EP0169201A1 - Compositions de caoutchouc stabilisees - Google Patents

Compositions de caoutchouc stabilisees

Info

Publication number
EP0169201A1
EP0169201A1 EP19840901382 EP84901382A EP0169201A1 EP 0169201 A1 EP0169201 A1 EP 0169201A1 EP 19840901382 EP19840901382 EP 19840901382 EP 84901382 A EP84901382 A EP 84901382A EP 0169201 A1 EP0169201 A1 EP 0169201A1
Authority
EP
European Patent Office
Prior art keywords
rubber
unsubstituted
group
substituted
alkyl
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.)
Withdrawn
Application number
EP19840901382
Other languages
German (de)
English (en)
Inventor
Gerald Scott
Lakshman Premal Nethsinghe
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.)
Individual
Original Assignee
Individual
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
Application filed by Individual filed Critical Individual
Publication of EP0169201A1 publication Critical patent/EP0169201A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen

Definitions

  • This invention relates to stabilised rubber compositions ; more particularly, this invention relates to additives which have static antiozonant properties when incorporated in organic rubbers ; and to stabilised rubber compoundings and vulcanised rubber incorpo rating these additives, possibly by chemical binding.
  • the most successful class of antiozonant additive for rubbers comprises the N-aryl-substituted p-phenylenediamines, notably the N-aryl , N '-alkyl-substituted p-phenylenediamines .
  • the pre-eminent example is N-phenyl, N'-isopropyl-pphenylenediamine (IPPD) commercially available as SANTOFLEX IP
  • SANTOFLEX is a registered Trade Mark of Monsanto Company
  • a major disadvantage of these additives is that, in service , a small fraction thereof becomes converted into an intensely coloured by-product which not only prevents their use in white or coloured rubber compositions but also prevents carbon black-containing rubber compositions containing them being used contiguous with white or coloured polymer compositions into which the discoloration could migrate .
  • R 1 represents a (+ I) or a (+ M) group
  • R 2 and R 3 which may be the same or different, each represent a substituted or unsubstituted (alkyl or alkoxy) group
  • R 4 and R 5 which may be the same or different, each represent a hydrogen atom or a substituted or unsubstituted (alkyl or alkoxy) group;
  • R 6 represents a substituted or unsubstituted (branched alkyl or cycloalkyl) group.
  • R 1 may represent an unsubstituted or alkyl substituted hydroxy group or an unsubstituted or mono- or di-alkyl substituted amino group; or R 2 and R 3 , which may be the same or different, each represent an unsubstituted C 1 to C 5 alkyl or alkoxy group, preferably each represents an unsubstituted C 1 to C 4 alkyl group.
  • Suitable substituents include a halogen atom, for example a fluorine, chlorine, bromine or iodine atom, a hydroxyl group, an alkoxy group, an alkyl carboxylic ester group, a mercapto group, a thioether group, a substituted or unsubstituted amino or amido group.
  • a halogen atom for example a fluorine, chlorine, bromine or iodine atom, a hydroxyl group, an alkoxy group, an alkyl carboxylic ester group, a mercapto group, a thioether group, a substituted or unsubstituted amino or amido group.
  • R 2 and R 3 are the same. It is also preferred that at least one of R 4 and R 5 represents a hydrogen atom.
  • R 6 may suitably be a branched alkyl group , preferably a C 3 to
  • R 6 represents an isopropyl , sec . butyl or tert. butyl group .
  • This invention also provides the compound ⁇ -C-4-hydroxyphenylN-tert. butyl nitrone melting at 212o -215oC ; the compound ⁇ -C-4hydroxy-3 , 5-dimethylphenyl-N-tert . butyl nitrone melting at 178o 180oC ; the compound ⁇ -C-phenyl-N-tert.
  • the compounds of the invention may be prepared in a variety of ways ; for example :
  • a compounding which comprises at least one compound of the invention as herein described in intimate admixture with a rubber .
  • the rubber may comprise natural rubber, polybutadiene , polyisoprene, chloroprene , butyl rubber, ABS, nitrile rubber, ethylene-propylene rubber , the toughening phase in high-impact polystyrene or polyacrylonitrile .
  • the compound may comprise from 0.1 to 10, preferably, 0.5 to 6, especially 1 to 4 pph of the rubber.
  • the compound is chemically bound to the rubber, preferably by the method disclosed in UK 1503501. It is especially preferred to premill the additive, in the absence of oxygen, with the rubber.
  • a process for preparing a compounding as aforesaid which process premilling a compound of the invention with the rubber for a time not exceeding 10 minutes, preferably not exceeding 6 minutes, particularly preferably not exceeding 2 minutes.
  • the premilling is effected in the presence of oxygen.
  • This invention further provides a compounding prepared by this process.
  • This invention also provides a rubber compounding as herein described which has been vulcanised.
  • This invention provides a synergistic mixture of a nitrone of this invention and a rubber antioxidant.
  • 2-Methyl-2-nitropropane was prepared by the oxidation of tertiarybutylamine using hydrogen peroxide according to the procedure described by Stowell (J. Org. Chem., 36, p. 3055 (1977)). 36.6 g (52 ml); 0.5 moles) of tertiarybutylamine was used. The yield was 25.8 g (0.293 moles; 59% of theoretical). Boiling point 126-128°C. The corresponding hydroxylamine was then synthesised by the reduction of the 2-methyl-2-nitropropane using zinc dust and ammonium chloride according the method described by Greene et al (J. Org. Chem., 34, p. 2269 (1969)). 25 g (0.28 moles) of the 2-methyl-2-nitropropane was used. The yield was 18.2 g
  • Example 2 ⁇ -C-4-hydroxyphenyl-N-tert. butyl nitrone. Yield: 30% ; melting point; 212-215°C.
  • Example 3 ⁇ -C-phenyl-N-tert . butyl nitrone . Yield: 70%; melting point; 75-77oC .
  • Examples 4 ⁇ -C-4-hydroxy-3 ,5-dimethylphenyl-N-isopropyl nitrone. Yield: 58%; melting point: 192-195oC.
  • Example 5 ⁇ -C-4-methoxyphenyl-N-isopropyl nitrone .
  • Example 6 ⁇ -C-4-chlorophenyl-N-isopropyl nitrone. Melting point : 183-185oC .
  • the experimental run was repeated premilling for 4 minutes, and also for 6 minutes. In all cases the premilling and compounding time totalled 15 minutes.
  • the vulcanising, antifatigue and antiozonant properties are shown, and compared with those of a control and a sample comprising IPPD, in the following Tables. Referring to Table 3, the colour rating (arbitrary scale) of the sample containing the additive of Example 2, at 20% strain, was 2, compared with 8 for the control and IPPD samples at the same strain.
  • Example 7 was essentially repeated using the nitrone of Example 4.
  • the maximum torque was 60 lbs -1 ; the number of hours to break was 130; and the time of ozone exposure to failure was 70 hours.
  • the colour rating was 3.
  • Example 7 was essentially repeated using the nitrone of Example 4 in admixture with 1 g of Nonox WSP:

Landscapes

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

Abstract

Nitrone d'alcoyle ramifié ou de cycloalcoyle, C-substitué ou non substitué, alryle-N-substitué ou non substitué, possèdant des propriétés anti-fatigue et/ou anti-ozonante dans du caoutchouc.
EP19840901382 1983-03-30 1984-03-26 Compositions de caoutchouc stabilisees Withdrawn EP0169201A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8308840 1983-03-30
GB8308840 1983-03-30

Publications (1)

Publication Number Publication Date
EP0169201A1 true EP0169201A1 (fr) 1986-01-29

Family

ID=10540511

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840901382 Withdrawn EP0169201A1 (fr) 1983-03-30 1984-03-26 Compositions de caoutchouc stabilisees

Country Status (3)

Country Link
EP (1) EP0169201A1 (fr)
JP (1) JPS60500957A (fr)
WO (1) WO1984003883A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE59915B1 (en) * 1986-07-25 1994-04-20 Microsi Inc Contrast enhancement layer compositions, alkylnitrones, and use
US5091449A (en) * 1990-08-02 1992-02-25 The Goodyear Tire & Rubber Company Alpha-(2,4-dihydroxy)phenyl N-phenyl nitrone and its use in the modification of diene containing polymers
US7186845B2 (en) * 2004-10-20 2007-03-06 Bridgestone Corporation Polymer-filler coupling additives
JP2007070439A (ja) * 2005-09-06 2007-03-22 Bridgestone Corp ゴム組成物及びそれを用いたタイヤ
JP5578249B1 (ja) * 2013-03-08 2014-08-27 横浜ゴム株式会社 ホットメルト接着剤組成物
FR3021315B1 (fr) * 2014-05-23 2017-11-03 Michelin & Cie Compose 1,3-dipolaire portant une fonction ester d'acide carboxylique et composition de caoutchouc le contenant

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3917700A (en) * 1974-01-30 1975-11-04 Goodyear Tire & Rubber Nitrone compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8403883A1 *

Also Published As

Publication number Publication date
JPS60500957A (ja) 1985-06-27
WO1984003883A1 (fr) 1984-10-11

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