Phenylenediamines rubber antioxidants

Rubber antioxidants are commonly of an aromatic amine type, such as dibeta-naphthyl-para-phenylenediamine and phenyl-beta-naphthylamine. Usually, only a small fraction of a percent affords adequate protection. Some antioxidants arc substitute phenolic compounds (butylatcd hydro -vamsole, di-tert-butyl-para-cresol, and propyl gallate). 

Diaminodiphenylamine p,p -Diaminodiphenylamine Di(p-aminophenyljamine Diazol Black C Diphenylamine, 4,4-diamino- EINECS 208-673-4 4,4-lminodianiline Indamine NSC 33417 p-Phenylenediamine, N-(p-aminophenyl)-. A proprietary trade name for a rubber antioxidant. Also used to dye fur and to detect hydrogen cyanide. Leaflets mp = 158° bp dec very soluble in EtOH, Et20. 

Methyl oleate N,N,N, N -Tetramethylethylenediamine Triethylamine intermediate, rubber accelerators Allyl mercaptan t-Butylamine Diethylamine Isopropylamine 2-Methylpropanal p-Phenylenediamine Piperidine intermediate, rubber additives Benzoyl chloride intermediate, rubber antioxidants 2-Methylpropanal intermediate, rubber chemicals Benzonitrile Bisphenol A n-Butylamine Cyclopentanone Diethanolamine Ethylene carbonate Ethylenediamine Hexamethyleneimine dl-Limonene 2-Mercaptoethanol... 

APPLICATION OF INTERCALATED COMPOUND OF MONTMORILLONITE AND N, N -DIPHENYL-p-PHENYLENEDIAMINE TO ANTIOXIDANT FOR RUBBER MATERIALS... 

Mixed diaryl—y -phenylenediamines, antioxidant of The Goodyear Tire Rubber Co. Accelerator of Monsanto Co. 

Plasticiser/oil in rubber is usually determined by solvent extraction (ISO 1407) and FTIR identification [57] TGA can usually provide good quantifications of plasticiser contents. Antidegradants in rubber compounds may be determined by HS-GC-MS for volatile species (e.g. BHT, IPPD), but usually solvent extraction is required, followed by GC-MS, HPLC, UV or DP-MS analysis. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out. The determination of antioxidants in rubbers by means of HPLC and TLC has been reviewed [58], The TLC technique for antidegradants in rubbers is described in ASTM D 3156 and ISO 4645.2 (1984). Direct probe EIMS was also used to analyse antioxidants (hindered phenols and aromatic amines) in rubber extracts [59]. ISO 11089 (1997) deals with the determination of /V-phenyl-/9-naphthylamine and poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMDQ) as well as other generic types of antiozonants such as IV-alkyl-AL-phenyl-p-phenylenediamines (e.g. IPPD and 6PPD) and A-aryl-AL-aryl-p-phenylenediamines (e.g. DPPD), by means of HPLC. 

Diaryl-phenylenediamines have very good antioxidant activity with good to moderate antiozonant characteristics, with low volatility but will possibly bloom to the rubber surface. They give very good flex cracking resistance. 

A number of amines and phenols are known to be effective stabilizers - for rubber (2, 20). They are capable of protecting unsaturated polymers from the attack of oxygen and ozone, but the effects of the stabilizers on antioxidation and antiozonization are not always the same —e.g., N,N -diphenyl-p-phenylenediamine (A) is an antioxidant, whereas jV,N -phenylcyclohexyl-p-phenylenediamine (B) is an antiozonant. 

Other Uses for Aniline. Aniline currently is used as a raw material in most of the major groups of rubber-processing chemicals accelerators, antioxidants and stabilizers, and anti-ozonants. The most important of these are the thiazole derivatives and substituted para-phenylenediamines. The demand for aniline in these rubber-processing uses is expected to grow at less than 1 percent/year. In agricultural chemicals, the major use for aniline is as a raw material in the manufacture of amide herbicides for controlling annual... 

Also, antioxidants were found to decrease the aging rate of natural rubber. Among the antioxidants more frequently used are N-phenyl-p-naphthylamine, 2,6-di-tert-butyl-4-methyl-1-hydroxybenzene (BHT), N-isopropyl-N -phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N -p-phenylenediamine, and poly-(2,2,4-trimethyl-1,2-dihydroquinoline). 

Over half of the remaining market for products used in the processing of rubber is made up of antioxidants, antiozonants and stabilizers, either amino compounds or phenols. Aniline is used to manufacture vulcanization accelerators, antioxidants and antidegradants. Of the latter, several are A-substituted derivatives of p-phenylenediamine and octyl dipheny-lamine. Diphenylamines terminate free-radical reactions by donating the amino hydrogen, and are used to protect a wide range of polymers and elastomers. Many synthetic rubbers incorporate alkylated diphenylamine antioxidants. Other antioxidants include aryl amine resinous products from, e.g. condensation of aniline and acetone in the presence of... 

Staining antioxidants such as AJ-isopropyl-AT-phenyl-/>-phenylenediamine [101-72-4] (36) are preferred for the manufacture of tires (see also Amines, AROMATIC, PHEN YLENEDI amines). These potent antioxidants also have antiozonant activity and retard stress cracking of the vulcanized rubber. Carbon black (qv), used in tires for reinforcement, hides the color developed by the antioxidant. According to use requirements, up to 3% of an amine antioxidant having antiozonant activity is added prior to vulcanization. 

Beilstein Handbook Reference) Aceto DIPP Agerite White AgeRite W AI3-14324 Antigene F Antioxidant 123 Antioxidant DNP ASM-DNT 1,4-Benzenediamine, N,N -di-2-naphthalenyl- N,N -Bis-(2-naftyl)-p-fenylendiamin 1,4-Bis(2-naphthylamino)-benzene N,N -Bis((3-naphthyl)-p-phenylenediamine N,N -Bis(2-naphthyl)-p-phenylenediamine BRN 2224419 CCRIS 6026 Oi-(3-naphthyl-p-phenyldi-amine Di-(J-naphthyl-p-phenylenediamine s-Di(P-naphthyl)-p-phenylenediamine N,N -Di-p-naphlhyl-p-phenylene-diamine N,N -Di-2-naphthalenyl-1,4-benz-enediamine N,N -Di-2-naphthyl-p-phenylenediamine Diafen NN DNPD Dnpda Dwu-p-naftylo-p-fenylodwuamina EINECS 202-249-2 Nonox CL NSC 3410 p-Phenylenediamine, N,N -(di-2-naphthyl)- N,N -p-Phenylenebis(2-naphthylamine) Santowhite CL Tisperse MB-2X. Antioxidant, An antidegradant for latex, nitrile rubber, styrene-butadiene and nitrile-butadiene rubber. Solid mp = 224-230° d n 1.22-1.28 insoluble in H2O, EtOH, soluble in organic solvents LDso (rat orl) = 4500 mg/kg. Vanderbilt R. T. Co. Inc. 

Rubber Chemicals. Sodium nitrite is an important raw material in the manufacture of rubber processing chemicals. Accelerators, retarders, antioxidants (qv), and antiozonants (qv) are the types of compounds made using sodium nitrite. Accelerators, eg, thiuram [137-26-8], greatly increase the rate of vulcanization and lead to marked improvement in mbber quality. Retarders, on the other hand (eg, N-nitrosodiphenylamine [156-10-5]), delay the onset of vulcanization but do not inhibit the subsequent process rate. Antioxidants and antiozonants, sometimes referred to as antidegradants, serve to slow the rate of oxidation by acting as chain stoppers, transfer agents, and peroxide decomposers. A commonly used antioxidant is N,IV-disubstituted /)-phenylenediamine which can employ sodium nitrite in its manufacture (see Rubber chemicals). 

The reaction of aniline and aniline derivatives with p-chloronitrobenzene is the critical coupling reaction practiced by Bayer and Monsanto for the manufacture of 4-nitrodiphenylamine, 2. Hydrogenation of 2 produces 4-aminodiphenylamine (4-ADPA), 3, which is a key intermediate in the p-phenylenediamine class of antioxidant used in rubber products (Figure 8). 

It has been known for a number of years that FD-MS is an effective analytical method for direct analysis of many rubber and plastic additives. Major components and impurities in commercial additives can be assessed quickly, and the FD-MS data can be used to help determine what (if any) additional analytical characterization is needed. Lattimer and Welch showed that FD-MS gives excellent molecular ion spectra for a number of polymer additives, including rubber accelerators (diWocarbamates, guanidines, benzothiazyl, and thiuram derivatives) antioxidants (hindered phenols, aromatic amines) p-phenylenediamine-based antiozonants, processing oils, and phthalate plasticizers. Zhu and Su characterized alkylphenol ethoxylate surfactants by FD-MS. Jackson et al. analyzed some plastic additives (hindered phenol antioxidants and a benzotriazole UV stabilizer) by FD-MS. ... 

IR, EPDM, NBR limited sol. in BR and SBR Uses Nonstaining antioxidant and antiozonant in rubber limited sol. in syn. rubbers N-(1,4-Dimethylpentyl)-N -phenyl-p-phenylenediamine CAS 3081-01-4... 

Manuf/Distn b. Aldrich http //www.sigma-aldrich.com, Fluorochem USA http //www.fiuorochemusa.com-, ICN Biomed. Research Prods, http //www.icnbiomed.com, Lancaster Synthesis Oakwood Prods. http //www. oakwoodchemical. com Pfaltz Bauer http //www.pfaltzandbauer.com, Sumitomo Seika TCI Am. http //www.tciamerica. com N-Phenyl-N -(p-toluenesulfonyl)-p-phenylenediamine CAS 100-93-6 Empirical C19H18N2O2S Uses Antioxidant for rubbers Manuf./Distrib. Crompton/Uniroyal http //WWW. cromptoncorp. com... 

Di-t-butyl-4-hydroxybenzoic acid, n-hexadecyl ester antioxidant, mastic adhesives Phenol, styrenated antioxidant, meat Citric acid monohydrate antioxidant, mech./molded rubber goods Phenol, styrenated antioxidant, mercaptans N,N -Di (n-octyl)-p-phenylenediamine antioxidant, metal-catalyzed breakdown Disodium EDTA antioxidant, metals Hydrogen... 

BHT Bisphenol A, polybutylated Diphenylamine-acetone Distearyl thiodipropionate Nickel dibutyidithiocarbamate Zinc diisobutyidithiocarbamate Zinc 2-mercaptotoluimidazole antioxidant, SR rubber food-contact Cyclohexyl-N -phenyl-p-phenylenediamine antioxidant, stabilized polymers Perchloropentacyclodecane antioxidant, staining carpet backcoating latex foams... 

N,N -Diphenyl-p-phenylenediamine antioxidant/antiozonant, flex-resistant rubber N,N -Diphenyl-p-phenylenediamine antioxidant/antiozonant, footwear... 

Another important product from 2-toluidine is a mixture of arylated p-phenyl-enediamines, which is widely used as an antioxidant material in rubber processing it is manufactured by the reaction of hydroquinone, aniline and 2-toluidine and consists of N,N -ditolyl- and N,N -diphenyl-p-phenylenediamine (DTPD, DPPD) and N-o-tolyl-N -phenyl-p-phenylenediamine (Goodyear). 

Rubber-based products permeate our lives, forming part of the many materials used for personal, domestic and industrial purposes. Rubber may be natural, synthetic or a mixture of the two. Since the vast majority of rubberized materials are unlabeled, it is difficult to determine whether a product contains natural or synthetic rubber. The overlap between rubber and plastic further complicates the matter, especially since plastics contain many of the same catalysts, stabilizers, antioxidants and pig-ments/dyes that are present in rubber products. Fregert (1981) listed a number of naphthylamines, substituted para-phenylenediamines, alkylphenols and hydroquinone derivatives, which are utilized in the manufacturing of both rubber and plastic. Although completely cured plastics are rare sensitizers, fully cured rubber products produce allergic reactions as the sensitizers in rubber can leach out or bloom over time. 

Running shoes and athletic gear contain rubber additives, accelerators, and antioxidants, which are common causes of contact allergy. Among the potential allergens are thioureas, thiurams, N-isopro-pyl-N-phenyl-p-phenylenediamine (IPPD), and me-... 

N-Phenyl-AT-Cyclohexyl-p-Phenylenediamine (CPPD) is a rubber chemical used as an antioxidant. Cross reactions are frequently observed with isopropylphe-nylparaphenylenediamine (IPPD). 

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