Liquid antioxidant composition for raw rubbers

Patent metadata

Field	Value
Publication number	US-11084909-B2
Application number	US-201716328947-A
Country	US
Kind code	B2
Filing date	Aug 21, 2017
Priority date	Aug 30, 2016
Publication date	Aug 10, 2021
Grant date	Aug 10, 2021

Abstract

The present invention provides a liquid antioxidant composition used for raw rubbers comprising 5% to 30% by weight of at least one aromatic amine-based antioxidant agent, 20% to 70% by weight of at least one hindered phenol-based antioxidant agent, 0% to 40% by weight of at least one phosphite-based antioxidant agent; and 20% to 40% by weight of at least one solvent having boiling point higher than 185° C. and freezing point lower than −10° C. under 101.325 KPa, the weight percentage of component a), b), c) or d) is based on the total weight of antioxidant composition, wherein the mixture of component a), b) and c) is liquid at 25° C. under 101.325 KPa. The weight percentage is based on the total weight of antioxidant composition. The present invention further provides an application of said liquid antioxidant composition in raw rubbers such as natural rubber and raw rubbers synthesized via solution polymerization.

First claim

The invention claimed is:

1. A liquid antioxidant composition, comprising:
a) 5% to 30% by weight of at least one aromatic amine-based antioxidant agent;
b) 20% to 70% by weight of at least one hindered phenol-based antioxidant agent;
c) 0% to 40% by weight of at least one phosphite-based antioxidant agent; and
d) 20% to 40% by weight of at least one solvent having boiling point higher than 185° C. and freezing point lower than −10° C. under 101.325 KPa, wherein the weight percentage of component a), b), c) or d) is based on the total weight of antioxidant composition,
wherein the mixture of component a), b) and c) is liquid at 25° C. under 101.325 KPa, wherein said solvent is at least one selected from the group consisting of linear or branched alkane having C 9 to C 30 , arene having C 6 to C 18 , cyclane having C 10 to C 30 , linear saturated carboxylic acid having C 8 to C 18 , branched saturated carboxylic acid having C 8 to C 12 , linear saturated alcohol having C 8 to C 18 and branched saturated alcohol having C 8 to C 12 , alkyl-substituted phosphonic acid having C 6 to C 12 , saturated or unsaturated monobasic aromatic acid ester having Formula I:

wherein, R 1 to R 5 are independently selected from hydrogen, saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 ; R 6 is selected from saturated or unsaturated linear or branched alkylene groups having C 1 to C 15 or represents a covalent bond; R 7 is selected from saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 , and
saturated or unsaturated dibasic aromatic acid ester having Formula II-(a) and/or Formula II-(b) and/or Formula II-(c):

wherein, R 1 ′ to R 4 ′ are independently selected from hydrogen, saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 ; R 5 ′ and R 7 ′ are independently selected from saturated or unsaturated linear or branched alkylene groups having C 1 to C 15 or represents a covalent bond; R 6 ′ and R 8 ′ are independently selected from saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 , and
saturated or unsaturated tribasic aromatic acid ester having Formula III-(a) and/or Formula III-(b) and/or Formula III-(c):

wherein, R 1 ″ to R 3 ″ are independently selected from hydrogen, saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 ; R 4 ″, R 6 ″ and R 8 ″ are independently selected from saturated or unsaturated linear or branched alkylene groups having C 1 to C 15 or represents a covalent bond; R 5 ″, R 7 ″ and R 9 ″ are independently selected from saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 , and
alkylated phosphate having Formula IV:

wherein, R 1 ′″ to R 3 ′″ are independently selected from hydrogen, saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 , and
saturated or unsaturated monobasic carboxylic acid ester having Formula V:

wherein, R a and R b are independently selected from saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 , and
saturated or unsaturated dibasic carboxylic acid ester having Formula VI:

wherein, R a ′ and R c ′ are independently selected from saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 ; R b ′ is selected from saturated or unsaturated linear or branched alkylene groups having C 1 to C 15 , and
saturated or unsaturated tribasic carboxylic acid ester having Formula VII:

wherein, R a ″, R c ″ and R d ″ are independently selected from saturated or unsaturated linear or branched alkyl groups having C 1 to C 15 ; R b ″ is selected from saturated or unsaturated linear or branched alkylidene groups having C 1 to C 15 .

2. The antioxidant composition according to claim 1 , wherein said aromatic amine-based antioxidant agent is at least one selected from the group consisting of N,N′-di-sec-butyl-1,4-phenylenediamine, N-phenylbenzenamine reaction products with 2,4,4-trimethylpentene, bis(4-octylphenyl)amine, 4,4′-bis(α,α-dimethylbenzyl)diphenylamine, N,N′-di-2-naphthyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N′-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine, and N,N′-bis(methyl-phenyl)-1,4-benzendiamine.

3. The antioxidant composition according to claim 1 , wherein said hindered phenol-based antioxidant agent is at least one selected from the group consisting of poly(oxy-1,2-ethanediyl)-alpha-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-omega-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(dodecylthio)methyl]-o-cresol, octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid C7-C9-branched alkyl ester, 4,4′-butylidene bis-(3-methyl-6-tert-butylphenol), 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, and 2,2-thio-diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

4. The antioxidant composition according to claim 1 , wherein said phosphite-based antioxidant agent is at least one selected from the group consisting of diphenyl-mono(2-ethylhexyl)phosphite, diphenyl-monotridecyl-phosphite, diphenyl-isodecylphosphite, diphenyl-isooctyl-phosphite, diphenyl-nonylphenyl-phosphite, triphenyl phosphite, triisodecyl phosphite, tris(2-ethylhexyl)phosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl)butane, 4,4′-butylidene bis(3-methyl-6-tert-butyl-di-tridecyl phosphite), 2,2′-ethylidene bis(4,6-di-tert-butyl-phenol)fluorophosphite, 4,4′-isopropylidene-diphenyl alkyl (C 12 to C 15 ) phosphites, bis(nonylphenyl)pentaerythritol diphosphite, hydrogenated bisphenol A-pentaerythritol phosphite polymers, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 2-ethylhexyldiphenyl phosphite, tris((mono and di)-nonylphenyl)phosphite, tri-(2,4-di-tert-butylphenyl)phosphite, tetraphenyl dipropylene glycol diphosphite, and distearylpentaerythritoldiphosphite.

5. A liquid antioxidant composition, comprising:
a) 5% to 20% by weight of solid aromatic amine-based antioxidant agent;
b) 20% to 50% by weight of solid hindered phenol-based antioxidant agent;
c) 0% to 30% by weight of solid phosphite-based antioxidant agent; and
d) 30% to 40% by weight of solvent having boiling point higher than 185° C. and freezing point lower than −10° C. under 101.325 KPa, wherein the weight percentage of component a), b), c) or d) is based on the total weight o

Assignees

• Basf Se

Inventors

• Zhou Yi Qiong
• Fan Chang Liang
• Yuan Guo Liang
• Zhou zhong yi

Classifications

• C08K5/524

  Esters of phosphorous acids, e.g. of H3PO3 · CPC title

• C08L91/00

  Compositions of oils, fats or waxes; Compositions of derivatives thereof · CPC title

• C08L9/00

  Compositions of homopolymers or copolymers of conjugated diene hydrocarbons · CPC title

• C08J2321/00

  Characterised by the use of unspecified rubbers · CPC title

• C08J3/20

  Compounding polymers with additives, e.g. colouring · CPC title