Note: Descriptions are shown in the official language in which they were submitted.
204~19~
A- 18035/A
Isoindolinone compounds as stabilisers for or anic materials
The present invention selates to compositions comprising an organic material liable to
oxidative, thermal and/or actinic degradation and at least one isoindolinone compound.
The invention further relates to the use of these compounds as additives for thestabilisation of organic material and to novel isoindolinone compounds.
2,3-Benzofuran and indolin-2-one compounds have already been proposed as stabilisers in
polymeric organic materials (WO-A 80/01566). Nuclear (per)chlorinated indolinone,
isoindolinone and indolinedione compounds were mentioned in DE-A 3 230 593 as high
pressure additives for lubricants. Certain isoindolinones were proposed as UV slabilisers
in DE-A 1 770 439.
Isoindolinone compounds containing a further fused (hydro)pyridine ring were described
in 1972 (C.H. Gaozza et al., J. Het. Chem. _, 883 (1972)), to be precise with the aim of
testing their pharmacological activity. Similar compounds were later also investigated for
their suitability as DNA intercalators (S.E. Piatti et al. Anales Asoc. Quim. Argentina 70,
65 L (1982)). Polycyclic, sulfur-containing compounds are additionally proposed in US-A
3 591 599 as inflammation-inhibiting and analgesic agents which contain the
isoindolinone ring system. Pharrnaceutically active isoindolinone derivatives were also
prepared, the best-known of which is etomidoline, a spasmolytic (Merck Index, 10th ed.,
3829, US-A 3 624 206). The use of isoindolinone derivatives containing a fused
(benzo)thiophene ring as fogging preventers in photographic silver halide emulsions is
furthermore known (US-A 2 860 985).1n addition, a large number of documents are
known which describe 8,9,10,11-tetrahydro-12-phthaloperinones as dye. As an example,
see DE-A 1 569 613.
Other polycyclic compounds which contain a fused isoindole ring system have beeninvestigated, for example, in the following literature references: Liebigs Ann. Chem.
1985, 657; J. Org. Chem. 34 (1969), 165; Chem. Pharm. Bull. 20 (1972), 69; Chem.Pharm. Bull. 22 (1974), 2142; US-A 3 994 920; DE-A 1 670 446; US-A 3 507 867; DE-A
2 062 022.
2~4~195
- 2 -
In the present application, isoindolinone compounds containing fused rings are now
proposed for the first time in compositions containing organic materials to improve their
stability and processibility.
Novel isoindolinone compounds have furthermore been found which are likewise
excellently suited for the protection of organic material from therrnal, oxidative and/or
actinic degradation.
The present invention relates to compositions comprising an organic material liable to
thermal, oxidative and/or actinic degradation and at least one compound of the formula (I)
R~ (1),
in which R is hydrogen, Cl-CI8alkyl, Cl-CI8alkoxy, halogen, nitro, phenyl-CI-C4alkoxy,
C2-Cl8alkanoyl, benzoyl, (Cl-C6alkyl)benzoyl, C2-CI8alkenoyl, -N(R7)(R7a), -OH or
-CO-A, Rl has the same possibilities of meaning as R, R2 is hydrogen or Cl-C4alkyl and
R3 is hydrogen or halogen, A is hydroxyl, Cl-Cl8alkoxy, Cs-CI2cycloalkoxy, benzyloxy or
benzyloxy substituted by Cl-C4aLlcyl and/or halogen, -N(R7)(R78), -NH-NH-R8 or
~GI-(G)n~ n is a number from 1 to 3 and G is a radical of the formula
R2 R3
R~
O
Gl in the case where n = 1 is -O-R20-O-, -NH-R21-NH- or-NH-NH-,
in the case where n = 2 is a group of the forrnula
2~019~
- 3 -
-Q~ -M I - I -M2-Q2-
M3
(III)
IQ3
and in the case where n = 3 is (-O-CH2)4C or
-OCH2CH-CH2-0-CH2IH-CH2--
o
where D is N, CH or C(CI-C4alkyl), Ql, Q2 and Q3 independently of one another are O or
NH and Ml, M2 and M3 independently of one another are C1-C6alkylene or
C2-CI2alkylene which is interrupted by -O-, or in the case where D = CH or C(CI-C4alkyl)
-M3-Q3 iS also -O- or in the case where D = N -M3-Q3 iS also a direct bond,
R5 and R6 together forrn a group of the fonnula
~x ~xRlo ~xl
(IV) ~b~12 1CO-A2
Rl3 R
Rl3 ~
X~ ~ (VII)
Rl8 Rl7
O O
Il 11
X is -O-, -S-, -S- , -S- or -N-
OR13
2~0~9~
-4 -
O O
Il 11
Xl is-S-, -S- or -S- and
X2 is -CH2 or a direct bond, R7 and R7a independently of one another are hydrogen,
Cl-Cl8alkyl, phenyl-CI-C4alkyl, C2-CI8alkanoyl, C2-CI8alkenoyl, C2-C4hydroxyalkyl,
benzoyl or (Cl-C6alkyl)benzoyl or, together with the N atom to which they are bonded,
are piperidyl, nnorpholinyl, piperazinyl or 4-methylpiperazinyl, R8 is hydrogen,C2-CIgalkanoyl, benzoyl or (C1-C6alkyl)benzoyl, R9, Rlo, Rll and Rl2 have Ihe same
possibiliti~.s of meaning as R, Rl, R2 and R3 (in this sequence), where -CO-A is to be
replaced by -CO-AI, Rl3 is hydrogen, Cl-Cl8alkyl, C2-CI8alkenyl, C5-C12cycloalkyl,
phenyl-CI-C4alkyl, C2-CI8alkanoyl, C2-CI8alkenoyl, benzoyl, (Cl-C6alkyl)benzoyl,
cyano-CI-C4alkyl, C2-CIgalkoxycarbonyl-CI-C4alkyl, carboxy-CI-C4alkyl,
hydroxy-CI-C4alkyl or tCH2ClH203~cH2lcH--~Rl3b
Rl3a Rl3a
Rl3a is hydrogen or methyl and Rl3b is hydrogen, Cl-CI8alkyl, phenyl-CI-C4alkyl,Cl-Cl8alkanoyl, benzoyl, C2-CIgalkenoyl or (Cl-C6alkyl)benzoyl and a is a number from
O ~o 6, Rl4, Rl5, Rl6, Rl7, R18 and Rlg independently of one another are hydrogen,
Cl-C4alkyl, halogen, hydroxyl, Cl-Cl8alkoxy or -N(R7b)(R7C), in which R7b and R7C
independently of one another are hydrogen or Cl-Cl8alkyl, R20 is Cl-Cl2alkylene,C2-C8alkenylene, C3-C6alkynylene or C2-C24alkylene which is interrupted by 0, S and/or
-N(R22)-, R2l is Cl-CI2alkylene and R22 is hydrogen, Cl-CIgalkyl, phenyl,
(Cl-C6alkyl)phenyl or phenyl-CI-C4alkyl, Al is hydroxyl, Cl-C24alkoxy,
C5-CI2cycloaL~;oxy, benzyloxy or benzyloxy substituted by Cl-C6alkyl and/or halogen,
-N(R7)(R7a), -NH-NH-R8 or -Gl-(G2)n~ and A2 is hydroxyl, Cl-C24alkoxy,
C5-CI2cycloalkoxy, benzyloxy or benzyloxy substituted by Cl-C6alkyl and/or halogen,
-N(R7)(R7a), -NH-NH-R8 or-Gl-(G3)n, where Gl and n are as deflned above, G2 is aradical of the forrnula
o
Rl~-- and
2~401~
G3 is a radical of the formula
o o
with the proviso that only one substituent -CO-A, CO-AI or -CO-A2 is present in the
molecule, in which A, Al or A2 is a radical ~~I~(G)n~ ~GI-(G2)n or GI-(G3)n~
If in the above formulae R, Rl, R9, Rlo, R7, R7a~ R,b, R7c~ Rl3, Rl3b or R22 are Cl-Cl8alkyl
radicals they are branched or unbranched. Examples of these are methyl, ethyl, propyl,
isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl,
2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl,
1,1,3,3-tetramethylbutyl, l-methylhexyl, isoheptyl, l-methylheptyl, 1,1,3-trimethylhexyl
or 1-methylundecyl; the radicals R, Rl, R2, R7, R7a~ R7b, R7c~ Rg, Rlo, R,3b and R22 in this
case preferably have 1-12, in particular 1-4 C atoms. Possible Cl-C4alkyl R2 and Rl4 to
Rl9 radicals are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and
t-butyl. Further alkyl groups in the above formulae which are not mentioned in more detail
here have the same exemplary meanings.
Examples of C~-C18(or C~-C24)alkoxy groups R, Rl, Rg, Rlo, A, Al, A2 and Rl4-RI9 are
derived from the radicals enumerated above for Cl-CI8alkyl groups plus eicosyl and
docosyl as further examples and can be formally defined by appending the suffice -oxy.
If the substituents in forrnula I are halogen, these are to be understood as meaning, Cl, Br,
F and I, in particular Cl and Br, especially Cl.
R, Rl, R7, R7a~ R8, R9, Rlo, Rl3 and R13b as C2-CI8alkanoyl are groups of the formula
-CO-Cl-CI7alkyl. Examples of such radicals are obtainable by employing the radicals
mentioned above for Cl-Cl8alkyl (without octadecyl). C2-CsAlkanoyl is preferred for the
radicals R, Rl, Rg and Rlo.
R, Rl, Rg and Rlo as phenyl-CI-C4alkoxy is, for exarnple, benzyloxy, phenethoxy,
2~40195
a-methylbenzyloxy, or ~ dimethylbenzyloxy. Benzyloxy is preferred. The same
substituents and also R7, R7a~ R8, Rl3 and Rl3b as (Cl-C6alkyl)benzoyl can carry, for
example, 1-3, especially I or 2, in particular I Cl-C6alkyl group(s) in the phenyl radical.
Examples of alkyl are mentioned further above. Cl-C4Alkyl is preferred here, in particular
methyl.
Rl3 as C2-CI8alkenyl can be branched or unbranched and is, for example, vinyl, allyl,
2-methallyl, hexenyl, undecenyl, heptadecenyl and oleyl.
R, Rl, R7, R7a~ R9, Rlo, R13 and R13b as C3-CI8alkenoyl are radicals of the fo~nula
-CO-C2-CI7alkenyl. Examples of such radicals are obtainable by employing the radicals
mentioned above for C2-CI8alkenyl (without oleyl).
Rl3 as Cs-CI2cycloalkyl can be, for example, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl or cyclododecyl. Cyclopentyl and cyclohexyl are preferred, in particular
cyclohexyl
Rl3 as C2-C~galkoxycarbonyl-C~-C4alkyl is in particular C2-CIgalkyloxycarbonylmethyl.
The alkoxy moiety preferably has 1 to 12 C atoms.
Cycloalkoxy as a substitutent A, Al or A2 is, for example, cyclopentyloxy, cyclohexyloxy,
cyclooctyloxy, cycloheptyloxy or cyclododecyloxy, cyclopentyloxy and in particular
cyclohexyloxy being preferred.
Substituted benzyloxy as a substituent A, Al or A2 contains, for example, 1 to 3substituents from the series comprising halogen (in particular chlorine) and Cl-C6alkyl.
Either halogen or alkyl are preferably present as substituents. I or 2, especially 1
substituent, is expedient. Alkyl is especially Cl-C4alkyl, in particular methyl.
Cl-C6Alkylene (substituents M1, M2, M3) and C~-CI2alkylene (R20, R21) can be
straight-chain or branched and is, for example, methylene, ethylene, propylene, butylene
or hexylene and for R20 and R21 is additionally octylene, decylene and dodecylene,
straight-chain radicals being preferred.
R20 as C2-C8alkenylene or C3-C6alkynylene is, for example, Yinylene, butenylene,hexenylene and octenylene or butynylene.
- 2~4019~
Examples of C2-CI2alkylene (Ml, M2, M3) and C2-C24alkylene (R20) interrupted by -O-
are, for example, methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl,
-CH20CH2CH20CH2CH2-, -CH2CH20CH2CH2-, -CH(CH3)CH20CH2CH(CH3)-,
-CH2cH2 tOCH2cH2~ where n = l to 5 (for Ml, M2, M3) or 1 to l l (for R20).
Examples of R20 as C2-C24alkylene interrupted by -S- or -N(R22)- are methylthiaethylene,
ethylthiapropylene, octylthiapropylene or -cH2cH2NHc4H8-~ -(CH2)3NHCsHI6-
~t CH2t~ N(cH3)cH2cH(c2Hs)c4H8-
R7, R7a~ Rl3, Rl3b and R22 as phenyl-CI-C4alkyl are, for example, benzyl, phenethyl,
3-phenylpropyl, a-methylbenzyl or a~a-dimethylbenzyl. Benzyl is preferred.
C2-C4Hydroxyalkyl as substituents R7, R7~, and Rl3 contains, for example, 1 to 4 OH
groups, for example 1-2, in particular 1 OH group. 2-Hydroxyethyl is preferred.
R22 as (Cl-C6alkyl)phenyl contains, for example, 1-3, especially 1 or 2, in particular 1
alkyl group (preferably having 1 to 4 C atoms, in particular methyl) on the phenyl radical.
Examples are tolyl, dimethylphenyl, trimethylphenyl, t-butylphenyl and di-t-butylphenyl.
-Ql-Ml-D-M2-Q2-
Examples of groups of the formula IM3 are the following:
Q3
I
N(CH2CH2-)3.CH3C(CH2-)3.CH3CH2C(CH20-)3,-OCH2CHCH20-,
o
I
-NHCH2CH2 I CH2CH2NH- .
R and Rl or Rg and Rlo are expediently hydrogen, hydroxyl, Cl-C4alkyl, chlorine,Cl-C4alkoxy, benzoyl, N(R7)(R7a) or -CO-A, where R7 and R7a are expediently hydrogen,
Cl-C6alkyl, benzyl, C2-C4hydroxyalkyl or, together with the N-atom ~o which they are
bonded, are piperidyl, morpholinyl, piperazinyl or 4-methylpiperazinyl. Advantageous
2~40~ 93
compounds containing the radical -CO-A as R or Rl are those in which A is hydroxyl,
Cl-Cl8alkoxy, Cs-C6cycloalkoxy, benzyloxy or benzyloxy substituted by Cl-C4alkyland/or chlorine or N(R7)(R7a). R2 and R3 or Rll and Rl2 are preferably hydrogen. At most
one of the radicals R, R" R2 and R3 or Rg, Rlo, Rll and R12 is particularly preferably
different from hydrogen and is then in particular hydroxyl, Cl-C4aLkyl, chlorine or
Cl-C4alkoxy.
Of particular interest are compositions according to the invention comprising compounds
of the forrnula I in which R is hydrogen, hydroxyl, Cl-C4alkyl, chlorine, nitro,Cl-C4alkoxy, benzoyl, -N(R7)(R7a) or -CO-A, Rl has the same possibilities of meaning as
R, R2 is hydrogen or Cl-C4alkyl and R3 is hydrogen or chlorine, A is hydroxyl,
Cl-Cl8alkoxy, C5-C6cycloalkoxy, benzyloxy or benzyloxy substituted by Cl-C4alkyland/or chlorine, -N(R7)(R7a) or -Gl-(G)n, n is a number from 1 to 3 and G is a radical of
the forrnula
R2 R3
Rl~ (II)
O
Gl in the case where n = 1 is -O-R20-O- or -NH-R21-NH-,
in the case where n = 2 is a group of the forrnula
-Q~-MI-I -M2-Q2-
M3
(III)
p
and in the case where n = 3 is (-OCH2)4C, where D is equal to N, CH or C(CI-C4alkyl),
Ql, Q2 and Q3 independently of one another are O or NH and Ml, M2 and M3
independently of one another are Cl-C6alkylene or C2-CI2alkylene interrupted by -O-,
or in ~he case where D = CH or C(CI-C4alkyl) -M3-Q3 is also -O- or in the case where
D = N -M3-Q3 is also a direct bond, R5 and R6 together forrn a group of the formula IV, V,
Vl or VII, R7 and R7a independently of one another are hydrogen, Cl-C6alkyl, benzyl,
C2-C4hydro~yalkyl or, together with the N atom to which they are bonded, are piperidyl,
~8~9~
morpholinyl, piperazinyl or 4-methylpiperazinyl, Rg, Rlo, Rll and Rl2 have the same
possibilities of meaning as R, Rl, R2 and R3 (in this sequence), where -CO-A is to be
replacecl by -CO-AI, Rl3 is hydrogen, Cl-CI8alkyl, C2-Cl8alkenyl, Cs-C6cycloalkyl,
phenyl-CI-C4alkyl, C2-CI8alkanoyl, C2-CI8alkenoyl, benzoyl, (Cl-C6alkyl)benzoyl,C2-Clgalkoxycarbonyl-cl-c4alkyl~ carboxy-CI-C4alkyl, cyano-CI-C4alkyl or
hydroxy-C2-C4alkyl, Rl4, Rls, R~6, Rl7, Rl8 and Rl9 independently of one another are
hydrogen, Cl-C4alkyl, chlorine, hydroxyl, Cl-C4alkoxy or -N(R7b)(R7C), in which R7b and
R7c independently of one another are hydrogen or Cl-C6alkyl, R20 is Cl-Cl2alkylene,
C2-C8alkenylene, C3-C6alkynylene or C2-C24alkylene interrupted by 0, S and/or -N(R22),
R21 is Cl-Cl2alkylene and R22 is hydrogen or Cl-C4alkyl, Al is hydroxyl, Cl-Cl8alkoxy,
C5-C6cycloalkoxy, benzyloxy or benzyloxy substituted by Cl-C4alkyl and/or halogen,
-N(R7)(R7a) or -Gl-(G2)n and A2 is hydroxyl, Cl-Cl8alkoxy, C5-C6cycloalkoxy, benzyloxy
or benzyloxy substituted by Cl-C4alkyl and/or halogen, -N(R7)(R7a) or -Gl-(G3)n, where
Gl and n are as defined above, G2 is a radical of the formula
I
R I ~=ROo and
o R12 Rll
G3 is a radical of the formula
R2 R3
Rl ~--~C--
R 1~
O O
Advantageous compositions contain compounds of the formula I in which R is hydrogen,
chlorine, hydroxyl or Cl-C4alkyl, Rl is hydrogen, chlorine, Cl-C4alkyl or hydroxyl,
R2 and R3 are hydrogen, R5 and R6 together form a group of the formula IV, V, VI or VII,
R9, Rlo. Rll and Rl2 have the same possibilities of meaning as R, Rl, R2 and R3 (in this
sequence), R13 is hydrogen, Cl-Cl8alkyl, C5-C6cycloalkyl, benzyl,
C2-CI9alkoxycarbonyl-Cl-C4alkyl, carboxy-CI-C4alkyl, C2-CI8alkanoyl or benzoyl,
Rl4, Rl5, Rl6, Rl7, R,8 and Rl9 are hydrogen and A2 is hydroxyl, Cl-CI8alkoxy,
C5-C6cycloalkoxy or benzyloxy.
2~40~9~
- 10 -
Compositions which contain compounds of the formula I are preferred in which R and Rg
independently of one another are hydrogen, Cl-C4alkyl or chlorine and R~, R2, R3, Rlo,
Rll, R~2, R14, Rls, R16, Rl7, R18 and Rl9 are hydrogen, and also those in which A, Al and
A2 are different from -GI-(G)n, -GI-(G2)n or -Gl-(G3)n
Particularly preferred compositions contain compounds of the formula I in which R is
hydrogen, methyl or chlorine, R~, R2 and R3 are hydrogen, and Rs and R6 together are a
group of the formula IV, V, VI or VII in which X is -S-, -S- or -S-, Xl is -S-, X2 is
O O
-CH2-, Rg is hydrogen, -CH3, Cl or -COO-(CI-C24alkyl), Rlo, R1l and Rl2 are hydrogen,
Rl3 is hydrogen, Cl-CI8alkyl, benzoyl, C2-CIgalkoxycarbonyl-methyl or C2-CI8aL~canoyl,
Rl4 to Rl9 are hydrogen and A2 is Cl-C24alkoxy.
In contrast to inorganic substances, which are usually stable up to high temperatures, the
special feature of organic substances is that they are easily decomposed under the
influence of heat, light or radiation, mechanical loading (in particular by shear forces) and
chemical reagents (particularly atmospheric oxygen).
The compounds of the formula I, which should expediently be present in the compositions
according to the invention to 0.01 to 10, for example to 0.05 to 5, preferably to 0.05 to 3,
but in particular to 0.1 to 2 % by weight in the organic materials, serve to protect from
such influences. One or more of these compounds can be present in the compositions, and
the percentage by weight data relate to the total amount of these compounds. The basis of
calculation is in this case the total weight of the organic material without the compounds
of the formula I.
The materials contained in the compositions according to the invention are those which
are sensitive to oxidative, thermal and/or actinic degradation. Living organisms are to be
understood as not coming under these organic materials.
The following preferably do not come under the definition "organic material": gelatin- and
silver halide-containing photographic emulsions.
9 ~
I I
E,Yamples of organic materials which may be mentioned which can be stabilised according
to the invention with the aid of the compounds of the formula I are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene,
polybut-1-ene, polymethylpent-1-ene, polyisoprene or polybutadiene, as well as polymers
of cycloolefins, for example of cyclopentene or norbornene; as well as polyethylene
(which additionally if desired can be crosslinked), for example high-density polyethylene
(HDPE), low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene
with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE,
PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl
monomers, such as, for example, ethylene/propylene copolymers, linear low-density
polyethylene (LLDPE) and its mixtures with low-density polyethylene (LDPE),
propylene/but- I -ene copolymers, propylene/isobutylene copolymers, ethylene/but- 1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers,
ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene
copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers,ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or
ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene
with propylene and a diene, such as hexadiene, dicyclopentadiene or
ethylidenenorbornene; as well as mixtures of such copolymers with each other and with
polymers mentioned in 1), for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinylacetate copolymers, LDPE/ethylene-acrylic acid copolymers,
LLDPE/ethylene-vinylacetate copolymers and LLDPE/ethylene acrylic acid copolymers.
3a. Hydrocarbon resins (for example Cs-C9) and hydrogenated modifications thereof (for
example tackifier resins).
4. Polystyrene, poly-(p-methylstyrene), poly-(-methylstyrene).
S. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for
example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacr;ylate,
styrene/bu~adiene/alkyl acrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl
204019~
acrylate; mixtures of high impact strength from copolymers of styrene and another
polymer, such as, for example, from a polyacrylate, a diene polymer or an
ethylene/propylene/diene terpolymer; and block copolymers of styrene, for example,
styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene-butylene/styrene or
styrene/ethylene-propylene/styrene.
6. Graft copolymers of styrene or ~-methylstyrene, for example styrene on polybutadiene;
styrene on copolymers of polybutadiene-styrene or polybutadiene-acrylonitrile; styrene
and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and
methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene;
styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and
maleimide on polybutadiene; styrene and alkyl acrylates or alkyl methacrylates on
polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene
and acrylonitrile on polyalkylacrylates or polyalkylmethacrylates; styrene and acrylonitrile
on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed
under 5), for example those known as so-called ABS, MBS, ASA and AES polymers.
7. Halogen-containing polymers, such as polychloroprene, chlorinated rubber, chlorinated
or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated e~hylene,
epichlorohydrin homo- and copolymers, in particular polymers from halogen-containing
vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride, polyvinylidene fluoride, as well as copolymers thereof, such as vinyl
cllloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl
acetate.
8. Polymers which are derived from ,~-unsaturated acids and derivatives thereof, such as
polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles.
9. Copolymers of Ihe monomers mentioned under 8) with each other or with other
unsaturated monomers, for example, acrylonitrile/butadiene copolymers,
acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers,
acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene
~erpolymers.
10. Polymers which are derived from unsaturated alcohols and amines, or acyl derivatives
thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate,
2 0 a~
polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate orpolyallylmelamine; as well as their copolymers with olefins mentioned in 1).
11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols,
polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.
12. Polyacetals, such as polyoxymethylene and polyoxymethylenes which contain
comonomers, ethylene oxide for example; polyacetals modified with thermoplastic
polyurethanes, acrylates or MBS.
13. Polyphenylene oxides and sulfides, and mixtures thereof with styrene polymers or
polyamides.
14. Polyurethanes which are derived from polyethers, polyesters and polybutadienes with
terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the
other hand, as well as precursors thereof.
15. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids
and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4,
polyamide 6, polyamide 6/6, polyamide 6/10, 6/9, 6/12 and 4/6i polyamide 11, polyamide
12, aromatic polyamides obtained starting from m-xylenediamine and adipic acid;
polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid
and if desired an elastomer as modifier, for example poly-2,4,4-trimethyl-hexamethylene
terephthalamide or poly-m-phenylene-isophthalamide. Block copolymers of the
aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically
bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol. In addition, polyamides or
copolyamides modified with EPDM or ABS; as well as polyamides condensed during
processing (RIM-polyamide systems).
16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
17. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from
hydroxy- carboxylic acids or the corresponding lactones, such as polyethylene
~erephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate,
polyhydroxybenzoate, as well as block polyether-esters derived from polyethers having
2~4~ 93
- 14-
hydroxyl end groups; in addition polyesters modi~led with polycarbonates or MBS.
18. Polycarbonates and polyester-carbonates.
19. Polysulfones, polyether-sulfones and polyether-ketones.
20. Crosslinked polymers which are derived from aldehydes on the one hand and phenols,
urea or melamine on the other hand, such as phenol/formaldehyde resins,
urea/formaldehyde resins and melamine/formaldehyde resins.
21. Drying and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from copolyesters of saturated and
unsaturated dicarboxylic acids with polyhydric alcohols ar~d vinyl compounds as
crosslinking agents, and also halogen-containing modi~lcations thereof of low
flammability.
23. Crosslinkable acrylic resins, derived from substituted acrylic esters, for example
epoxy-acrylates, urethane-acrylates or polyester-acrylates.
24. Alkyd resins, polyester resins or acrylate resins which are crosslinked with melamine
resins, urea resins, polyisocyanates or epoxy resins.
25. Crosslinked epoxy resins which are derived from polyepoxides, for example from
bis-glycidyl ethers or from cycloaliphatic diepoxides.
26. Natural polymers, such as cellulose, rubber, gelatin and derivatives thereof which are
chernically modi~led in a polymer-homologous rnanner, such as cellulose acetates,
cellulose propionates and cellulose butyrates, or cellulose ethers, such as methylcellulose;
and rosins and their derivatives.
~7. Mixtures (polyblends) of the polymers mentioned above, for example PP/EPDM,
polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTPIABS,
PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PU~, PC/thermoplastic
PUR, POM/acrylate, POM/MBS, PPO/HIPSj PPO/PA 6/6 and copolymers, PA/HDPE,
PA/PP, PA/PPO.
2 ~ ii 3
28. Na~urally occurring and synthetic organic materials which are pure monomericcompounds or mixtures of such compounds, for example mineral oils, animal and
vegetable fats, oil and waxes, or oils, waxes and fats based on synthetic esters (e.g.
phthalates, adipates, phosphates or tlimellitates~ and also mixtures of synthetic esters with
mineral oils in any weight ratio, which mixtures may be used as spinning preparations, as
well as aqueous emulsions thereof.
29. Aqueous emulsions of natural or synthetic rubbers, for example natural latex or
latices of carboxylated styrene/butadiene copolymers.
As organic material, the compositions according to the invention preferably contain
natural, semisynthetic or synthetic polymers, a lubricant, a metal processing fluid or a
hydraulic fluid. Compositions are particularly preferred which contain a synthetic
polymer, in particular a thermoplastic or an elastomer. Compositions are to be emphasised
in particular which~ as an organic material, comprise a polyolefin. Examples of such
polymers are to be taken from the above enumeration of suitable materials.
Compositions are also preferred which contain a lubricant, a metal processing fluid or a
hydraulic ~luid, in particular a lubricant.
Suitable lubricants are based, for example, on mineral or synthetic oils or mixtures
thereof. The lubricants are familiar to the person skilled in the art and are described in the
relevant specialist literature, for example in Dieter Klamann, "Schmierstoffe und
verwandte Produkte" [Lubricants and Related Products] (Verlag Chemie, Weinheim,
1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch" [The Lubricant ~Iandbook]
(Dr. Alfred HUthig-Verlag, Heidelberg, 1974) and in "Ullmanns Enzyklopadie der
technischen Chemie" [Ullmann's Encyclopaedia of Industrial Chemistry], vol~ 13, pages
~5-94 (Verlag Chemie, Weinheim, 1977)~
The lubricants are in particular oils and fats, for example based on a mineral oik Oils are
preferred.
A further group of lubricants which can be used are vegetable or animal oils, fats, tallows
and waxes or mixtures thereof with each other or mixtures with the mineral or synthetic
oils mentioned. Vegetable and animal oils, fats, tallows and waxes are, for example, palm
2~0~9~
- 16-
kernel oil, palm oil, olive oil, rapeseed oil or rape oil, linseed oil, groundnut oil, soya bean
oil, cotton oil, sunflower oil, pumpkin seed oil, coconut oil, maize oil, castor oil, walr.ut
oil and mixtures thereof, fish oils, tallow from slaughtered animals such as bovine tallow,
neatsfoot oil and bone oil and their modified, epoxidised and sulfoxidised forrns, for
example epoxidised soya bean oil.
The mineral oils are based in particular on hydrocarbon compounds.
Examples of synthetic lubricants include lubricants based on aliphatic or aromatic
carboxylic esters, Ihe polymeric esters, the polyalkylene oxides, the phosphoric acid
esters, the poly-~-olefins or the silicones, on a diester of a dibasic acid with a monohydric
alcohol, for example dioctyl sebacate or dinonyl adipate, on a triester of
trimethylolpropane with a monobasic acid or with a mixture of such acids, for example
trimethylolpropane tripelargonate, tTimethylolpropane tricaprylate or mixtures thereof, on
a tetraester of pentaerythritol with a monobasic acid or with a mixture of such as acids,
such as, for example, pentaerythritol tetracaprylate, or on a complex ester of monobasic
and dibasic acids with polyhydric alcohols, for example a complex ester of
trimethylolpropane with caprylic and sebacic acid or on a mixture thereof. Particularly
suitable in addition to mineral oils are, for example, poly-c-olefins, lubricants based on
esters, phosphates, glycols, polyglycols and polyalkylene glycols, and mixtures thereof
with water.
Metal processing fluids and hydraulic fluids can be prepared based on the same substances
as described above for the lubricants. Frequently, these are also emulsions of such
substances in water or other fluids.
Incorporation into the organic materials can be carried out, for example, by mixing in the
compounds of the formula I and, if desired, other additives by the methods customary in
industry. If they are polymers, in particular synthetic polymers, incorporation can be
carried out before or during moulding, or by applying the dissolved or dispersedcompounds to the polymers, if appropriate with subsequent evaporation of the solvent. In
the case of elastomers, these can also be stabilised as latices. A further possibility for
incorporation of the compounds of the formula I in polymers comprises their addition
before or during polymerisation of the corresponding monomers or before crosslinking. In
the case of addition before or during polymerisation, the compounds of the formula I can
also act as regulators for the chain length of the polymers (chain terminators).
2~
- 17-
The compounds of the formula I or mixtures thereof can also be added to the plastics to be
stabilised in the form of a masterbatch which contains these compounds, for example, in a
concentration of 2.5 to 25 % by weight.
The incorporation of the compounds of the formula I can expediently be carried out by the
following methods:
- as an emulsion or dispersion (for example to give latices or emulsion polymers)
- as a dry mixture during mixing of additive components or polymer mixtures
- by direct addition to the processing apparatus (for example extruders, internal mixers
etc.)
- as a solution or melt.
Polymer compositions according to the invention can be used in various forms or
processed to give various products, for example as (to give) foils, fibres, tapes, moulded
materials, profiles or as binders for paints, adhesives or cement.
Lubricant compositions according to the invention are used, for example, in internal
combustion motors, for example in motor vehicles.
In addition to the compounds or mixtures according to the invention, the compositions
according to the invention can contain still other customary additives, in particular if they
contain organic, preferably synthetic polymers. Examples of such additives are:
1. Antioxidants
I I A~m~, for example 2,6-di-tert-butyl-4-methylphenol,
2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol.
1.2. AlkYlated hvdroquinones, for example 2j6-di-tert-butyl-4-methoxyphenol,
2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,
2 ~
- 18 -
2,6-diphenyl-4-octadecyloxyphenol.
1.3. HvdroxYlated thiodiphenvl ethers, for example 2,2'-thiobis(6-tert-bulyl-
4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-lhiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol).
1.4. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2~2~-methylenebis[4-methyl-6-(a-methylcyclohexy})phenol]~
2,2 '-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-i-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2 '-ethylidenebis(4,6-di-tert-butylphenol),
2,2 '-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(a-methylbenzyl)-4-nonylphenol~,
2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
I ,1 -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-S-methyl-2-hydroxybenzyl)-4-methylphenol,
I, I ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
I, I -bis(S-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,
ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-ten-butyl-4-hydroxy-S-methylphenyl)-dicyclopentadiene,
bis[2-~3 '-tert-butyl-2'-hydroxy-S '-methylbenzyl)-6-tert-butyl-4-methylphenyl]
terephthalate.
I .:~. BenzYI comPounds, for example
1 ,3 ,S - tri s(3 ,S-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
bis(3,~-di tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-
4-hydroxybenzylmercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)
dithiolterephthalate, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2.6-dimethylbenzyl) isocyanurate,
dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium salt of monoethyl
3,j-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-dicyclohexyl-
4-hydroxybenzyl) isocyanurale.
2~40195
- 19-
1.6. Acvlaminophenols, for example lauric acid 4-hydroxyanilide, stearic acid
4-hydroxyanilide, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine,
octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
1.7. Este s of ,s-(3,5-di-tert-butyl-4-hvdroxYphenYl)propionic acid with mono- or
polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl~ isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.8. Esters of ~-(S-tert-butvl-4-hvdroxv-3-methvlphenvl)propionic acid with mono- or
polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
thiodiethylene glycol, diethylene ~Iycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'bis(hydroxyethyl)oxalic acid diamide.
1.9. Esters of ~-(3~5-dicvclohexvl-4-hvdroxvphenvl)propionic acid with mono- or
polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid diamide.
I .1(). Amides of s-(3.5-di-tert-butvl-4-hvdroxvphenvl)propionic acid for example
N .N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,
N,N ' -bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,
N,N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
2. UV absorbers and li~ht stabilisers
2.1. 2-(2'-Hvdroxvphenvl~benzotriazoles, for example the S'-methyl, 3',5'-di-tert-butyl,
S'-lert-butyl, 5'-(1,1,3,3-tetramethylbutyl), S-chloro-3',5'-di-tert-butyl,
5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert butyl, 4'-octoxy, 3',5'-di tert amyl
and 3',5'-bis(a,a-dimethylbenzyl) derivative.
2.2. 2-Hvdroxvbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy,
4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and
2'-hydroxy-4,4'-dimethoxy derivative.
_.3. Esters of variouslv substituted benzoic acids, for example 4-tert-butylphenyl
- 2~a~9~
- 20 -
salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrvlates, for example ethyl ~-cyano-~,~-diphenylacrylate, isooctyl
~-cyano-~,~-diphenylacrylate, methyl -carbomethoxycinnamate, methyl
c~-cyano-~-methyl-p-methoxycinnamate, butyl a-cyano-~-methyl-p-methoxycinnamate,methyl a-carbomethoxy-p-methoxycinnamate and
N-(~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of
2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or
without additional ligands such as n-butylamine, triethanolamine or
N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl
or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl
undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands.
2.6. Stericallv hindered amines, for example bis(2,2,6,6-tetramethylpiperidyl) sebacate,
bis(l,2,2,6,6-pentamethylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethylpiperidyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of
l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the
condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine
nnd 4-tert-octylamino-2,~dichlor~1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)
ni~rilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,
I, I '-(1 ,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone).
_.7. Oxalic acid diamides, for example, 4,4'-dioctyloxyoxanilide,
2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide,
2-ethoxy-2'-elhyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with
2-e~hoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of o- and p-methoxy-
disubstituted oxanilides, and o- and p-ethoxy-disubstituted oxanilides.
_.~. 2-(2-Hvdroxv~henvl)-1~3.5-triazines, for example
2~4~19a
- 21 -
,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine,
~-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)- 1 ,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide
N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine,
N,N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalicdihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl
phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,
trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)
phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)
pentaerythritol diphosphite, tristearyl sorbitol triphosphite,
tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite,
3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.
5. Compounds which destrov Peroxides, for example esters of ,s-thiodipropionic acid, for
example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc
salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide,
pentaerythritol tetrakis(~-dodecylmercapto)propionate.
6. Polvamide stabilisers, for example copper salts in combination with iodides and/or
phosphorus compounds and salts of divalent manganese.
7. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide,
triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides,polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for
example calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate and
potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
~. Nucleatin~ a~ents, for example 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic
acid
t 9~
- 2~ -
9. Fillers and reinforcin a~.en~s, for example calcium carbonate, silicares, glass fibres,
asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black,
graphite.
10. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, fluorescent
whitening agents, flameproofing agents, antistatic agents and blowing agents.
If the compositions according to the invention are those based on lubricants and hydraulic
fluids or metal processing fluids. they can also contain other additives which are added to
improve certain use properties, for example other antioxidants, metal deactivators, rust
inhibitors, viscosity index improvers, pour point reducers, dispersants/surfactants and
abrasion resistance additives.
Examples of antioxidants are to be taken from the listing reproduced further above under
the title "1. Antioxidants", in particular items 1.1 to 1.10. Examples of other additional
additives are the following:
Examples of amine antioxidants-
~I,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine,
N ,N ' -bis( I ,4-dimethyl-pentyl)-p-phenylenediamine,
N,N '-bis( I -ethyl-3-methyl-pentyl)-p-phenylenediamine,
N,N'-bis(l-methyl-heptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine, N,N'-di-(naphthyl-2)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-( I ,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-( I -melhyl-heptyl)-N '-phenyl-p-phenylenediamine,
N-cyclohe1~yl-N'-phenyl-p-phenylenediamine, 4-(p-toluene-sulfonamido)-diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, such as
p,p'-di-lert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylamino-phenol,
4-nonanoylamino-phenol, 4-dodecanoylamino-phenol, 4-octadecanoylamino-phenol,
di-( l-methoxyphenyl)-amine, 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol,
?,~'-diamino-diphenylmethane, 4,4'-diamino-diphenylmethane,
N ,N ,N ' ,N '-tetramethyl-4,4'-diamino-diphenylmethane,
2~ 9~
.
- 23 -
1,2-di-[(2-methyl-phenyl)-amino]-ethane, 1,2-di-(phenylamino)-propane,
(o-tolyl)-biguanide, di-[4-(1',3'-dimethyl-bu~yl)-phenyl]amine, tert-octylated
N-phenyl- 1-naphthylamine, mixture of mono- and dialkylated
tert-butyUtert-octyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H- 1 ,4-benzothiazine,
phenothiazine, N-allylphenothiazine.
Examples of other antioxidants: aliphatic or aromatic phosphites, esters of thiodipropionic
acid or thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid.
Examples of metal deactivators. for example for copper, are: triazoles, benzotriazoles and
derivatives thereof, tolutriazoles and derivatives thereof, 2-mercaptobenzothiazole,
2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 2,5-dimercaptobenzothiadiazole,
5,5'-methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole,
salicylidenepropylenediamine, salicylaminoguanidine and salts thereof.
Examples of rust inhibitors are:
a) Organic acids, their esters, metal salts and anhydrides, for example: N-oleoylsarcosine,
sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydride, for example
dodecylsuccinic anhydride, alkenylsuccinic acid partial esters and partial amines,
4-nonylphenoxyacetic acid.
b) Nitrogen-containing compounds, for example:
i. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of
organic and inorganic acids, for examples oil-soluble alkylammonium carboxylates.
ii. I~eterocyclic compounds, for example: substituted imidazolines and oxazolines.
c) Phosphorus-containing compounds, for example: amine salts of phosphoric acid partial
esters or phosphonic acid partial esters, zinc dialkyldilhiophosphates.
d) Sulfur-containing compounds, for example: barium dinonylnaphthalenesulfonates,
calcium petroleumsulfonates.
Examples of viscositv index improvers are: polyacrylates, polymethacrylates,
vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones, polybutenes, ole~m
copolymers, styrene/acrylate copolymers, polyethers.
Examples of pour point reducers are: polymethacrylate, alkylated naphthalene derivatives.
- 2040~9~
- 24 -
Examples of dispersants/surfactants are: polybutenylsuccinamides or -imides,
polybutenylphosphoric acid derivatives, basic magnesium, calcium, and barium sulfonates
and phenolates.
Examples of abrasion resistance additives are: sulfur- andlor phosphorus- andlorhalogen-containing compounds, such as sulfurised vegetable oils, zinc
dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl di- and
tri-sulfides, triphenyl phosphorothionates, diethanolaminomethyltolyltriazole,
di(2-ethylhexyl)aminomethyltolyltriazole.
It is particularly advantageous to employ the compounds of the formula I in combination
with organic phosphites or phosphonites, in particular for the stabilisation of ~hermoplastic
polymers. The invention therefore also relates to compositions which contain at least one
compound of the formula I and at least one organic phosphite and/or phosphonite.Examples of such phosph(on)ites are those of ~he formulae
RxO\ Rx 1 ORy
P--ORz Rx--p--Ro--P--RyO
RyO
(A) (B)
R~O--P X P--RyO
O O
(C)
in which Rx, Ry and Rz independently of one another are C6-C20alkyl, Cs-C8cycloalkyl,
phenyl or phenyl substituted by one to three Cl-Cl2alkyl and Ro is phenylene, naphthylene
or diphenylene which is unsubstituted or substituted by C1-C~2alkyl or is a radical
-O-Rv-O-, in which Rv is phenylene, naphthylene or diphenylene which is unsubstituted or
substituted by Cl-Cl2alkyl or Ro is a radical -phen-Rw-phen- in which phen is phenylene
and Rw is -O-, -S-, -S02-, -CH2- or -C(CH3)2-.
2~4~ 9~ `
- 25 -
Among the compounds of the formula A, those are preferred in which Rx, Ry and Rz are
C6-C20alkyl, phenyl or phenyl substituted by one to three, in particular one to two,
Cl-Cl2alkyl groups.
Among the compounds of the formula B, those are preferred in which R" and Ry arephenyl or phenyl substituted by one to two Cl-Cl2alkyl groups and Ro is a diphenylene
radical.
Among the compounds of the formula C, those are preferred in which Rx and Ry arephenyl or phenyl which is substituted by one to three Cl-CI2alkyl groups.
Phosphites and phosphonites which contain at least one P-O-Ar gtoup are preferably used,
Ar being a mono- or dialkylphenyl radical. Examples of these are:
triphenyl phosphite, decyl diphenyl phosphite, phenyl didecyl phosphite, tris(nonylphenyl)
phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite,
bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite,
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphospllite.
The amount of phosph(on)ite added depends on the amount of compound of the formula I
added. In general, 0.01 to 1 % by weight, in particular 0.05 to 0.5 % by weight, is used,
relative to the polymer.
The invention further relates to novel isoindolinone compounds which have the formula X
R~ (X)
in which R is hydrogen, Cl-CI8alkyl, Cl-Cl8alkoxy, halogen, nitto, phenyl-CI-C4alkoxy,
C2-CI8alkanoyl, benzoyl, (Cl-C6alkyl)benzoyl, C2-C18alkenoyl, -N(R7)(R7a), -OH or
-CO-A, Rl has the same possibilities of meaning as R, R2 is hydrogen or Cl-C4alkyl and
2~)'1019~
- 26 -
R3 is hydrogen or halogen, A is hydroxyl, Cl-Cl8alkoxy, Cs-C12cycloalkoxy, benzyloxy or
benzyloxy substituted by Cl-C4alkyl and/or halogen, -N(R7)(R7a), -NH-NH-R8 or
-Gl-(G)n, n is a number from 1 to 3 and G is a radical of the forrnula
R2 R3
R
C=O
O
Gl in the case where n = 1 is -O-R20-O-, -NH-R21-NH- or-NH-NH-,
in the case where n = 2 is a group of the forrnula
-Ql-Ml-l -M2-Q2-
M3
(III)
l3
and in the case where n = 3 is (-O-CH2)4C or
-OCH2f H-CH2-0-CH2Cl H-CH2--
o
where D is N, CH or CtCI-C4alkyl), Ql. Q2 and Q3 independently of one another are O or
NH and Ml, M2 and M3 independently of one another are Cl-C6alkylene or
C2-CI2alkylene which is interrupted by -O-, or in the case where D = CH or C(CI-C4alkyl)
-M3-Q3 is also -O- or in the case where D = N -M3-Q3 is also a direct bond, Rs and R6
together forrn a group of the formula IV, V or VII
X ~RIoR ~XI
(IV? ~1~ 1CO_A2
R13 R14
~N ~
~--R15
R19~; 16 (VII)
Rl8 R17
2~19~
- 27 -
O O
Il 11
X is -S-, -S- or -S-
o
O O
Il 11
Xl is -S-, -S- or -S-
where if X is S or S=0 and one of the substituents R9-R12 is H, alkoxy or halogen, the
remaining 3 of these substituents cannot simultaneously be H,
R7 and R7a independently of one another are hydrogen, Cl-C18alkyl, phenyl-CI-C4alkyl,
C2-CI8alkanoyl, C2-Cl8alkenoyl, C2-C4hydroxyalkyl, benzoyl or (Cl-C6alkyl)benzoyl or,
together with the N atom to which they are bonded, are piperidyl, morpholinyl, piperazinyl-
or 4-methylpiperazinyl, R8 is hydrogen, CrCI8alkanoyl, benzoyl or (Cl-C6alkyl)benzoyl,
R9, Rlo, Rll and Rl2 have the same possibilities of meaning as R, Rl, R2 and R3 (in this
sequence), where -C0-A is to be replaced by -C0-AI, R13 is hydrogen, Cl-Cl8alkyl,
C2-CI8alkenyl, C5-CI2cycloalkyl, phenyl-CI-C4alkyl, C2-CI8alkanoyl, C2-CI8alkenoyl,
benzoyl, (Cl-C6alkyl)benzoyl, benzyl, C2-CIgalkoxycarbonyl-Cl-C4alkyl,
carboxy-CI-C4alkyl, cyano-CI-C4alkyl, hydroxy-C2-C4alkyl or
tCH2CI H20~CH2 ICH--O--Rl3
Rl3a Rl3a
Rl3a is hydrogen or methyl and Rl3b is hydrogen, Cl-Cl8alkyl, phenyl-CI-C4alkyl,C2-CI8alkanoyl, benzoyl, C2-CI8alkenoyl or (Cl-C6alkyl)benzoyl and a is a number from
0 to 6, Rl4, Rls, Rl6, Rl7, Rl8 and Rl9 independently of one another are hydrogen,
Cl-C4alkyl, halogen, hydroxyl, Cl-C18alkoxy or -N(R7b)(R7C), in which R7b and R70
independently of one another are hydrogen or Cl-CI8alkyl, R20 is Cl-CI2alkylene,C2-C8alkenylene, C3-C6alkynylene or C2-C24alkylene interrupted by 0, S and/or -N~R22)-,
R2l is Cl-CI2alkylene and R22 is hydrogen, Cl-CI8alkyl, phenyl, (Cl-C6-alkyl)phenyl or
phenyl-CI-C4aLkyl, Al is hydroxyl, Cl-C24alkoxy, Cs-CI2cycloalkoxy, benzyloxy orbenzyloxy substituted by Cl-C4alkyl and~or halogen, -N(R7)(R7a), -NH-NH-R8 or
-G,-(G2)n, and A2 is hydroxyl, Cl-C24alkoxy, C5-CI2cycloalkoxy, benzyloxy or
benzyloxy substituted by Cl-C4alkyl and/or halogen, -N(R7)(R7a), -NH-NH-R8 or
-Gl-(G3)n, where Gl and n are as defined above, G2 is a radical of the formula
2~0~
~o 1~ R~ ld
G3 is a radical of the formula
(IX) ~
o o
with the provisos, (1) that only one substituent -CO-A, CO-AI or -CO-A2 is present in the
molecule, in which A, Al or A2 is a radical -Gl-(G)n, -G,-(G2)n or -Gl-(G3)n and (2) that
in the case where X = S a maximum of one of these substituents R and Rl is
Cl-CI8alkoxy.
Advantageous compounds of the formula X are those in which R is hydrogen, hydroxyl,
Cl-C4alkyl, chlorine, nitro, Cl-C4alkoxy, benzoyl, -N(R7)(R7a) or-CO-A, Rl has the same
possibilities of meaning as R, R2 is hydrogen, chlorine or Cl-C4alkyl and R3 is hydrogen
or chlorine, A is hydroxyl, Cl-Cl8alkoxy, Cs-C6cycloalkoxy, benzyloxy or benzyloxy
substituted by Cl-C4alkyl and/or chlorine, -N(R7)(R7a) or -GI-(G)n, n is a number from 1
to 3 and G is a radical of the formula
R2 R3
Rl~ (lI)
O
Gl in the case where n = 1 is -O-R20-0- or -NH-R2l-NH-,
in the case where n = 2 is a group of the formula
-Ql-Ml-l -M2--2-
(III)
2 ~
- 29 -
and in the case where n = 3 is (-OCH2)4C, where D is equal to N, CH or C(CI-C4alkyl),
Ql, Q2 and 03 independently of one another are O or NH and Ml, M2 and M3
independently of one another are Cl-C6alkylene or C2-CI2alkylene interrupted by -O-,
or in the case where D = CH or C(CI-C4alkyl) -M3-Q3 is also -O- or in the case where
D = N -M3-Q3 is also a direct bond, Rs and R6 together forrn a group of the forrnula IV, V
or Vll, R7 and R7a independently of one another are hydrogen, Cl-C6alkyl, benzyl,
C2-C4hydroxyalkyl or, together with the N atom to which they are bonded, are piperidyl,
morpholinyl, piperazinyl or 4-methylpiperazinyl, Rg, Rlo, Rl I and Rl2 have the same
possibilities of meaning as R, Rl, R2 and R3 (in this sequence), where -CO-A is to be
replaced by -CO-AI, Rl3 is hydrogen, Cl-CI8alkyl, C2-CI8alkenyl, Cs-C6cycloalkyl,
phenyl-CI-C4alkyl, C2-CI8alkanoyl, C2-CI8alkenoyl, benzoyl, (C~-C6alkyl)benzoyl,cyano-CI-C4alkyl, C2-CIgaikoxycarbonyl-Cl-C4alkyl, carboxy-CI-C4alkyl or
hydroxy-C2-C4alkyl, Rl4, Rl5, Rl6, Rl7, Rl8 and Rlg independently of one another are
hydrogen, Cl-C4alkyl, chlorine, hydroxyl, Cl-C4alkoxy or -N(R7b)(R7C), in which R7b and
R7c independently of one another are hydrogen or Cl-C6alkyl, R20 is C~-CI2alkylene,
C2-C8alkenylene, C3-C6alkynylene or C2-C24alkylene interrupted by 0, S and/or -N(R22),
R2l is Cl-Cl2alkylene and R22 is hydrogen or Cl-C4alkyl, Al is hydroxyl, Cl-Cl8alkoxy,
Cs-C6cycloalkoxy, benzyloxy or benzyloxy substituted by Cl-C4alkyl and/or halogen,
-N(R7)(R7a) or ~GI-(G2)n and A2 is hydroxyl, Cl-CI8alkoxy, C5-C6cycloalkoxy, benzyloxy
or benzyloxy substituted by Cl-C4alkyl and/or halogen, -N(R7)(R7a) or -Gl-(G3)n, where
Gl and n are as defined above, G2 is a radical of the forrnula
o
Rl~--A and
G3 is a radical of the forrnula
RI~N--
R 11
O O
- 204als~
- 30-
Preferred compounds of the formula X are those in which R is hydrogen, chlorine,hydroxyl or Cl-C4alkyl, Rl is hydrogen, chlorine, Cl-C4alkyl or hydroxyl, R2 and R3 are
hydrogen, R5 and R6 together form a group of the formula IV, V or VII,R9, Rlo, Rll and
R~2 have the same possibilities of meaning as R,RI, R2 and R3 (in this sequence), Rl3 is
hydrogen, Cl-CIgalkyl, Cs-C6cycloalkyl, benzyl, C2-Cl8alkanoyl or benzoyl, Rl4, Rl5,
Rl6, Rl7, R18 and Rlg are hydrogen, and A2 is hydroxyl, Cl-CI8alkoxy, Cs-C6cycloalkoxy
or benzyloxy, in particular those in which Ris hydrogen, methyl or chlorine, Rl, R2 and
R3 are hydrogen, and Rs and R6 together are a group of the formula IV, V or VII, in which
O
X is -S-, -S- or -S-, Xl is -S-, R9is hydrogen, -cH3~clor-coo-(cl-c24alkyl)~
O O
Rlo, Rll and Rlz are hydrogen, Rl3 is hydrogen, Cl-CI8alkyl, benzoyl,
C2-Clgalkoxycarbonylmethyl or C2-CI8alkanoyl, Rl4to R~g are hydrogen and A2 is
C~-C2,,alkoxy.
Particularly preferred compounds of the formula X are those in which R and Rg
independently of one another are hydrogen, Cl-C4alkyl or chlorine and R,,R2,R3,R4,
RIo~Rll~Rl2~Rl4~Rls~ Rl6, Rl7, Rl8 and Rlg are hydrogen.
.
The invention further relates to the use of compounds according to the formulae I and X
for stabilising organic material against oxidative, thermal and/or actinic degradation.
The use of compounds according to the formulae I and X as stabilisers in lubricants, metal
processing fluids and hydraulic fluids and in synthetic, natural or semisynthetic polymers
is preferred.
The invention accordingly also comprises a process for stabilising organic ma~erial, in
particular lubricants, metal processing fluids and hydraulic tluids and natural, synthetic or
semisynthetic polymers, which comprises adding compounds of the formula I or X to this
matenal as stabilisers or applying them to this.
The compounds according to the invention and the isoindolinone compounds employed in
the compounds according to the invention are prepared, for example, by the processes
described in C.H. Gaozza et al., J. Heterocycl. Chem. 2, 883 (1972) and US-A 3 591 599
and can be summarised by the following reaction scheme:
R1 ~C02H H N~
(XI) R12
R1 ~ R11
~COA2 ~ 5
o COA2
(Xl) +H2N~cH2t~NH2 ~ R~
1 R13Br
2~19~
NH2 NH2 R~3~ R,6
R18--~ R~4 -- R~,~ R17
1 R13Br
Rl3
R~ ~ ~16
The reactions are expediently carried out with the addition of customary solvents which
are inert under the reaction conditions, preferably ethanol. The sulfur-containing products
can be oxidised to the corresponding sulfoxide and sulfone compounds using oxidising
agents. m-Chloroperbenzoic acid, for example, is preferred as an oxidising agent.
Of course, after ring construc~ion has taken place, possible substituents can be converted
into one another or introduced by customary processes known in organic chemistry.
To prepare compounds of the formula I in which A, Al or A2 are -Gl-(G)n, -GI-(G2)n or
-Gl-(G3)n in the radicals -COA, -COAI or -COA2, the corresponding acids (A, Al,
A2 = OH), for example, are used as starting materials and the re~ction (oligomerisation) is
carried out from the esters or amides formed therefrom.
If oligomerisation takes place via esters, this is carried out, for example, by conversion of
the free acid (A, Al, A2 = OH) into the corresponding acid chloride tfor example with
PCI5, SOCI2) and reaction with the di-, tri- or tetrahydric alcohol corresponding to the
radical Gl, preferably with base catalysis. The acid can also be reacted with the
corresponding higher valency alcohol directly in the presence of heat, or else gently by
treatment with dicyclohexylcarbodiimide (DCC) in the presence of the higher valency
alcohol (Tetrahedron Letters 1978, 4475-8), or by further gentle processes described, for
20~19~
- 33 -
example, in Tetrahedron 36, 2409 (1980). A further possibility to obtain the compounds
oligomerised via ester groups comprises esterification with a diol, triol or tetraol starting
from the lower monoesters. Catalysts suitable for this are, for example, strong acids such
as H2SO4, HCI, p-toluenesulfonic acid, methanesulfonic acid, acid ion exchangers or
alternatively bases, for example LiNH2, CH3ONa or else dialkyltin oxides or titanium
tetraalkoxylates. The lower alcohol is removed from the reaction mixture by distillation in
this case. The amount of catalyst is as a rule 0.1-5 mol %, relative to the monoester.
If oligomerisation takes place via amides, the acid chlorides are formed as described
above and are then reacted with the di- or triamine corresponding to a radical Gl. ~n the
case of sensitive compounds, for example, the method using DCC is also suitable in
addition to the other processes described in Tetrahedron 36, 2409 (1980). In addition,
lower esters (A, Al, A2 = methyl, ethyl, isopropyl, propyl etc.) can be reacted directly with
the amines mentioned to give the corresponding amines in the presence of heat.
The reactions can be carried out with or without addition of customary inert solvents.
Some of the preparation processes described are illustrated in detail in the following
examples.
The starting compounds required for the preparation processes described above are known
or can be prepared by customary methods in a manner known per se.
The following examples illustrate the invention further. If not stated otherwise, paTts and
percentage data therein and in the remaining description are parts by weight andpercentages by weight.
Example 1: (compound 1, Table 1)
12.5 g of 2-aminothiophenyl and 15.0 g of phthalaldehydic acid are boiled under nitrogen
for 12 hours in 100 ml of ethanol. The reaction mixture is then cooled, and the precipitated
solid is filtered off with suction and recrystallised from ethanol/methylene chloride (1:1).
1~.2 g of colourless crystals of melting range 173-174C are thus obtained, which
correspond to the structure of compound 1.
Example 2: (compound 2, Table 1)
6.2~ g of 3-amino-4-mercaptobenzoic acid and 5.54 g of phthalaldehydic acid are boiled
under nitrogen for 17 hours in 40 ml of ethanol and 10 ml of water. The reaction mixture
2 ~ 1 9 5
- 34 -
is then cooled and the precipitated solid is filtered off with suction and dried. 6.9 g of
while crystals of melting point 256-260C are thus obtained. 4.8 g of this compound are
stirred at room temperature for 20 hours in 50 ml of methylene chloride with 4.58 g of
stearyl alcohol, 3.5 g of dicyclohexylcarbodiimide and 0.1 g of 4-dimethylaminopyridine.
The reaction mixture is then filtered, the filtrate is evaporated on a rotary evaporator and
the residue is recrystallised from acetonitrile. 6.7 g of colourless crystals of melting range
93-95C are thus obtained, which correspond to the structure of compound 2.
Example 3: (compound 3, Table 1)
1.86 g of L-cysteine ethyl ester hydrochloride and 1.50 g of phthalaldehydic acid are
boiled under nitrogen for 4 hours in 20 ml of ethanol. The reaction mixture is then
evaporated on a rotary evaporator, the residue is ~reated with 2.70 g of stearyl alcohol and
0.05 g of p-toluenesulfonic acid and the mixture is then stirred at 200C for 90 min in a
weak vacuum (20 kPa). After cooling, column chromatography on silica gel (methylene
chloride/hexane = 19: 1) and recrystallization from acetonitrile, 3 g of the compound 3 are
obtained having a melting point of S1-3C.
Example 4: (compound 4, Table 1)
12.0 g of the compound 1 in 120 ml of methylene chloride are cooled to -30C and treated
at this temperature with 10.2 g of m-chloroperbenzoic acid (85 %). The temperature of the
reaction mixture is then increased to +20C in the course of 3 hours. The mixture is then
washed with lN KOH and then with water and evaporated on a rotary evaporator. 8.35 g
of the compound 4 having a melting point range of 178-82C are obtained from theresidue by chromatography on silica gel (methylene chloride/ethyl acetate = 19:1).
ExamPle 5: (compound 5, Table 1)
9.59 g of the compound 1 are oxidised at 20C for 20 hours using 24.0 g of
m-chloroperbenzoic acid (85 %) as described in Example 4. 9.4 g of the compound 5,
which melts between 214 and 216C, are obtained by crystallisation from toluene.
Example 6: (compound 6, Table 1)
7.41 g of diaminopropane and 15.01 g of phthalaldehydic acid are dissolved in 100 ml of
ethanol and the mixture is boiled under nitrogen for 3 hours. The solvent is then removed
by distillation and the residue is recrystallised from toluene/hexane (1:1). 16.41 g of the
compound 6, which melts between 128 and 130C, are thus obtained.
2~4019~
- 35 -
E~aml)le 7: (compound 7, Table 1)
9.4 g of the compound 6, 15.56 g of cetyl bromide and 0~ 1 g of potassium iodide are boiled
under nitrogen for 15 hours in 50 ml of dimethylformamide. The reaction mixture is then
cooled, diluted with 50 ml of methylene chloride and washed 3~c with 500 ml of water.
5.7 g of the compound 7 of melting range 50-51C are obtained from the residue, after
evaporating off the methylene chloride, by chromatography on silica gel (methylene
chloride/ethyl acetate 1: l) and subsequent crystallisation from hexane.
Example 8: (compound 8, Table 1)
6.63 g of the compound 6 are dissolved in 20 ml of pyridine and the solution is treated
with 4.92 g of benzoyl chloride and 0.5 g of 4-dimethylaminopyridine. The reaction
mixture is stirred at room temperature for 3 hours, then it is diluted with 100 ml of
methylene chloride, and washed with water, dilute hydrochloric acid and again with water.
The residue is crystallised from methanol after evaporating off the solvent.7.4 g of the
compound 8 of melting point 143-5C are thus obtained.
Examples 9 and 10: (compounds 9 and 10, Table 1)
15.82 g of 1,8-diaminonaphthalene and 15.02 g of phthalaldehydic acid are dissolved in
150 ml of ethanol and the solution is boiled under nitrogen for 1 hour. The reaction
mixture is then cooled and the precipitated solid is filtered off with suction, washed with
ethanol and dried. 24.7 g of the intermediate of melting range 230-240C are thus obtained
(compound 9).
10.0 g of the above interrnediate are dissolved in 30 ml of dimethylformamide and the
solution is then treated with 12.33 g of cetyl bromide and 1.0 g of potassium iodide and
the mixture is boiled under nitrogen for 24 hours. The reaction mixture is then diluted with
100 ml of methylene chloride and washed with water, 12~8 g of the compound 10, which
melts between 54 and 56C, are obtained from the residue, after evaporatin~ the solvent,
by chromatography on silica gel (methylene chloride) and crystallisation from ethanol.
Example 11: (compound 11,Table 1)
28.2 g of the compound 6, 45 ml of methyl bromoacetate, 1 g of sodium iodide and 20.8 g
of potassium carbonate are slowly heated to reflux and boiled for 15 min. The reaction
mixture is diluted with 100 ml of toluene and filtered. After evaporing the filtrate in vacuo
(150 mbar), the residue is chromatographed on silica gel (ethyl acetate/isopropanol 3: 1)
and recrystallised from toluene/hexane (1:1). 21.3 g of the compound 11 are obtained.
2~019~
- 36-
Melting point 70-73C.
Example 12: (compound 12, Table 1)
7.8 g of the compound 11, 5.65 g of n-dodecanol and 0.13 g of dibutyltin oxide are heated
to 150C for 4 h in a weak vacuum (0.15 bar). 8.7 g of the compound 12 are obtained after
cooling and chromatography on silica gel (dichloromethane/ethyl acetate 4:1) andrecrystallisation from acetonitrile. Melting point 44-45C.
2~40~ 9~
- 37 -
Table 1
No. Compound m.p. ~C [calculated/foundl %
~ 70.27 3.79 5.85 13.40
1 ~N~ 173-4 70.31 3.82 5 90 13.42
H S _
2 ~ ~ 93-S 73.98 8.47 2.61 5.98
~ ~ 73.49 8.53 2.53 6.09
C18H370C
H
3 ~S~ 51-S 71.41 9.30 2.87 6.57
CO C H 72.12 9.19 2.79 6.48
. o 2 1a 37
H \ +
65.87 3.55 5.49 12.56
4 ~ ~N~ ~ ¦ 65.85 3.68 5.21 12.84 ¦
_ H \\ ~,
S ~S~ 214-16 61.98 3.34 5.16 11.82
_ ~ ~ 62.01 3.32 4.91 11.8D
Table 1 (continuation)
No.Compound m.p. C [calculated/found] Yo
H NH 70.19 6.43 14.88 --
6 O 1:!8- 130 70.18 6.55 15.02 --
7 Cl6H33 50-1 78.59 10.75 6.79 --
~\) 78.51 10.73 6.72 -- .
O
COC6Hs 73.96 5.52 9.59 --
8 ~ 143-5 73.74 5.52 9.70 --
_ _
~ N ~I~q
9 I~N~I 230-240
-- lC16H33
~,N~ 54-6 82.21 8.93 5.64 --
O ~ 82.16 9.01 5.63 --
- 2~4~19~
- 39-
Table 1 (continuation)
No. Compound m.p C [calculated/found] %
CH2cO2cH3 64.60 6.20 10.76 --
11 e~ ~ ) 70-73 64.65 6.20 10.92 --
_ CH2CO2C12H25 .
~ ~ ~ 72.60 9 02 6.77 --
12 ~ I 44-45
_ ~ ~N~ 72.42 9.29 6.63 --
Example 13: Test for stabilisation of an industrial oil a~ainst oxidative de radation
(TFOUT: Thin Film Oxygen Uptake Test)
This test is a modified forrn of the rotary bomb lest for mineral oils (ASTM D 272). A
detailed description can be found in C.S. Ku, S.M. Hsu, Lubrication Engineering 40
(1984) 75-83. The test oil in this case is a commercial 15W40 motor oil, with about half
the usual content of zinc dithiophosphates (0.75 % ZnDTP, 550 ppm P, 1160 ppm Zn).
The additive to be tested (compound of the formula I) is tested for its stabilising effect in
the oil in the presence of water (2 %), an oxidised/nitrated petroleum fraction (4 %) and a
mixture of liquid metal naphthenates (4 %) at an oxygen pressure of 6.1 bar and 160C.
The water and the two liquid catalysts for the test are obtained from the National Bureau
of Standards (NBS), with certification for the analysis, under the designation Standard
Reference Material 1817. The test is concluded when a clear kink in the pressure/time
graph indicates the oxidation setting in at the end of the induction period (min.).
A long induction period denotes a good stabilising effect of the additive. The results are
summarised in Table 2.
2 ~ 9 ~
- 40 -
Table 2
Compound Amount added Induc~ion pcrio~l
rrom Examplc (% by wci~ht) (min.)
9 0.5 153
Rcrercllco ~ 83
Example 14: Test for stabilisation of the melt index of polvpropvlene on multiple
extrusion
1.3 kg of polypropylene powder (melt index 3.2 gllO min, measured at 230C using2.16 kg) are mixed with 0.05 % of calcium stearate and 0.05 % of Irganox 1010 and O.OS
% of processing stabiliser. This mixture is extruded in an extruder having a cylinder
diameter of 20 mm and a length of 20 d = 400 mm at 100 rpm, the 3 heating zones being
adjusted to the following temperatures: 260C, 270C, 280C. The extrudate is drawn
through a water bath to cool it and then granulated. These granules are extruded a second
and third time. The melt index is measured after these 3 extrusions ~at 230C using 2.16
kg). A large increase in the mel~ index denotes marked chain degradation, i.e. poor
stabilisation. The results are summarised in Table 3.
204~1~a
- 41 -
Table 3
Compound Melt tnde~
irom Exnmple
1 4.9
2 5.5
3 9.3
6.7
6 11.1
wilhout additive 16.5
Example 15: Test for retention of the impact stren th of ABS (aclvlonitrile/butadiene/
stvrene copolvmer)
ABS (Terluran~) 996S, BASF) having a base stabilisation comprising 0.6 % of
4,4'-thiobis(2-t-butyl-5-methylphenol), 0.1 % of
1,1,3-tris(2'-methyl-4'-hydroxy-5'-t-butylphenyl)butane and 0.2 % of dilauryl
thiodipropionate is mixed with 0.15 % of compound I (Table 1) and 0.3 % of
tris(2,4-di-t-butylphenyl) phosphite (= compound A). This mixture is extruded in a
Plamver extruder at 100 rpm, the 3 headng zones being set to the following temperatures:
260C, 270C, 280C. Sample articles are manufactured from the I st, 3rd and 5thextrudate using an Aarburg injecdon-moulding machine (heating zone temperatures:230C/240C/240C, moulding temperature: 60C, cycle duration: 35 seconds). These are
tested in accordance with DIN 53753 for the retention of impact strength with the
following results:
.
- 42 -
Table 4:
Stabiliser Notch impact stren~th according to Charpy
(DIN 53753) (KJ/m )
lx 3x Sx
.
49+6 36+5 29+5
0.15% of compound 1 57 + 5 56 + 5 51 + 7
+ 0.3% of compound A
The results show that the notch impact strength is considerably better retained by the
addition of the two additives.
Example 16: Test for stabilisation of butadiene (BR) and butadiene/stvrene coPolvmer
(SBS~ durin~ Brabender processing
Polybutadiene [BR BUNA CB HX 529C, comprising 0.3 % of
2,6-di-tert-butyl-4-methylphenol (BHT) as base stabilisation] or butadiene/styrene
copolymer ~SBS Finapren 416, comprising BHT and trinonyl phosphite (TNPP) as base
stabilisation] respectively are mixed with the processing stabiliser to be tested in the
mixing chamber of a Brabender plastograph. The mixtures are kneaded at 60 rpm at the
temperature indicated in Table 5 for 60 minutes. During this time, the kneading resistance
is continuously recorded as the torque. Owing to the crosslinking of the polymer, a rapid
increase in the torque occurs in the course of the kneading period after initial constancy.
The activity of the stabilisers shows itself in a lengthening of the period of constancy. The
values obtained can be taken from Table 5.
~ .. ~ ,.
2~0~9~
- 43 -
Table 5:
Compound from Amount Butadiene SBS
Table I added 160C 200C
induction induction
% penod [min] period [min]
Reference without 9 7.5
addltlve
1 0.25 23.5 40
1 + A* (mixture of 0.25 20 33
I pan of 1 and
2 parts of A)
0.40 30.5
*) A: Tri(2.4-di-lert-butylphenyl) phosphite
