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GB915638A - Substituted o-aminophenols and their use in rubber technology - Google Patents

Substituted o-aminophenols and their use in rubber technology

Info

Publication number
GB915638A
GB915638A GB1339360A GB1339360A GB915638A GB 915638 A GB915638 A GB 915638A GB 1339360 A GB1339360 A GB 1339360A GB 1339360 A GB1339360 A GB 1339360A GB 915638 A GB915638 A GB 915638A
Authority
GB
United Kingdom
Prior art keywords
tert
hydrocarbon group
butyl
bis
methylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB1339360A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DEF28212A external-priority patent/DE1104522B/en
Priority claimed from DEF29491A external-priority patent/DE1119297B/en
Priority claimed from DEF29896A external-priority patent/DE1133883B/en
Application filed by Bayer AG filed Critical Bayer AG
Publication of GB915638A publication Critical patent/GB915638A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C215/76Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
    • C07C215/82Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the amino groups further bound to a carbon atom of another six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C215/76Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • C08K5/18Amines; Quaternary ammonium compounds with aromatically bound amino groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Natural and synthetic rubbers vulcanizates are rendered less susceptible to cracking by adding to mixture to be vulcanized 0,4 to 6% by weight of a substituted o-aminophenol of the general formula <FORM:0915638/IV(a)/1> wherein R1 is a hydrogen atom or a hydrocarbon group containing up to 16 carbon atoms, R2 is a hydrocarbon group containing up to 16 carbon atoms, and R3 and R4 represent a tertiary C4 to C9 hydrocarbon group, or by adding 0,4 to 6% by weight of a bisaminophenol having the structure obtained by substituting the radical <FORM:0915638/IV(a)/2> (wherein R8 and R6 are tertiary C4 to C9 hydrocarbon groups, and R5, R6 and R7 each represent a hydrogen atom or a hydrocarbon group containing up to 16 carbon atoms) in place of R2 in the first formula. All the examples relate to the resistance to cracking, under stretching, in the presence of ozonized air, of vulcanizates of pale crepe to which had been added specific substituted o-aminophenols or bis-aminophenols and various other additives. The specified aminophenols used in these tests were 2-methylamino-4,6-di-tert.-butyl phenol, and the corresponding 2-ethylamino-, n-propylamino-, 2-sec. butylamino-, 2-n-dodecylamino-, 2-phenylamino-, and 2-cyclohexylamino-compounds, also N-methyl-2-hydroxy-41-methyl-3,5-di -tert.-butyl-diphenylamine, N,N1-methylene-bis-(2-n-propylamino-4,6-di-tert.-butyl phenol) and the corresponding 2-tert.-butylaminocompound, N,N1-C-methyl-methylene-bis-(2-cyclohexylamino-4, 6-di-tert.-butyl phenol), N,N-C-isopropyl - methylene - bis - (2 - methylamino - 4,6-di-tert.-butyl phenol) and N,N1-methylene-bis[2-ethylamino - 4,6 - di - (alpha - methylcyclohexyl)-phenol]. Examples of synthetic rubbers which may be stabilized against the action of ozone by these compounds are polymers obtained from butadiene, dimethyl butadiene, and isoprene, and copolymers of such conjugated diolefines with styrene, alpha-methylstyrene, acrylonitrile, methacrylonitrile, acrylates or methacrylates, copolymers of isobutylene with small quantities of conjugated diolefines.ALSO:Substituted o-aminophenols of the general formula <FORM:0915638/IV (b)/1> wherein R1 is a hydrogen atom or a hydrocarbon group containing up to 16 carbon atoms, R2 is a hydrocarbon group containing up to 16 carbon atoms, and R3 and R4 each represent a tertiary C4 to C9 hydrocarbon group, are produced by reacting a 1,2-dihydroxybenzene, substituted in the 4-, 6-positions by the appropriate tertiary hydrocarbon groups, with a primary amine in the presence of oxygen, followed if necessary (i.e. when R1 is to be a hydrocarbon group) by alkylation. Bisaminophenols having the structure obtained by substituting the radical <FORM:0915638/IV (b)/2> (wherein R8 and R9 are tertiary C4 to C9 hydrocarbon groups, and R5, R6 and R7 each represent a hydrogen atom or a hydrocarbon group) in place of R2 in the first formula (R1 = H), are prepared by reacting the appropriate o-aminophenol (prepared as above) with an aliphatic aldehyde. In Example 1, isobutylamine is added to a suspension of 4,6-di-tert.-butylpyrocatechol in light benzene, and the mixture is then stirred for 7 hours in an open vessel. After drying with sodium sulphate, and removing the solvent in vacuo, there is obtained 2-sec.-butylamino-4,6-di-tert.-butylphenol, which may be converted into its hydrochloride. Example 3 describes the preparation of the corresponding (a) ethylamino- (b) n-propylamino- and (c) cyclohexylamino-compounds; and Example 4 describes the preparation of the corresponding dodecylamino-and phenylamino-compounds. When the reaction is effected with a primary arylamine, it is advantageous to work in the presence of a secondary or tertiary amine or an alkali metal hydroxide. Example 4 also describes the preparation of N-methyl-2-hydroxy-41-methyl-3,5-di-tert.-butyl diphenylamine by the action of dimethyl sulphate on 4,6-di-tert.-butyl-2-(N-p-tolyl)-aminophenol. Example 5 describes the preparation of N,N1-methylene-bis-(2-tert.-butylamino-4,6 - di-tert.-butyl-2-(N-tert.-butyl)-aminophenol with formaldehyde. It is stated that N,N1 - C - methyl-methylene-bis-(2-cyclohexylamino-4,6-di-tert.-butyl phenol) may be prepared, in an analogous manner, using acetaldehyde. These substituted o-aminophenols have use as anti-ozonants for natural and synthetic rubber (Group IV(a)). A list of suitable compounds is given; this list includes 2-(p-methoxyphenylamino)-4,6-di-tert.-butyl phenol and the corresponding ethoxyphenylamino-, phenoxy-phenylamino-, chlorophenylamino-, gamma-dimethyl-alpha-amino-, propylamino-, beta-hydroxyethylamino-, pyrenylamino-, and naphthylamino-compounds.
GB1339360A 1959-04-15 1960-04-14 Substituted o-aminophenols and their use in rubber technology Expired GB915638A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DEF28212A DE1104522B (en) 1959-04-15 1959-04-15 Process for the preparation of o-aminophenols
DEF29491A DE1119297B (en) 1959-09-29 1959-09-29 Process for the preparation of o-aminophenols
DEF29896A DE1133883B (en) 1959-11-21 1959-11-21 Non-discoloring anti-ozone agents for rubber goods

Publications (1)

Publication Number Publication Date
GB915638A true GB915638A (en) 1963-01-16

Family

ID=27210105

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1339360A Expired GB915638A (en) 1959-04-15 1960-04-14 Substituted o-aminophenols and their use in rubber technology

Country Status (2)

Country Link
FR (1) FR1254322A (en)
GB (1) GB915638A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5889125A (en) * 1996-08-14 1999-03-30 Vianova Resins Gmbh Curing component for epoxy resins and the use thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2998196A1 (en) 2012-11-22 2014-05-23 Valeo Sys Controle Moteur Sas METHOD FOR REGENERATING ZEOLITE

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5889125A (en) * 1996-08-14 1999-03-30 Vianova Resins Gmbh Curing component for epoxy resins and the use thereof

Also Published As

Publication number Publication date
FR1254322A (en) 1961-02-17

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