Nonylated diphenylamines

Details Nonylated diphenylamines Nonylated diphenylamines

2000-02-14

2001-11-13

Warden, Jill (Department: 1743)

Compositions

Preservative agents

Anti-oxidants or chemical change inhibitants

C508S563000, C564S409000

Reexamination Certificate

active

06315925

ABSTRACT:

The invention relates to a mixture of nonylated diphenylamines, to a process for the preparation of that mixture and to the use thereof as an additive for stabilising organic products that are subjected to oxidative, thermal and/or light-induced degradation.
Additives are added to numerous organic products widely used in engineering, for example to lubricants, hydraulic fluids, metal-working fluids, fuels or polymers, to improve their performance properties. In particular, there is a need for additives that effectively inhibit the oxidative, thermal and/or light-induced degradation of those products and thereby considerably increase their useful life.
U.S. Pat. No. 2,943,112 describes anti-oxidants from the group of the alkylated diphenylamines that are prepared by reaction of diphenylamine with alkenes in the presence of mineral acids and large quantities of acid clays as catalysts. Alkylation of the diphenylamine with alkenes, for example nonene, results in mixtures of mono- and di-alkylated diphenylamine. In that process, relatively large quantities of the starting material, generally from 6 to 12% diphenylamine, are not reacted, which reduces the anti-oxidative efficacy of the alkylated diphenylamines, leads to the deposition of sludge and imparts undesirable toxic properties to the product. Reaction with additional alkenes is proposed as an alternative to the distillative separation of the starting material from the products.
U.S. Pat. No. 3,496,230 describes the preparation of a mixture of 80% dinonyidiphenylamine and 15% nonyldiphenylamine in the presence of Friedel-Crafts catalysts of the aluminium chloride type, but that mixture still has a diphenylamine content of 2% (see therein the information in Example 2). The preparation of that mixture is especially disadvantageous since it is contaminated by traces of chlorine, metal compounds and undesirable by-products, e.g. N-alkylated diphenylamines and diphenylamines alkylated in the 2- and 2′-positions, is black in colour and is very viscous.
European Patent Application No. 387 979 describes the reaction of diphenylamine with an eight-fold excess of tripropylene. That process is also disadvantageous since, in addition to the large excess of tripropylene, it is also carried out in the presence of large quantities of acid-activated clays.
The problem underlying the present invention is to prepare a mixture of nonylated diphenylamines that comprises as large as possible amounts of dinonyidiphenylamine, especially 4,4′-dinonyldiphenylamine, in addition to nonyldiphenylamine, e.g. 4-monononyidiphenylamine, and as small as possible amounts of undesirable by-products, e.g. N-alkylated diphenylamines and diphenylamines alkylated in the 2- and 2′-positions.
That problem is solved by a inventive process which comprises alkylating diphenylamine with an excess of nonene or a mixture of isomeric nonenes in the presence of from 2.0 to 25.0% by weight, based on diphenylamine, of an acid earth and in the absence of a free protonic acid.
The invention relates to a mixture of nonylated diphenylamines that has a content in a gas chromatogram (GLC, on-column method) of:
a) at least 68.0% by area dinonyldiphenylamine;
b) from 20.0 to 30.0% by area nonyidiphenylamine;
c) not more than 3.5% by area trinonyldiphenylamine; and
d) not more than 1.0% by area diphenylamine.
Preference is given to mixtures wherein the nonyl groups in the main component dinonyldiphenylamine and in the co-component nonyidiphenylamine are in the 4,4′-position and the 4-position, respectively, of the diphenylamine. Also preferred are mixtures wherein the nonyl groups are derived by reacting the diphenylamine with tripropylene.
In a preferred embodiment, the invention relates to a mixture comprising in a gas chromatogram:
a) from 70.0 to 75.0% by area dinonyldiphenylamine;
b) from 25.0 to 30.0% by area nonyidiphenylamine;
c) not more than 3.5% by area trinonyldiphenylamine and
d) not more than 1.0% by area diphenylamine.
In an especially preferred embodiment, the invention relates to a mixture comprising in a gas chromatogram:
a) from 70.0 to 75.0% by area dinonyldiphenylamine;
b) from 25.0 to 28.0% by area nonyldiphenylamine;
c) not more than 3.0% by area trinonyldiphenylamine and
d) not more than 0.8% by area diphenylamine.
The statement “at least 68.0% by area dinonyidiphenylamine” means preferably from 68.0 to 78.0% by area, especially from 70.0 to 75.0% by area, dinonyldiphenylamine.
In the preferred embodiments, the statements “not more than 3.5% by area trinonyldiphenylamine” means from 1.0 to 3.5% by area, preferably from 1.5 to 3.5% by area, also preferably from 2.0 to 3.5% by area and especially from 2.5 to 3.5% by area. The statement “not more than 3.0% by area trinonyldiphenylamine” means preferably from 1.0 to 3.0% by area, preferably from 1.5 to 3.0% by area, also preferably from 2.0 to 3.0% by area and especially from 2.5 to 3.0% by area, of that component.
The statement “not more than 1.0% by area diphenylamine” means preferably from 0.1 to 1.0% by area, especially from 0.3 to 0.8% by area, and the statement “not more than 0.8% by area diphenylamine” means preferably from 0.3 to 0.8% by area, especially from 0.3 to 0.6% by area, of that component in a gas chromatogram.
The invention also relates to the product of the inventive process obtainable by alkylation of diphenylamine with an excess of nonene or a mixture of isomeric nonenes in the presence of from 2.0 to 25.0% by weight, based on diphenylamine, of an acid earth and in the absence of a protonic acid.
The invention also relates to the product of that inventive process, which has a kinematic viscosity of <500 mm
2
/sec at 40° C.
The invention further relates to the process for the preparation of a mixture of nonylated diphenylamines comprising in a gas chromatogram
a) at least 68.0% by area dinonyidiphenylamine;
b) from 20.0 to 30.0% by area nonyidiphenylamine;
c) not more than 3.5% by area trinonyldiphenylamine; and
d) not more than 1.0% by area diphenylamine,
which comprises alkylating diphenylamine with an excess of nonene or a mixture of isomeric nonenes in the presence of from 2.0 to 25.0% by weight, based on diphenylamine, of an acid earth and in the absence of a free protonic acid.
Preference is given to obtainable products for which from 5.0 to 20.0% by weight, especially from 5.0 to 10.0% by weight, of an acid earth is used in the process.
Suitable acid clays are, for example, active catalysts based on layered silicate, e.g. montmorillonites activated by mineral acids, such as sulfuric acid and/or hydrochloric acid, that preferably have a moisture content below 10%, especially below 5%, e.g. of the clays of the so-called Fuller type, e.g. types obtainable commercially under the names Fulcat®, e.g. types 20, 22 B and 40 (argillaceous earths activated by sulfuric acid), Fulmont® (Laporte Industries), e.g. types XMP-4, XMP-3, 700 C and 237, or acid earths of types K5 and K10 (activated by hydrochloric acid), KS and KSF (activated by sulfuric acid) or KSF0 (activated by hydrochloric acid and sulfuric acid) produced by Südchemie, and earths based on bentonite, e.g. products of the type Filtrol® or Retrol® (Engelhard Corp.).
The expression “absence of a free protonic acid” defines a feature of this process in which, in contrast to the process described in U.S. Pat. No. No. 2,943,112, no inorganic or organic acids are added to the reaction mixture.
Preference is given to obtainable products for which, as the nonene, tripropylene, especially a 4- to 10-fold molar excess of nonene, based on diphenylamine, is used in the process.
Special preference is given to obtainable products for which a from 4- to 8-fold, especially a 4- to 6-fold, molar excess of nonene, that is to say tripropylene, is used in the process.
The products of the process are obtained when the alkylation is carried out, for example, at a temperature range from 120° to 250° C., especially at a temperature of from 150° to 220° C.
The process can be carried out by introducing the starting materials and the a

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