises 2-tert-butyl-4-hydroxyanisole. In an embodiment, component (b) comprises 3-tert-butyl-4-hydroxyanisole and / or 2-tert-butyl-4-hydroxyanisole.

[0136] In an embodiment, component (b) comprises 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole or is composed 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 (e.g., 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 80:1 to 1:10, or 50:1 to 1:1, or 50:1 to 2:1.

[0137] In an embodiment, component (a) comprises vitamin E 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.

[0138] In an 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.

[0139] Based on the total weight of the antioxidant composition, the amount of component (b) can be in the range of 2 to 60 wt%, for example 2 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 50 wt%, or 60 wt%, preferably 5 to 50 wt%, or 6 to 40 wt%, or 8 to 30 wt%.

[0140] In the antioxidant composition of the present disclosure, the weight ratio of component (a) to component (b) can be 10:1 to 1:10 (e.g., 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.

[0141] Hindered Phenol

[0142] In embodiments, the antioxidant composition of the present disclosure further comprises a hindered phenol, ie, a sterically hindered phenol, which is different from the compound of formula (I) and the compound of formula (II).

[0143] Hindered phenols include phenols having one or more phenolic hydroxyl groups on an aromatic ring, and preferably those having substituents (preferably alkyl groups) in the ortho position, most preferably in the ortho and para positions, to the phenolic hydroxyl group.

[0144] It should be understood that the above description is not intended to limit the scope of hindered phenols applicable to the present disclosure. The present disclosure is not limited to sterically hindered phenols as long as they have antioxidant properties.

[0145] Examples of suitable hindered phenols include alkylphenols, for example, 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-butyl 2-(1'-methylcyclohexyl-1'-yl)-4,6-dimethylphenol, 2- or 4-(1'-phenylethyl-1'-yl)phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tri-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, bisphenol B from BASF AG 3,5-di-tert-butyl-4-hydroxybenzoic acid methyl ester, 4-tert-butylcatechol, 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, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate n-octadecyl ester, 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)iso Cyanurate, 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 ester, 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate hexadecyl ester, 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate octyl ester, 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'-hydroxyphenyl) propionate], 1,9-nonanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate], 1,7-heptanediol Amine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionamide], 1,1-methylenediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionamide], 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionhydrazide, 3-(3',5'-dimethyl-4'-hydroxyphenyl) propionhydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphenyl-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphenyl-1-yl)methane, bis[3-(1'-methylcyclohexyl-1'-yl)-5-methyl-2-hydroxyphenyl-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphenyl-1-yl)methane, 1,1-Bis(5-tert-butyl-4-hydroxy-2-methylbenz-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylbenz-1-yl)sulfide, bis(3-tert-butyl-2-hydroxy-5-methylbenz-1-yl)sulfide, 1,1-bis(3,4-dimethyl-2-hydroxybenz-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxybenz-1-yl)butane, 1,3,5-tris[1'-(3",5"-di-tert-butyl-4"-hydroxybenz-1"-yl)-methyl-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4' -hydroxy-2'-methylphenyl-1'-yl)butane, aminophenols such as p-aminophenol, 3-diethylaminophenol, nitrosophenols such as p-nitrosophenol, p-nitroso-o-cresol, alkoxyphenols such as 2-methoxyphenol (guaiacol, catechol 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 (syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1-(4-hydroxy-3-methoxyphenyl)ethanone (acetylvinal), eugenol, dihydroeugenol, isoeugenol, tocol, α-tocopheryl hydroquinone, 4-methylcatechol, 3-methylcatechol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2,5-di-tert-amyl hydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid, Butylated products of p-cresol and dicyclopentadiene, and their derivatives.

[0146] Corresponding sterically hindered phenol products are available, for example, under the following trade names: (BASF), such as pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (e.g. 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., 3114), thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate] (e.g., 1035), 3,5-bis(1,1-dimethylethyl)-4-phenylpropionic acid branched C7-C9-alkyl esters (e.g., 1135), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (e.g., 1076), esters of polyethylene glycol ethers terminated with phenol derivatives (e.g., 2000), 4,6-bis(octylthiomethyl)-o-cresol (e.g. 1520); 3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid branched chain C 13 -C 15 -alkyl esters (e.g. 1315), butylated products of p-cresol and dicyclopentadiene (Wingstay L).

[0147] In an embodiment, the hindered phenol comprises or consists of octadecyl 3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate and a 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.

[0148] Based on the total weight of the antioxidant composition, the amount of hindered phenol can be in the range of 0 to 40 wt% or 2 to 40 wt%, such as 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 0 to 30 wt% or 2 to 30 wt%, or 0 to 25 wt% or 4 to 25 wt%.

[0149] Thiosynergist

[0150] In an embodiment, the antioxidant composition of the present disclosure further comprises a thiosynergist. The thiosynergist may comprise a thioether and / or a thioester.

[0151] Thioethers used according to the present disclosure include compounds comprising at least one thioether group (i.e., a sulfur atom substituted by two identical or different organic substituents). The organic substituents may each 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 thioethers disclosed herein. The present disclosure has no restrictions on thioethers.

[0152] Suitable thioethers have the structure of formula (III)

[0153] R 31 -SR 32 (III)

[0154] in

[0155] R 31 and R 32 Can be C1-C independently of each other 18 -alkyl, interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups. 18 -alkyl, C2-C 18 -Alkenyl, C6-C 12 -Aryl, C5-C 12 - cycloalkyl or a five- or six-membered oxygen-, nitrogen- and / or sulfur-containing heterocycle, wherein the groups mentioned are optionally substituted by hydroxy, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocycle, heteroatom and / or heterocycle.

[0156] Here, R 31 and R 32 can each be independently selected from the group consisting of:

[0157] 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-hetadecyl), n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, diphenylmethyl, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl 2-(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxane-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-methylamino propyl, 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;

[0158] 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaodecyl, 15-hydroxy-4,8,12-trioxapentadecanyl, 9-hydroxy-5-oxanoyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaodecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxaodecyl, 15-hydroxy-4,8,12-trioxapentadecanyl, 9-hydroxy-5-oxanoyl, 14-hydroxy-5,10-oxatetradecyl, 8-dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxopentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl;

[0159] 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;

[0160] phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenyl, 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;

[0161] cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl or a saturated or unsaturated bicyclic ring system, such as norbornyl or norbornenyl; and

[0162] furanyl, thienyl, pyrrolyl, pyridinyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridinyl, methylquinolyl, dimethylpyrrolyl, methoxyfuranyl, dimethoxypyridinyl, difluoropyridinyl, methylthienyl, isopropylthienyl or tert-butylthienyl.

[0163] In some embodiments, the thioether is selected from the group consisting of 2-methyl-1-propenyl tert-dodecyl sulfide, cyclohexylene methyl n-dodecyl sulfide, 3-cyclohexene-(1)-ylidene methyl-n-octadecyl sulfide, 3-cyclohexene-(1)-ylidene methyl-n-dodecyl sulfide, 3-cyclohexene-(1)-ylidene methyl-n-octyl sulfide, 3-cyclohexene-(1)-ylidene methyl cyclohexyl sulfide, 3-methyl-(3)-cyclohexene-(1)-ylidene methyl n-dodecyl sulfide, 3-cyclohexene-(1)-ylidene methyl p-tolyl sulfide, 3-cyclohexene-(1)-ylidene methyl benzyl sulfide, and preferably 3-cyclohexene-(1)-ylidene methyl n-dodecyl sulfide and 1-hexenyl-n-dodecyl sulfide.

[0164] In other embodiments, the thioether is a compound having a structure of formula (IV)

[0165]

[0166] in

[0167] R 33 and R 35 Can be C1-C independently of each other 18 -alkyl, interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups. 18 -alkyl, C6-C 12 -Aryl or C5-C 12 - cycloalkyl, wherein the mentioned radicals are optionally substituted by hydroxy, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic, and

[0168] R 34 Can be C1-C 20 -alkylene or C3-C 12 -cycloalkylene, wherein the radicals mentioned are optionally substituted by hydroxy, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocycle, heteroatom and / or heterocycle.

[0169] Here, R 33 and R35 can each be independently selected from the group consisting of:

[0170] 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-hetadecyl), n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, diphenylmethyl, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl 2-(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxane-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-methylamino propyl, 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;

[0171] 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaodecyl, 15-hydroxy-4,8,12-trioxapentadecanyl, 9-hydroxy-5-oxanoyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaodecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxaodecyl, 15-hydroxy-4,8,12-trioxapentadecanyl, 9-hydroxy-5-oxanoyl, 14-hydroxy-5,10-oxatetradecyl, 8-dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxopentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl;

[0172] phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenyl, 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

[0173] Cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl or a saturated or unsaturated bicyclic ring system, such as norbornyl or norbornenyl.

[0174] Here, R 34 Can be selected from the group consisting of:

[0175] 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

[0176] Cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene and cyclododecylene.

[0177] In some preferred embodiments, R 33 is an 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 an optionally substituted C1-C 18 -alkyl, preferably unsubstituted C1-C 18 -alkyl; and / or R 4 It is methylene, 1,2-ethylene or 1,2-propylene, preferably 1,2-ethylene.

[0178] In some embodiments, compounds having the structure of formula (V) are particularly preferred.

[0179]

[0180] Where R 34 and R 35 As defined above.

[0181] In a preferred embodiment, the thioether is at least one selected from the group consisting of: thiodipropionate, such as dimethyl 3,3'-thiodipropionate, didodecyl 3,3'-thiodipropionate (e.g., BASF Corporation PS 800), dilauryl thiodipropionate (DLTDP), ditridecyl 3,3'-thiodipropionate (DTDTP) (e.g., from Songwon International AG)

[0063] Examples of the invention include dioctadecyl 3,3'-thiodipropionate (DSTDP), dimyristyl thiodipropionate (DMTDP), and 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diylbis[3-(dodecylthio)propionate] (e.g., Seenox 412S).

[0182] The thioester may include, for example, dilauryl thiodipropionate, dimyristyl thiodipropionate, or distearyl thiodipropionate.

[0183] In an embodiment, the thiosynergist comprises or consists of dilauryl thiodipropionate (DLTDP).

[0184] Based on the total weight of the antioxidant composition, the amount of the thiosynergist can be in the following range: 0 to 30wt% or 2 to 30wt%, for example 2wt%, 4wt%, 5wt%, 6wt%, 8wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, or 0 to 25wt% or 2 to 25wt%, or 0 to 20wt% or 4 to 20wt%.

[0185] In an embodiment, the antioxidant composition comprises component (a), component (b), a hindered phenol other than the compound of formula (I) and the compound of formula (II), and a thiosynergist.

[0186] The ratio of the sum of component (a) and component (b) to the sum of the hindered phenol and the thiosynergist may be in the range of 10:1 to 1:100 (e.g., 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 5:1 to 1:80, or 2:1 to 1:50. The ratio of the hindered phenol to the thiosynergist may be in the range of 10:1 to 1:10 (e.g., 8:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:8, or 1:10), preferably 5:1 to 1:5, or 3:1 to 1:3.

[0187] Protective colloids and / or surfactants

[0188] In an embodiment, the antioxidant composition further comprises a protective colloid and / or a surfactant.

[0189] Examples of suitable protective colloids are polyvinyl alcohol, starch derivatives and cellulose derivatives or vinylpyrrolidone copolymers. A detailed description of further suitable protective colloids is given in Houben-Weyl, Methoden der Organischen Chemie [Organic Chemistry Methods], Volume XIV / 1, Makromolekulare Stoffe [macromolecular substances], Georg-Thieme-Verlag [Georg-Thieme Verlag], Stuttgart 1961, pages 411-420.

[0190] The surfactant may be selected from nonionic surfactants, anionic surfactants and / or cationic surfactants, preferably nonionic surfactants.

[0191] Suitable nonionic surfactants (b) may include:

[0192] - Alkoxylated C8-C 22 Alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol ethoxylates: The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. Block copolymers or random copolymers may be present. They generally contain 2 to 50 mol, preferably 3 to 20 mol, of at least one alkylene oxide per mole of alcohol. The preferred alkylene oxide is ethylene oxide. The alcohol preferably has 10 to 18 carbon atoms.

[0193] - alkylphenol alkoxylates, in particular alkylphenol ethoxylates, which contain C6-C 14 - an alkyl chain and 5 to 30 mol of alkylene oxide / mol.

[0194] -alkyl polyglucoside, which contains C8-C 22 -alkyl chain, preferably C 10 -C 18 - an alkyl chain and generally 1 to 20, preferably 1.1 to 5 glucoside units.

[0195] - N-Alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

[0196] Suitable anionic surfactants are, for example:

[0197] - 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.

[0198] -Sulfated alkoxylated C8-C 22 -Alcohol (alkyl ether sulfate): This type of compound is prepared, for example, by first reacting a C8-C 22 - alcohol, preferably C 10 -C 18 - Alkoxylation of alcohols (eg fatty alcohols) and subsequent sulfation of the alkoxylation products. For the alkoxylation, preference is given to using ethylene oxide.

[0199] - Straight chain C8-C 20 - alkylbenzene sulfonate (LAS), preferably linear C9-C 13 -Alkylbenzenesulfonates and -alkyltoluenesulfonates.

[0200] - Alkane sulfonates, especially C8-C 24 - Alkanesulfonates, preferably C 10 -C 18 - Alkane sulfonates.

[0201] - Soaps, such as C8-C 24 - Na and K salts of carboxylic acids.

[0202] Anionic surfactants are preferably added to the detergent in the form of salts. Suitable salts in this context 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.

[0203] Suitable cationic surfactants which may be mentioned are:

[0204] -C7-C 25 - alkylamines;

[0205] -N,N-dimethyl-N-(hydroxy-C7-C 25 -alkyl)ammonium salts;

[0206] -mono- and di-(C7-C 25 -alkyl)dimethylammonium compounds;

[0207] - ester quaternary ammonium compounds, especially C8-C 22 - carboxylic acid-esterified quaternary mono-, di- and trialkanolamines;

[0208] - imidazoline quaternary ammonium compounds, in particular 1-alkylimidazolinium salts of formula (VI) or (VII)

[0209]

[0210] These variables have the following meanings:

[0211] R 41 It is C1-C 25 -alkyl or C2-C 25 -alkenyl;

[0212] R 42 is C1-C4-alkyl or hydroxy-C1-C4-alkyl;

[0213] R 43is C1-C4-alkyl, hydroxy-C1-C4-alkyl or a group R 44 -(CO)-X-(CH2) p -(X: -O- or -NH-; p: 2 or 3),

[0214] At least one group R 44 It is C7-C 22 -alkyl.

[0215] Based on the total weight of the antioxidant composition, the amount of protective colloid and / or surfactant can be in the range of 0.2 to 12 wt%, for example 0.2 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, or 12 wt%, or 0.4 to 10 wt% or 0.6 to 8 wt%.

[0216] In an embodiment, the antioxidant composition of the present disclosure is in the form of an aqueous dispersion. In an embodiment, the average particle size (D50) of the aqueous dispersion is no greater than 10 μm, or no greater than 5 μm, or no greater than 2 μm. The dispersion can be a suspension or an emulsion.

[0217] The term "particle size" refers to the diameter of particles formed by solid components dispersed in a continuous phase or the diameter of oil droplets formed by liquid components dispersed in a continuous phase. Typical particle / droplet size parameters include D10, D50, D90. The term "median particle size" or "average particle size" refers to the D50 value, wherein 50% of the particles / droplets by volume have a diameter less than or equal to the D50 value. The average particle size is measured by diluting 1.0 ml of sample in 40 ml of deionized water with a Malvern Mastersizer 2000 spectrometer and recorded as the median particle size (D50) in microns.

[0218] In an embodiment, the antioxidant composition comprises

[0219] 2 to 60 wt% of component (a);

[0220] 2 to 60 wt% of component (b);

[0221] 0 to 40 wt% or 2 to 40 wt% of hindered phenol;

[0222] 0 to 30 wt% or 2 to 30 wt% of a thiosynergist;

[0223] 0.2 to 12 wt% of protective colloid and / or surfactant; and water: the balance to 100 wt%,

[0224] in each case based on the total weight of the antioxidant composition.In an embodiment, the antioxidant composition comprises 5 to 50 wt% of component (a);

[0225] 5 to 50 wt% of component (b);

[0226] 0 to 30 wt% or 2 to 30 wt% of hindered phenol;

[0227] 0 to 25 wt% or 2 to 25 wt% of a thiosynergist;

[0228] 0.4 to 10 wt% of a protective colloid and / or a surfactant; and water: the balance to 100 wt%,

[0229] in each case based on the total weight of the antioxidant composition.In an embodiment, the antioxidant composition comprises 6 to 40 wt % of component (a);

[0230] 6 to 40 wt% of component (b);

[0231] 0 to 30 wt% or 2 to 30 wt% of hindered phenol;

[0232] 0 to 20 wt% or 2 to 20 wt% of a thiosynergist;

[0233] 0.6 to 8 wt% of protective colloid and / or surfactant; and water: the balance to 100 wt%,

[0234] in each case based on the total weight of the antioxidant composition.In an embodiment, the antioxidant composition comprises 8 to 30 wt% of component (a);

[0235] 8 to 30 wt% of component (b);

[0236] 0 to 30 wt% or 2 to 30 wt% of hindered phenol;

[0237] 0 to 20 wt% or 2 to 20 wt% of a thiosynergist;

[0238] 0.6 to 8 wt% of a protective colloid and / or surfactant; and

[0239] Water: balance to 100wt%,

[0240] In each case based on the total weight of the antioxidant composition.

[0241] The antioxidant composition of the present disclosure may further comprise other additives, such as epoxidized vegetable oil. The epoxidized vegetable oil is present in an amount of no more than 20 wt % based on the weight of the antioxidant composition, preferably in a range of 0 to 15 wt % based on the weight of the antioxidant composition, more preferably in a range of 0 to 10 wt %. An example of an epoxidized vegetable oil is epoxidized soybean oil.

[0242] According to the present disclosure, the antioxidant composition is substantially free of organic solvents, especially methanol. "Substantially free of organic solvents" means that the content of organic solvents is no more than 5 wt%, preferably no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, or no more than 0.1 wt%, or no more than 0.05 wt%, based on the weight of the antioxidant composition.

[0243] According to the present disclosure, the pH value of the antioxidant composition is no greater than 7.5, or no greater than 7.3. The pH value can be measured, for example, using a Metrohm 744 pH meter at room temperature.

[0244] Preparation method, use and polymer composition

[0245] In a further aspect, the present disclosure provides a method for preparing an aqueous dispersion comprising the antioxidant composition of the present disclosure (or the antioxidant composition in the form of an aqueous dispersion), comprising homogenizing component (a), component (b), optional hindered phenols and optional thiosynergist, and a protective colloid and / or a surfactant in water.

[0246] It will be understood by those skilled in the art that if the antioxidant composition of the present disclosure is in the form of an aqueous dispersion, then “a method for preparing an aqueous dispersion containing the antioxidant composition of the present disclosure” means “a method for preparing an antioxidant composition in the form of an aqueous dispersion”.

[0247] In the examples, when component (a), component (b), hindered phenol or thiosynergist is solid, these solid components are heated to melt before homogenization, and homogenization is performed in water in the presence of a protective colloid and / or a surfactant.

[0248] In an embodiment, the protective colloid and / or the surfactant are dissolved in water prior to homogenization. If both a protective colloid and a surfactant are used, both the protective colloid and the surfactant are dissolved in water prior to homogenization.

[0249] In an embodiment, homogenization is carried out at an elevated temperature, preferably at a temperature above the melting point of component (a), component (b), hindered phenol (when present) and thiosynergist (when present).

[0250] In a further aspect, the present disclosure provides use of the antioxidant composition of the present disclosure as a chain terminator and / or stabilizer.

[0251] Generally, the antioxidant compositions of the present disclosure can be used as chain terminators and / or stabilizers in free radical polymerization.

[0252] As the radical polymerization, examples such as suspension polymerization, microsuspension polymerization and emulsion polymerization can be mentioned. In the radical polymerization, a radical polymerization initiator such as an organic peroxide or an azo compound can be used.

[0253] The monomer in the free radical polymerization comprises a radical polymerizable group. The radical polymerizable group can be selected from allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloyloxy, acrylamide, methacrylamide or ethynyl. Usually, the monomer can include vinyl monomers, conjugated diene monomers, acrylic monomers, methacrylic monomers, acrylonitrile and mixtures thereof, especially vinyl chloride, styrene, acrylonitrile, butadiene and (meth)acrylate.

[0254] Based on the weight of the monomers added to the polymerization system, the total dosage of component (a) and component (b) in the free radical polymerization system can be in the following range: 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 30 to 2000 ppm, or 40 to 1000 ppm, or 45 to 800 ppm.

[0255] In another aspect, the present disclosure provides a polymer composition comprising the antioxidant composition of the present disclosure. The polymer can be derived from monomers as mentioned above, especially selected from polyvinyl chloride, acrylonitrile butadiene styrene (ABS), methyl methacrylate butadiene styrene (MBS), nitrile rubber or styrene-butadiene rubber, etc.

[0256] The total amount of component (a) and component (b) in the polymer composition can be in the range of 20 to 4000 ppm (e.g., 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 30 to 2000 ppm, or 40 to 1000 ppm, or 45 to 800 ppm, based on the total weight of the polymer composition.

[0257] Examples

[0258] Material

[0259] Component (a): Vitamin E (Irganox E 201) from BASF. It is a phenolic antioxidant and is 2,5,7,8-tetramethyl-2-[4,8,12-trimethyltridecyl]chroman-6-ol, which is depicted below:

[0260]

[0261] Irganox E 201 is 100% D,L-α-tocopherol.

[0262] Component (b): BHA (butylated hydroxy-anisole) from DANISCO; containing 90% 3-tert-butyl-4-hydroxyanisole, the sum of 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole is 98%;

[0263] Protective colloid: Inool PA8 from Ineos, degree of hydrolysis: 86-90 mol% (TM / SA / 6), viscosity of 4% aqueous solution (mPa.s): 5-6 (TM / SA / 7);

[0264] Hindered phenols: Irganox 1076: octadecyl 3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate from BASF; Wingstay L: butylation product of p-cresol and dicyclopentadiene.

[0265] Thiosynergist: Irganox PS 800FL = DLTDP = 3,3'-di-dodecyl thiodipropionate;

[0266] Commercial Product P: A mixture of 33.3% Irganox 1076, 33.3% DLTDP and 33.3% Wingstay L.

[0267] Test Method

[0268] -Pressure drop: Read from the pressure gauge.

[0269] - Dehydrochlorination test: This test is based on an apparatus that heats PVC resin to 180°C, then collects HCl into water (i.e., obtains an aqueous HCl solution), and tests the conductivity of the aqueous HCl solution to determine how long it takes for the conductivity of the aqueous HCl solution to reach 200 microSiemens / cm.

[0270] - Whiteness Index: The whiteness index was checked on Datacolor SF 600X (color spectrophotometer), where the polymer sample was filled in a petri dish and the surface of the polymer sample was scratched before checking.

[0271] - D50: The particle size of solid antioxidants and the droplet size of liquid antioxidants in aqueous antioxidant suspoemulsions were measured with a Malvern Mastersizer 2000 spectrometer by diluting 1.0 ml of sample in 40 ml of deionized water and reported as the median particle size in microns (D50).

[0272] Example 1: Preparation of Sample 1

[0273] 1) Add 2.67 Kg BHA to a container, heat to 85°C, and then add 1.33 Kg Vitamin E and stir at 25 RPM until completely melted.

[0274] 2) Under stirring, add 3 Kg of 20% Poval 8-88 (polyvinyl alcohol) aqueous solution to the container, then increase the stirrer speed to 75 RPM and start the homogenizer at 3000 RPM.

[0275] 3) After 5 minutes, the homogenization speed was further increased to 6000 RPM to initiate emulsification.

[0276] 4) After 1 hour, check the average particle size (D50) to see if it is no greater than 2 μm. If not, continue homogenizing until the average particle size (D50) is no greater than 2 μm, then stop homogenizing.

[0277] 5) 3 Kg (30% by weight) of deionized water was added, and the mixture was then stirred well at 75 RPM to obtain Sample 1.

[0278] Example 2: Preparation of Sample 2

[0279] 1) Add 1.33 Kg BHA into a container and heat to 85°C, and then add 2.67 Kg Vitamin E and stir at 25 RPM until completely melted.

[0280] 2) Under stirring, add 3 Kg of 20% polyvinyl alcohol aqueous solution (30% by weight) to the container, then increase the stirrer speed to 75 RPM and start the homogenizer at 3000 RPM.

[0281] 3) The homogenization speed was further increased to 6000 RPM to initiate emulsification.

[0282] 4) After 1 hour, check the average particle size to see if it is no greater than 2 μm. If not, continue homogenizing until the average particle size (D50) is no greater than 2 μm, then stop homogenizing.

[0283] 5) 3 Kg (30% by weight) of deionized water was added, and the mixture was then stirred well at 75 RPM to obtain Sample 2.

[0284] Example 3: Preparation of Sample 3

[0285] 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 and heated to 85° C., and then stirred at 75 RPM until completely melted.

[0286] 2) Cool the temperature to 65°C and add Vitamin E (5 parts by weight) and stir well at 75 RPM.

[0287] 3) Add 20% polyvinyl alcohol aqueous solution (25 parts by weight) and start the homogenizer at 3000 RPM.

[0288] 4) Increase homogenization speed to 6000 RPM to begin emulsification.

[0289] 5) After 1 hour, check the average particle size to see if it is no greater than 2 μm. If not, continue homogenizing until the average particle size (D50) is no greater than 2 μm, then stop homogenizing.

[0290] 6) Deionized water (35 parts by weight) was added, and the mixture was then stirred at 75 RPM to obtain Sample 3.

[0291] Examples 4, 5 and Comparative Examples 1 and 2: Polymerization of PVC using Samples 1, 2, Vitamin E and BHA, respectively

[0292] These experiments were based on K67 grade PVC resin polymerized at 57°C. The detailed preparation of polyvinyl chloride is as follows:

[0293] (1) 666 g of deionized water, 0.250 g of cumyl peroxyneodecanoate (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;

[0294] (2) The reactor was evacuated to a vacuum, and then 444 g of vinyl chloride monomer was added under stirring, and the temperature was raised to 57° C. The internal pressure of the reactor for polymerization was 9 bar;

[0295] (3) When the internal pressure of the reactor was reduced to 8 bar (the conversion rate of the monomer was about 85%), each of samples 1, 2, vitamin E, or BHA was added at a dosage as shown in the following Table 1, wherein the dosage of the active substance in Table 1 is based on the initial addition of vinyl chloride, i.e., 444 g. In Examples 4 and 5, the dosage of the active substance is related to the sum of vitamin E and BHA.

[0296] (4) Maintain the temperature and observe the pressure drop for 1.5 hours and summarize in Table 1. A smaller pressure drop indicates a higher chain termination efficiency (because there is less further polymerization).

[0297] (5) Residual monomers are removed from the obtained polymer syrup, and then the polymer syrup is dried to obtain a polyvinyl chloride resin.

[0298] The whiteness index (initial) of the PVC resin and the whiteness index after the PVC resin was heated at 160° C. for 10 minutes were tested and summarized in Table 1.

[0299] Table 1

[0300]

[0301] The pressure drop results in Table 1 show that the chain termination effect of samples 1 and 2 of the present invention is not only better than that of single vitamin E, but also better than that of single BHA, which further shows the synergistic effect of components (a) and (b) in chain termination.

[0302] In addition, as indicated by the whiteness index (original), the inventive samples 1 and 2 are much whiter than single vitamin E. After heating at 160° C. for 10 minutes, the whiteness of the polymer of Example 5 (vitamin E: BHA = 2: 1) is 93, which is higher than both single vitamin E and single BHA, and thus shows a strong synergistic effect in anti-yellowing. In addition, Example 4 (vitamin E: BHA = 1: 2) also shows a relative synergistic effect, because its whiteness index (160° C., after 10 minutes), i.e., 91, is much higher than the mathematically expected whiteness index, i.e., 1 / 3*87 (Comparative Example 1, single VE) + 2 / 3*91 (Comparative Example 2, single BHA) = 89.6.

[0303] For the PVC resins obtained in Examples 4 and 5, the times when the conductivity of the HCl aqueous solution reached 200 microsiemens / cm in the dehydrochlorination test were 45 minutes and 46 minutes, respectively. The longer the time, the slower the release rate of HCl from the PVC resin, which means less degradation of the PVC resin.

[0304] Example 6 and Comparative Example 3: PVC polymerization by using Sample 3 and Commercial Product P respectively

[0305] These experiments were based on K67 grade PVC resin polymerized at 57°C. The detailed preparation of polyvinyl chloride is as follows:

[0306] (1) 666 g of deionized water, 0.250 g of cumyl peroxyneodecanoate (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;

[0307] (2) The reactor was evacuated to a vacuum, and then 444 g of vinyl chloride monomer was added under stirring, and the temperature was raised to 57° C. The internal pressure of the reactor for polymerization was 9 bar;

[0308] (3) When the internal pressure of the reactor was reduced to 8 bar (the conversion rate of the monomer was about 85%), Sample 3 or Commercial Product P was each added in a dosage as shown in Table 2 below, wherein the dosage of the active substance in Table 2 is based on the vinyl chloride initially added, i.e., 444 g. In Example 6, the dosage of the active substance is related to the sum of vitamin E, BHA, Irganox 1076, DLTDP, and Wingstay L. In Comparative Example 3, the dosage of the active substance is related to the sum of Irganox 1076, DLTDP, and Wingstay L.

[0309] (4) Maintain temperature and observe pressure drop for 1.5 hours and summarize in Table 2. Smaller pressure drop indicates higher chain termination efficiency (because less further polymerization).

[0310] (5) Residual monomers are removed from the obtained polymer syrup, and then the polymer syrup is dried to obtain a polyvinyl chloride resin.

[0311] The whiteness index (initial) of the PVC resin and the whiteness index after the PVC resin was heated at 160° C. for 10 minutes were tested and summarized in Table 2; the results of dehydrochlorination are also summarized in Table 2.

[0312] Table 2

[0313]

[0314]

[0315] In Example 6, the sum of vitamin E and BHA is 50 ppm, and this example also shows excellent chain termination characteristics (pressure drop is only 0.65), which is significantly better than the characteristics in Comparative Example 3 (without vitamin E and BHA). The results of the dehydrochlorination test show that the active substances in Sample 3 further show a synergistic effect on the thermal stability of the polymer.

Claims

1. An antioxidant composition comprising (a) Derivatives of chromanol of formula (I) in 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; and R3, R4, R5 are independently selected from hydrogen or C1-C4-alkyl; as well as (b) Compounds of formula (II) in R 21 is a C1-C6-alkyl group, R 22 is C1-C8-alkyl, and m is an integer of 1, 2 or 3, provided that if m is 2 or 3, at most one of the two ortho positions of the hydroxyl group carries R 22 .

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

3. The antioxidant composition according to claim 1 or 2, wherein 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; The above alkyl groups (C1-C6-alkyl, C1-C4-alkyl and C1-C3-alkyl) may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl groups may optionally be replaced by -(CO)-O-.

4. The antioxidant composition according to any one of claims 1 to 3, wherein 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, wherein the above alkyl (C1-C 30 -alkyl and C8-C 30 -alkyl) may optionally be interrupted by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl may optionally be replaced by -(CO)-O-.

5. The antioxidant composition according to any one of claims 1 to 4, wherein R3, R4, R5 are independently selected from hydrogen, methyl or ethyl.

6. The antioxidant composition according to any one of claims 1 to 5, wherein Component (a) comprises α-, β-, γ-, δ-tocopherol, or α-, β-, γ-, δ-tocotrienol, or a mixture thereof, preferably vitamin E, more preferably a compound of formula (I'-1):

7. The antioxidant composition according to any one of claims 1 to 6, wherein R 21 is C1-C4-alkyl; R 22 is C4-C8-alkyl, preferably tertiary C4-C8-alkyl; and m is an integer of 1 or 2, preferably 1, provided that if m is 2, at most one of the two ortho positions of the hydroxyl group carries R 22 .

8. The antioxidant composition according to any one of claims 1 to 7, wherein Component (b) comprises 3-tert-butyl-4-hydroxyanisole and / or 2-tert-butyl-4-hydroxyanisole, preferably 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 any one of claims 1 to 8, wherein The weight ratio of component (a) to component (b) is 5:1 to 1:5, preferably 3:1 to 1:3, more preferably 1:2 to 2:

1.

10. The antioxidant composition according to any one of claims 1 to 9, wherein The composition further comprises a hindered phenol different from the compound of formula (I) and the compound of formula (II), a thiosynergist, or a combination thereof.

11. The antioxidant composition according to any one of claims 1 to 10, wherein The composition is in the form of an aqueous dispersion, and the average particle size (D50) of the aqueous dispersion is not greater than 10 μm, preferably not greater than 5 μm, more preferably not greater than 2 μm.

12. The antioxidant composition according to any one of claims 2 to 11, wherein The composition comprises 2 to 60 wt% or 5 to 50 wt% of component (a); 2 to 60 wt% or 5 to 50 wt% of component (b); 0 to 40 wt% or 2 to 40 wt% of hindered phenol; 0 to 30 wt% or 2 to 30 wt% of a thiosynergist; 0.2 to 12 wt% or 0.4 to 10 wt% of a protective colloid and / or a surfactant; and Water: balance to 100wt%, In each case based on the total weight of the antioxidant composition.

13. The antioxidant composition according to any one of claims 1 to 12, wherein The composition is substantially free of organic solvents.

14. A method for preparing an aqueous dispersion comprising an antioxidant composition according to any one of claims 1 to 13, comprising homogenizing component (a) and component (b), optionally hindered phenols, optionally thiosynergists, and protective colloids and / or surfactants in water at elevated temperature.

15. The method according to claim 14, wherein: When component (a), component (b), hindered phenol or thiosynergist is solid, these solid components are heated to melt before the homogenization, and the homogenization is carried out in water in the presence of the protective colloid and / or surfactant.

16. The method according to claim 14 or 15, wherein: The homogenization is carried out at a temperature above the melting point of component (a), component (b), and optionally the hindered phenol and optionally the thiosynergist.

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

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

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