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US-20260125536-A1 - NEW ANTIDEGRADANTS BASED ON FATTY ACIDS OR DERIVATIVES FUNCTIONALIZED WITH PHENYLENEDIAMINES

US20260125536A1US 20260125536 A1US20260125536 A1US 20260125536A1US-20260125536-A1

Abstract

Antidegradant products are disclosed that may be made by a process comprising: hydroformylating one or more of: a fatty acid or fatty acid derivative having one or more unsaturations, e.g., carbon-to-carbon double bonds, and from 10 to 20 carbon atoms, or a fatty alcohol comprising one or more of a straight chain fatty alcohol having one or more unsaturations, e.g., unsaturated carbon-to-carbon double bonds, and from 10 to 20 carbon atoms, by reaction with carbon monoxide and hydrogen gases to obtain a hydroformylated intermediate; and functionalizing the hydroformylated intermediate by reaction with a substituted or unsubstituted paraphenylene diamine to obtain the antidegradant product.

Inventors

  • Jody Lee Rodgers
  • Judicael Jacques Chapelet
  • Donald L. Fields, Jr.
  • Frederick Ignatz-Hoover
  • Shanzuo Ji

Assignees

  • FLEXSYS AMERICA L.P.

Dates

Publication Date
20260507
Application Date
20220824

Claims (20)

  1. 1 . A compound represented by formula I: wherein R 1 is a group selected from —OH, —O-alkyl, —O-aryl, —O-(alkylaryl), —NH 2 , —NH(alkyl), —N(alkyl) 2 , —NH(aryl), —N(aryl) 2 , —NH(alkylaryl), —N(alkylaryl) 2 , —SH, —S-alkyl, —S-aryl, and —S-(alkylaryl), each R 4 is independently selected from the group consisting of C 5-26 alkyl and C 5-26 alkenyl, L 1 is a group selected from —(C═O)— and —(CH 2 )—, a+b+c is an integer from 9 to 17, each X, each Y, and each Z are groups independently selected from methylene, alkenediyl, and a substituted para-phenylenediamine having formula II: wherein each p is independently 0 or 1, each q is independently 0 or 1, each R 2 is a group independently selected from —H, -alkyl, -aryl, -alkylaryl, -arylalkyl, and a group having formula III: wherein each R 3 is a group independently selected from —OH, —O-alkyl, —O-aryl, —O-(alkylaryl), -NH 2 , —NH(alkyl), —N(alkyl) 2 , —NH(aryl), —N(aryl) 2 , —NH(alkylaryl), —N(alkylaryl) 2 , —SH, —S-alkyl, —S-aryl, and —S-(alkylaryl), each L 2 is a group independently selected from —(C═O)— and —(CH 2 )—, each V and each W are groups independently selected from methylene, alkenediyl, and a substituted para-phenylenediamine having formula II-A: wherein each R 5 is a group independently selected from —H, -alkyl, -aryl, -alkylaryl, and -arylalkyl, and wherein d+e+f is an integer from 9 to 17.
  2. 2 . The compound of claim 1 , wherein R 1 is L 1 is —(C═O)—, the total number of substituted para-phenylenediamine groups having formula II and/or formula IIa in the compound is 1, p is 1, q is 0, and R 2 is a phenyl group.
  3. 3 . The compound of claim 1 , wherein R 1 is L 1 is —(C═O)—, the total number of substituted para-phenylenediamine groups having formula II and/or formula IIa in the compound is 2, p is 1, q is 0, and R 2 is a phenyl group.
  4. 4 . The compound of claim 1 , wherein R 1 is L 1 is —(C═O)—, the total number of substituted para-phenylenediamine groups having formula II and/or formula IIa in the compound is 1, p is 1, q is 0, and R 2 is a phenyl group.
  5. 5 . The compound of claim 1 , wherein R 1 is L 1 is —(C═O)—, the total number of substituted para-phenylenediamine groups having formula II and/or formula IIa in the compound is 2, p is 1, q is 0, and R 2 is a phenyl group.
  6. 6 . The compound of claim 1 , wherein R 1 is a —OH group, L 1 is —(C═O)—, the total number of substituted para-phenylenediamine groups having formula II and/or formula IIa in the compound is 1, p is 1, q is 0, and R 2 is a methyl group.
  7. 7 . The compound of claim 1 , wherein R 1 and R 3 are —OCH 3 groups, L 1 and L 2 are —(C═O)— groups, the total number of substituted para-phenylenediamine groups having formula II and/or formula IIa in the compound is 1, p is 1, and q is 1.
  8. 8 . An antidegradant product made by a process comprising: i. hydroformylating one or more of: 1. a fatty acid or fatty acid derivative comprising one or more of a straight chain fatty acid having one or more carbon to carbon double bonds and from 10 to 20 carbon atoms, or an amide or thioester or thiocarboxylic acid thereof, or a mono-, di-, or triglyceride thereof, or an alkyl ester or an aryl ester or an alkylaryl ester thereof wherein the alkyl or aryl or alkylaryl group has from one to twelve carbon atoms, or 2. a fatty alcohol comprising one or more of a straight chain fatty alcohol having one or more carbon-to-carbon double bonds and from 10 to 20 carbon atoms, by reaction with carbon monoxide and hydrogen gases to obtain a hydroformylated intermediate; and ii. functionalizing the hydroformylated intermediate by reaction with a substituted or unsubstituted para-phenylene diamine having formula VII: wherein q is 0 or 1, each R 2 is a group independently selected from —H, -alkyl, -aryl, -alkylaryl, -arylalkyl, and a group having formula III: wherein each R 3 is a group independently selected from —OH, —O-alkyl, —O-aryl, —O-(alkylaryl), -NH 2 , —NH(alkyl), —N(alkyl) 2 , —NH(aryl), —N(aryl) 2 , —NH(alkylaryl), —N(alkylaryl) 2 , —SH, —S-alkyl, —S-aryl, and —S-(alkylaryl), each L 2 is a group independently selected from —(C═O)— and —(CH 2 )—, and each R 4 is independently selected from C 5-26 alkenyl, to obtain the antidegradant product.
  9. 9 . The antidegradant product of claim 8 , wherein the fatty acid or fatty acid derivative is derived from soybean oil.
  10. 10 . The antidegradant product of claim 8 , wherein the fatty acid or fatty acid derivative is derived from one or more of soybean oil, olive oil, canola oil, corn oil, cottonseed oil, grapeseed oil, flax oil, hempseed oil, peanut oil, or sunflower oil.
  11. 11 . The antidegradant product of claim 8 , wherein the fatty acid or fatty acid derivative comprises a mono-, di-, or triglyceride of a residue of one or more of palmitic acid, stearic acid, oleic acid, linoleic acid, or linolenic acid.
  12. 12 . The antidegradant product of claim 8 , wherein the fatty alcohol comprises one or more of palmitic alcohol, stearic alcohol, oleic alcohol, linoleic alcohol, or linolenic alcohol.
  13. 13 . The compound of claim 1 having formula X: wherein each X and each Z are groups independently selected from methylene and alkenediyl and b is 1.
  14. 14 . The compound of claim 1 having formula XI: wherein each X and each Z are groups independently selected from methylene and alkenediyl and b is 1.
  15. 15 . The compound of claim 1 having formula XII: wherein each X and each Z are groups independently selected from methylene and alkenediyl and b is 1.
  16. 16 . The compound of claim 1 having formula XIII: wherein each X and each Z are groups independently selected from methylene and alkenediyl and b is 1.
  17. 17 . The compound of claim 1 having formula XIV: wherein each X and each Z are groups independently selected from methylene and alkenediyl and b is 1.
  18. 18 . The compound of claim 1 having formula XV: wherein each X and each Z are groups independently selected from methylene and alkenediyl and b is 1.
  19. 19 . The compound of claim 1 having formula XVI: wherein each X and each Z are groups independently selected from methylene and alkenediyl and b is 1, and wherein each V and each W are groups independently selected from methylene and alkenediyl and e is 1.
  20. 20 . The compound of claim 1 having formula XVII: wherein each X and each Z are groups independently selected from methylene and alkenediyl and b is 1, and wherein each V and each W are groups independently selected from methylene and alkenediyl and e is 1.

Description

FIELD OF THE DISCLOSURE The present disclosure provides fatty acids and derivatives functionalized with phenylenediamines, and methods of making them. These phenylenediamine compounds are particularly useful as antidegradants for rubber applications. BACKGROUND OF THE DISCLOSURE Paraphenylene diamines are known to be useful as antidegradants. Thus, U.S. Pat. No. 3,409,586 discloses a diolefin rubber vulcanizate that contains an antiozonant amount of N-alkyl-N′-o-substituted-phenyl-para-phenylenediamine. U.S. Pat. No. 5,117,063 discloses methods of producing 4-ADPA, wherein aniline and nitrobenzene are reacted under suitable conditions to produce 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine and/or their salts, either or both of which are subsequently reduced to produce 4-ADPA. The 4-ADPA can be reductively alkylated to produce p-phenylenediamine products which are useful as antiozonants. U.S. Pat. No. 6,140,538 discloses processes for preparing an optionally substituted 4-aminodiphenylamine comprising reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the water content so as to ensure a molar ratio of water to the base charged of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine and/or salts thereof. The coupling reaction is followed by a hydrogenation reaction where the coupling reaction product is hydrogenated in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation. Aqueous and organic phases are obtained and the optionally substituted 4-aminodiphenylamine recovered from the organic phase. WO 2017/112440A1 likewise discloses p-phenylenediamine compounds useful as antidegradants. U.S. Pat. No. 5,134,200 describes polymers having chemically bound antidegradants that are prepared by reacting a polymer having olefinic unsaturation with carbon monoxide and hydrogen under hydroformylation conditions in the presence of a hydroformylation catalyst, an organic reaction solvent and a primary or secondary amine-containing antidegradant. U.S. Pat. No. 7,576,227 describes processes of preparing industrial chemicals starting from seed oil feedstock compositions which includes metathesis to form a reduced chain unsaturated acid or ester which may be hydroformylated with reduction. There remains a need in the art for antidegradants useful in rubber compositions, and especially those based on renewable raw materials. SUMMARY OF THE DISCLOSURE In a first aspect, the present disclosure provides compounds represented by formula I: wherein R1 is a group selected from —OH, —O-alkyl, —O-aryl, —O-(alkylaryl), glycerol, glycerol monoester or diester, —NH2, —NH(alkyl), —N(alkyl)2, —NH(aryl), —N(aryl)2, —NH(alkylaryl), —N(alkylaryl)2, —SH, —S-alkyl, —S-aryl, or —S-(alkylaryl),L1 is a group selected from —(C═O)— or —(CH2)—,a+b+c is from 9 to 17,and wherein X, Y, and Z are groups independently selected from methylene, alkenediyl, or substituted para-phenylenediamines corresponding to: wherein p is 0 or 1,q is 0 or 1,the number of methylene groups is from 8 to 16,the number of substituted para-phenylenediamine groups is from 1 to 3,the number of alkenediyl groups is from 0 to 2; and wherein R2 is a group selected from —H, -alkyl, -aryl, -alkylaryl, -arylalkyl, or a moiety corresponding to: wherein R3 is a group selected from —OH, —O-alkyl, —O-aryl, —O-(alkylaryl), glycerol, glycerol monoester or diester, —NH2, —NH(alkyl), —N(alkyl)2, —NH(aryl), —N(aryl)2, —NH(alkylaryl), —N(alkylaryl)2, —SH, —S-alkyl, —S-aryl, or —S-(alkylaryl),L2 is a group selected from —(C═O)— or —(CH2)—,V and W are groups independently selected from methylene, alkenediyl, or substituted para-phenylenediamine,and wherein d+e+f is from 9 to 17. the number of methylene groups is from 8 to 16,the number of substituted para-phenylenediamine groups is from 0 to 3, andthe number of alkenediyl groups is from 0 to 3. In another aspect, the disclosure provides antidegradant products made by a process comprising hydroformylating one or more of a straight chain fatty acid having one or more unsaturations, e.g., carbon-to-carbon double bonds, and from 10 to 20 carbon atoms, or an amide or thioester or thiocarboxylic acid thereof, or a mono-, di-, or triglyceride thereof, or an alkyl ester or an aryl ester or an alkylaryl ester thereof wherein the alkyl or aryl or alkylaryl group has from one to twelve carbon atoms, or hydroformylating one or more of a straight chain fatty alcohol having one or more unsaturations, e.g., carbon-to-carbon double bonds, and from 10 to 20 carbon atoms by reaction with carbon monoxide and hydrogen gases to obtain a hydroformylated intermediate; and thereafter func