Note: Descriptions are shown in the official language in which they were submitted.
1 164865
- 2 -
The invention relates to new poly-bis-triazinyl-
amines, a process for their preparation and their use as
light stabilizers having an antioxidative action for
synthetic polymers.
The new poly-bis-triazinylamines are descri-
bed by the general fQrmula (I)
Rl R2 R3 R \
E~--t ~ N - X - N r N ~ 1, - Y - N ~ E2 (I )
RS R . n
In this formula n denotes an integer from 1 to 200, pre-
ferably 1 to 50 and particularly 1 to 15, Rl and R2
are identical or different and represent hydroger., Cl
to C37 alkyl, preferably Cl to C18 alkyl and particu-
larly Cl to C10 alkyl which is unsubstituted or substi-
tuted by a hydroxyl group, or represent C5 to C12
cycloalkyl which is unsubstituted or substituted by up
to four Cl to C4 alkyl groups, preferably unsubstituted
C5 to C12 cycloalkyl, or represents C7 to Cl~ aralkyl,
preferably C7 to Cg phenylalkyl or a group of the formula
(II) CH2R6
H3C ~ R6
HN ~-
H3C ~ 6 (II)
~t~2R
'
1 164~6
-- 3 --
in which R6 ~enotes hydrogen or Cl to C6 alkyl, prefer-
~bly hydrogen or methyl, but especially hydrogen.
R3 and R4 are identical or different and have
the meanings indicated for Rl and R2 Preferably,
on~ of these radicals is hydrogen, but, in particular,
both radicals are hydrogen.
R5 is halogen, phenyl, -oR7 or -NR8R9, particu-
larly -NR8R9, R7 in these groups denoting hydrogen, C
to C18 alkyl, preferably Cl to C4 alkyl, C3 to C12
alkenyl, C5 to C12 cycloalkyl, C7 to C18 aralkyl, C6 to
C10 aryl or a radical of the formula (II). R radi-
cals which are preferred are Cl to C4 alkyl, phenyl or
the radical of the formula (II).
R8 and R9 are identical or different and repre-
sent hydrogen, Cl to C37 alkyl which, particularly inthe case of C2 and C3 alkyl, can be substituted by Cl
to C18 alkoxy and, in the case of C2 to C5 alkyl, can be
substituted by Cl to C4 dialkylamino, preferably Cl to
C2 dialkylamino, or represent C3 to C12 alkenyl, C5 to
C12 cycloalkyl which is unsubstituted or is substituted
by up to four Cl to C4 alkyl groups, C7 to C18 aralkyl,
preferably C7 to Cg phenylalkyl, phenyl or naphthyl,
preferably phenyl, C2 to C30 hydroxyalkyl, preferably
C2 to C18 hydroxyalkyl and particularly C2 to C4 hydroxy-
alkyl, or the radical of the ~ormula (II)
R8 and R9, together with the common nitrogenatom, can also form a pyrrolidine ring or a piperidine,
~ morpholine or hexamethyleneimine ring which is unsubsti-
tuted or substituted by up to four Cl to C4 alkyl groups
~ 16486~
X and Y are identical or different and denote C2
to C18 alkylene, preferably C2 to C12 alkylene and
particularly C2 to C6 alkylene, or C2 to C12 bis-
(propoxy)-alkylene, or C6 to C18, preferably C6 to C12,
'5 monocycloalkylene, dicycloalkylene or'tricycloalkylene
which is unsubstituted or substituted by up to four
methyl groups, but which is preferably unsubstituted,
and in which, in the case first mentioned, two C atoms
can be replaced by N atoms which can carry propylene
groups, or X and Y denote C6 to C18 arylene, preferably
phenylene, or C7 to C18 aralkylene, but, in particular,
X and Y are dicycloalkylene or tricycloalkylene, orpipera-
zinylene radi.cals are present instead of the groupings
Rl R2 R~ R4
-N-X-N- or -N-Y-N-, - R3 R4
15El is a halogen atom or a group -N-Y~N-H,
~ 4 R3
-N-~-N-H, -oR7 or -NR8R9,preferably chlorineandE2is
hydrogen or an acyl group, preferably hydrogen, R3, R4,
R7, R8 and R9 having the meanings indicated above and at
.least one of the radicals Rl, R2, R3, R4, R7, R8 and R9
being of necessity a group.of the formula (II).
Rl to R4 can be identical'if X and Y are differ-
ent. X and Y can be identical if at least one of the
radicals Rl or R2 is different from R3 and R4
The new poly-bis-triazinylamines are obtained by
using unsubstituted or partly substituted cyanuric halides
as starting ma-terials. The individual interme(liate
products can be isolated, but it i.s also possible to
1 16~6
effect the synthesis of the desired end products in a
so-called "one-pot process" without isolating the inter-
mediate compounds.
The synthesis can be carried out by two different
reaction routes, which are outlined in the simplified
reaction diagram below.
1 164865
Hal N Hal
~0~ .
HalR1R2
H-R5 (Vl) / \ HNXNH (UIII)
--5 to 40 ~
~ . ~I
Hal ~I~N~Hal Hal rO~ N-X- N ~ N~Hal
~ (VII) Hal ~rl ~IIIa)
R1B2 ¦ ~!t r ¦ R3R4
H!JXNH ( III I I ) HNYNH ( IV)
10 - 70 ~ ¦ 10 - 70 4C
,
_ _ _ _ _
R1 R2 / R1 R2 R R4 \
HalrN ~ N-X-N ~ N~, Hal ~al~ N~ N-X-N r N ~ ~~Y-;~ H
N~,N I~N ~N ;~N /n
Va ri a nt
HNYNH ( I V ) \ / H-R (
- 20D ~ \ / 50 - 200
R R2 R R4 \
~5
R R n
(I)
1 16~8~5
-- 7 --
The diamines (IV) and (VIII) can be employed`in
any desired sequence, but the sequence shown in the
diagram represents the pre~erred procedure. In the .
.~ormulae of the reaction diagram, Hal, n, Rl, R2, R3,
R4, R5, X, Y, El and E2 have the meanings indicated
above. In formula (VI), R5 cannot be halogen or
phenyl;
In accordance with variant A, a dihalogeno-bis-
triazinyldiamine of the formula (III) is reacted with a
0.8 to 1.4, preferably 1.0 to 1.2 and, particularly a
1 to 1 05, molar amount of a diamine of the formula (IV).
Variant B provides for reacting a poly-bis-
triazinylamine of the formula (V), which is accessible
from the compounds (IIIa) by reacting the latter with a
0.8 to 1.4, preferably 1.0 to 1.2 and, in particular, a
1 to 1,05, molar amount of a diamine of the formula (IV),
with 0 8 to 1,4, preferably 1.0 to 1.2 and, in parti-
cular, 1 O to 1.05, equivalents of a compound of the
formula (VI)
Variant C is a multi-stage one-pot process in
which a cyanuric halide, preferably cyanuric chloride,
is first reactedwit~ a 0.8 tolO3molar,preferably O.9to
- 1.1 molar and, in particular, an equimolar, amount of a
. compound of the formula (VI) in order to synthesize the
intermediate compounds (VII), or is reacted with a 0 4
2~ to 0 7, preferably 0.5 to 0 6 and, in particular, 0,5
to 0.502, molar amount of a diamine of the formula (VIII)
in order to prepare the intermediate compounds (IIIa).
The intex~ediate compo~mds thus obtained are then
-- 8 --
reacted, without being isolated, with a 0.4 to 0.7,
preferably 0~5 to 0.6 and, in particular, 0~5 to 0.502~
molar amount either of a diamine of the formula (VIII),
if the educt is a compound of the formula (VII), or with
5 a 0.8 to 1.4, preferably 1.0 to 1.2 and, in particular,
1,0 to 1.05, molar amount of a diamine of the formula
(IV), if the educt is a compound of the formula (IIIa).
The intermediate compounds (III) or (V) which have been
prepared in this manner are subseauently reacted, also
without intermediate isolation, under the conditions
indicated for the variants A or B, respectively, to give
the desired poly-bis-triazinylamine.
The variant A, and the t'multi-stage one-pot
reaction" which takes place as an intermediate stage
via this mode of implementation, is a preferred embodi-
ment
The ~eactions are carried out in inert organic
solvents, such as, for example, petroleum ether, petrol-.
eum fractions, acetone, ether, dioxane, benzene, toluene,
xylene, cumene, mesitylene or mixtures thereof
The variants A and B require reaction tempera-
tures of 50 to 200, preferably 80 to 100 and, in parti-
cular, 100 to 160, C In the process according to
~rariant C, the monosubstitution of the cyanuric halide
to give compound (VII) is carried out at -5 to 40, pre-
ferably -5 to 20 and, in particular, 0 to 10, C, the
monosubstitution of the cyanuric hali.de to ~ive com-
pound (IIIa) is carried out at -5 to 20, preferably 0 to
10, C, and the disubstitution of the dihalogenotriazine
1 ~64865
9 _
(VII) to give (III) and the disubstitution of the tetra-
llalogenoditriazine (IIIa) to give (V) are carried out at
:LO to 70, preferably 30 to 70 and, in particular, 40 to
60, C.
Inorganic bases are added in equivalent quan-
tities as hydrogen halide acceptors in the preparation
of the new compounds. Examples of suitable bases
are sodium hydroxide, potassium hydroxide, sodium car-
bonate and potassium carbonate, in solid form or in
aqueous solution.
The following are examples of dihalogenotriazine
intermediate compounds of the formula (VII): 2,4-di-
~chloro - 6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-3-
hydroxypropylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-
(2,2,6,6-tetramethyl-4-piperidyl)-2-methoxypropylamino]-
1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-
4-piperidyl)-3-etnoxypropylamino]-1,3,5-triazine, 2,4-
dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-3-octa-
decyloxypropylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-
(2,2,6,6-tetramethyl-4-piperidyl)-3-dimethylaminopropyl-
amino~-1,3,5-triazine, 2,4~dichloro-6-[N-(2,2,6,6-tetra-
methyl-4-piperidyl)-3-diethylaminopropylamino]-1,3,5-
triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-
piperidyl)-2-dimethylaminoethyl~mino]-1,3,5-triazine,
2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-4-
diethylaminobutylamino~-1,3,5-triazine, 2,4-dichloro-6-
~N-(2,2,6,6-tetramethyl-4-piperidyl)-4-diethylamino-1-
methylbutylamino]~l,3,~-triazine, 2,4-dichloro-6-dioc-ta-
decylamino-1,3,5-triazine, 2~4-dichloro-6-bu-tylamino-
116~865
-- 10 --
1,3,5-triazine, 2,4-dichloro-6-octadecylamino-1,3,5-
triazine, ~,4-dichloro-6-dicyclohexylamino-1,3,5--triazine,
2,4-dichloro-5-dibutylamino-1,3,5-triazin~, 2,4-dicl~oro-
5-amino-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-
tetramethyl-4-piperidyl)-amino]-1,3,5-triazine, 2,4-
~ichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-butyl-
amino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-
tetramethyl-4-piperidyl)-hexylamino]-1,3,5-triazine,
2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-
octadecylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-bis-
(2,2,6,6-tetramethyl-4-piperidyl)-amino 3 -1, 3,5-triazine,
2,4-dichloro-6-(1,1,3,3-tetramethyl)-butylamino-1,3,5-
triazine, 2,4-dichloro-6-morpholino-1,3,5-triazine and
2,4-dichloro-6-phenoxy-1,3,5-triazine
The following are examples of compounds of the
formula (VIII) and (IV): ethylenediamine, propylene-
diamine, 1,6-diaminohexane, 1,8-diaminooctane, 1,12-
diaminododecane, 1,2-diaminopropane, 2,~-diamino-2,5-
dimethylhexane, p-phenylene-diamine, 1,8-diamino-p-
menthane,l,3-bis-(aminomethyl)-cyclohexane, 4,4~-diamino-
dicyclohexylmethane, 3,3'-dimethyl-4,4~-diaminodicyclo-
hexylmethane, 4,4'-diaminodiphenylmethane, 2 (3), 5 (6)-
bis-(aminomethyl)-norbornane mixed isomers, 3 (4), 8 (9)-
bis-(aminomethyl)-tricyclo-[5.2.1 o2 6]-decane mixed iso-
mers, bis-(3-aminopropyl)-piperazine, 4,7-dioxadecane-
l,10-diamine, 4,g-dioxadodecane-1,12-diamine, 7-methyl-
L~,10-dioxatridecane-1,13-diamine, 3-amino-1-methylamino-
propane, 3-amino-1-cyclohexylaminopropane, 3-amino-].-(2-
ethyl)-hexylaminopropane, N-(cyclohex~ll)-ethylenediamine,
1 16486~
N-(cyclohexyl)-1,6-diamînohexane, N-(2-hydroxypropyl)-
ethylenediamine, N-(2,2,6,6-tetramethyl-4-piperidyl)-
ethylenediamine, N-(2,2,6,6-tetramethyl-4-piperidyl)-
]!,6-diaminohexane, N-(2,2,6,6-tetramethyl-L~-piperidyl)
5 1,3-bis-(aminomethyl)-cyclohexane, N-(2,2,6,6-tetra-
methyl-4-piperidyl)-3(4), 8(9)-bis-aminomethyl)-tri-
cyclo-~5.2 1 o2 6]-decane mixed isomers, N,N'-bis
(2,2,6,6-tetramethyl-4-piperidyl)-ethylenedi.amine, N,N~-
bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-diaminohexa~e,
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-3(!~), 8(9)-
bis-(aminomethyl)-tricyclo[5 2.1 02 6]-decane mixed
- isomers, N,N~-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-
bis-(aminomethyl)-cyclohexane, N,N'-bis-(2,2,6,6-tetra-
methyl-4-piperidyl)-4,9-dioxadodecane-1,12-diamine,
N,N'-bis-cyclododecyl-1,6-diaminohexane, N,N'-bis-iso-
propyl-1,6-diaminohexane, N,N'-bis-cyclohexyl-1,6-
diaminohexane, N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-
4,4'-diaminodicyclohexylmethane, N-(2,2,6,6-tetramethyl-
4-piperidyl)-N'-(cyclododecyl)-1,6-diaminohexane and
piperazine.
The ~ollowing are examples o~ compounds of the
~ormula VI: N-(2,2,6,6-tetramethyl~4-piperidyl)-3-
methoxypropylamine, N-(2,2,6-6-tetramethyl-4-piperidyl)-
3-ethoxypropylamine, N-(2,2,6,6-tetramethyl-4-piperidyl)--
3-octadecyloxypropylamine, N-(2,2,6,6-tetramethyl-4-
piperidyl)-3-dimethylaminopropylamine, N-(2,2,6,6-tetra-
methyl-4-piperidyl)-2-dimethylaminoethylamine, N-
(Z,2,6,6--tetramethyl-4-pi.peridyl)-4-diethylaminobutyl-
amine, 2,2,6,6-tetramethyl 4-piperldylaminopropan-3-ol,
1 16~8~5
-- 12 --
N-~2,2,6,6-~etramethyl-4-piperidyl)-4-diethylamino-1-
methylbutylamine, 2,2,6,6-tetramethyl-4-aminopiperidine,
N-(2,2,6,6-tetramethyl-4-piperidyl)-butylamine, N-
(2,2,6,6-tetramethyl-4-piperidyl)-octadecylamine, N-
5 (2,2,6,6-tetramethyl-4-piperidyl)-cyclododecylamine, N-
(2,2,6,6-tetramethyl-4-piperidyl)-hexylamine, di-
(2,2,6,6-tetram~thyl-4-piperidyl)-amine, arNmonia, butyl-
amine, dicyclohexylamine, cyclododecylamine, hexylamine,
dodecylamine J octadecylamine, dioctadecylamine, 2,3-
dimethylcyclohexylamine, 2,6-dimethylmorpholine, methyl-
cyclohexylamine, pyrrolidine, piperidine, 3,5,5-trimethyl-
hexylamine, 2,2-dimethylpropylamine, di-n-octylamine,
methanol, phenol and 2,2,6,6-tetramethylpiperidin-4-ol,
The following are examples of compounds of the
formula ~
1. N,N~-big-~2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-
3-methoxypropylamino~-1,3,5-triazin-6-yl]-N-(2,2,6,6-
tetramethyl-4-piperidyl)-1,6-diaminohexane .
2, N,N'-bis-~2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-
3-meth~xypropylamino)-1,3,~-triazin-6-yl]-N-(2,2,6,6-
tetramethyl-4-piperidyl)-1,3-bis-(aminomethyl)-cyclo-
hexane
3; N~N'-bis-[2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-
3-methoxypropylamino)-1,3,5-triazin-6-yl]-N,N'-bis-
(2,2,6,6-tetramethyl-4-piperidyl)-3(4), ~(9)-bis-(arnino-
methyl)-tricyclo-[~,2.1,02 6]-decane mixed isomers
4, N,N~ bis-[2-chloro-4-((2,2,6,6-tetramethyl~4-piperidyl)-
3-ethoxypropylamino~-1,3,~-triazin-6-yl~-N-(2,2,6,6-tetra--
methyl-4-piperidyl)-4,9-dioxadodecane-1,12-diamine
1 16~865
- 13 _
`5. ~,N'~bis-[2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-
butylamino~-1,3,5-triazin-6-yl]-N,NI-bis-(2,2,6,6-tetra-
methyl-4-piperidyl)-1,6-diaminohexane
6, N,N'-bis-[2-chloro-4~((2,2,6,6-tetramethyl-4-piperidyl)-
butylamino~-1,3,5-triazin-6-yl]-N,N'-bis-cyclododecyl-1,6-
diaminohexane
7. N,N'-bis-[2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-
butylamino)-1,3,5-triazin-6-yl~-N-cyclohexyl-1,3-diamino-
propane
8. N~N'-bis-[2-chloro-4-dibutylamino-1,3,5-triazin-6-yl]-
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-ethylene-
diamine
9, N,N'-bis-[2-chloro-4-morpholino-1,3,5-triazin-6-yl]-
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-ethylene-
diamine10, N,NI-bis-[2-chloro-4-octadecylamino-1,3,~-triazin-
6-yl]-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-
ethylenediamine ..
11. N,N'-bis- t 2-chloro-4-~(2,~,6,6-tetramethyl-4-piperidyl)-
octadecylamino)-1,3,5-triazin-6-yl]-piperazine
12, N,N'-bis-[2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl~-
3-ethoxypropylamino)-1,3,5-triazin-6-yl]-bis-(3-amino-
propyl)-piperazine
13. N,N'-bis-~2-chloro-4-phenoxy-1,3,5-triazin-6-yl~-
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-ethylenedi-
amine
14, N,N'-bis-[2-chloro-4-phenyl-1,375-triazin-6-yl]-
N,N'-bis-(2 3 2,6,6-tetramethyl-4-piperi~y'.)-4,9-dioxa-
dodecane-1,12-diamine,
1 1648~S
~.4 --
The reaction of cyanuric halides with primary
or secondary monoamines or polyamines and also alcohols
or phenols to give definite compounds or polymeric tri-
azines has been part of the state of the art for a con-
siderable time [J. Am. Chem. Soc. 73 (1951), No. 7,pages 2,981 et seq,; U.S. Patent Specificat~on 2,544,071;
and Swiss Patent Specifications 342,784 and 342,785].
Polytriazine compou~ds of the formula
~N
Z
in which X and Y and Z can be identical or different and
denote -0-, -S- or -N-, and one of these groups must
carry a polyalkylpiperidyl radical are also known
(German Patent.Specification 2,636,144), As
already explained in European Patent Application 13,66.~,
which also describes polymeric products related to the
above patent speci.ficatlon, it has been found that con-
siderable difficulties, due essentially to the formation
of insoluble by-products which are difficult to remove,
must be accepted in the preparation of these products.
A further disadvantage lies in the fact that an appreci-
able proportion of low~molecular constituents is present
in the end product, which causes a relatively high vola-
tility; To sum up, the disadvantages of -~he products
described in German Paten-t Specification 2,635,144 can
~ 1648~5
be regarded as due to the fact that the molecular
weight distribution is too broad: constituents of too
high molecular weight cause the insolubility, even in
the polymer, and constituents of too low molecular
weight cause an increase in the volatility The
disadvantages can only be eliminated by expensive
measures of separation and purification. It is a
disadvantage of the products of EP-A 13,665 that cross-
linked products can be formed to a considerable extent,
and these then cause compatability pro~lems with the
polymers to be stabilized.
It could not have been foreseen in any way that,
amongst the compounds according to the invention, it
would also be possible to prepare those in which R8 or
R9 has the meaning of a hydroxyalkyl, alkoxypropyl or
dialkylaminoalkyl group, since these groups can also
. react with acid chlorides, analogously to the NH group,
and it would therefore have been expected that bridges
would be formed between two different triazine rings,
which would have led to undesirable crosslinked products,
Such a course of the reaction appeared entirely possible~
i~ not indeed preferred, from publications concerning
the known formation of cyanur-c acid esters from alcohols,
which can also be formed from alkoxyalkyl groups by
cleavage o~ ethers as a result of unavoidable quantities
of hydrogen halide, and also publications concerning the
synthesis of cyanuric acid dialkylamides from cyanuric
chloride and tertiary amines ~Ullm~n volume 9 (1975),
page 651; E, Kober and R Ratz, J. Org, Chem 27 (1962),
1 16~865
-- 16
page 2,509 et seq.~.
The poly-bis-triazinylamines accordin~ to the
invention make it possible to solve the problem on which
the present invention is based, that is to say the pro-
5 vision of polymeric light stabilizers which have a linear
structure and are not crosslinked and which exhib.it an
excellent light stabilizing action and are free from the
disadvantages of the products of German Patent Specifica-
tion 2,636,144, since the new compounds possess the
desired prop~rties in a high degree, which could in no
way have been expected. This is because it could
not have been foreseen that the procedure of first pre-
paring dichloro-bis-triazinylamines (III) and reacting
the latter in a controlled manner with selected other
diamines (IV) would produce polymers which would have
met the desired pattern of properties. It would, on
the contrary, have been necessar~ to assume that the
properties of the new products would be largely similar
to those of German Patent Specification 2,636,144.
Surprisingly, however, it is possible by specific selec-
tion of the diamines (IV), to control the properties of
the new polytriazines according to the invention so that,
for example, the molecular weight can be influenced to a
very large extent and, if there is a high proportion of
groups of the formula (II), also to achieve high molecu-
lar weights wi~hin a short reaction time,
In addition to their excellent ac~ivity, mention
should also be made of the lo~J volatility of the new
products, which is in striking comparison with th~ best
1 1648~5
-- 17 --
example of the said German Patent Specification 2,636,144,
E~ample 6, a fact which is particularly manifest in the
case of those products in which the radicals R3 and/or
~4 are hydrogen. The new triazine stabilizers can
~e incorporated without problems in the polymers to be
stabilized and are excellently suitable for stabilizing
these polymers against oxidative degradation induced by
light. In addition to their excellent effectiveness
as stabilizers, the new stabilizers are distinguished by
10 their compatability with the polymers to be stabilized,
their migration resistance against extraction by aqueous
media, which plays an important part in outdoor weather-
ing, their heat stability, even at high processing
temperatures, and their low volatility, particularly in
comparison with Example 6 of German Patent Speci~ication
2,636,144.
As already stated, the new compounds are used as
stabilizers for plastics to counteract damage caused to
the latter through the action of oxygen, heat and light
The following are individual examples of such plastics:
Polymers derived from hydrocarbons with single
or double unsaturation, for example polyolefins such as
polyethylene, which can optionally be crosslinked, poly-
propylene, polybut-l-ene, polyisobutene, polymethylbut-
2~ 1 ene, poly~ethylpent-l-ene, polyisoprene, polybutadiene
and polystyrene, copolymers of the monomers on ~hich the
said homopolymers are based, such as e-thylene-propylene
copolymers, propylene-bu-t-l-ene copol~ers, propylene-
isobu-tene copolymers and styrene-butadiene copolymers,
1 164865
-- 18 --
and also terpolymers of ethylene and propylene with a
~iene, such as, for example, hexadiene, dicyclopenta-
~diene or ethylidenenorbornene; mixtures of the above-
mentioned homopol~ners, such as, for example, mixtures
of polypropylene and polyethylene, polypropylene and
polybut-l-ene, polypropylene and polyisobutylene or of
a butadiene-acrylonitrile copolyrner with a styrene-
butadiene copolymer.
Vinyl polymers containing halogen, such as poly-
vinyl chloride 7 polyvinylidene chloride, polyvinylfluoride, polychloroprene and chlorinated rubbers, and
copolymers of vinyl chloride and vinylidene chloride with
one another and ~ith other olefinically unsaturated
monomers.
Polymers derived from a,~-unsaturated acids and
derivativés thereof, such as polyacrylates and poly-
methacrylates, polyacrylamides and polyacrylonitrile
and copolyrners thereof with one another and with other
vinyl compounds, such as acrylonitrile/butadiene/styrene,
acrylonitrile/styrene and acrylonitrile/styrene/acrylic
ester copol~ners
Polymers derived from unsaturated alcohols and
amines or acyl derivatives or acetals thereof, such as
polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate,
polyvinyl benzoate, polyvinyl maleate, polyvinyl bu-~yral,
polyallyl phthalate, polyallylmelamine and copolymers
thereof with other vinyl compounds, such as ethylene/
vinyl acetate copolymers.
Homopolymers and copolymers der.ive~ frorn
1 164865
`- 19 --
epoxides, such as polyethylene oxide or the polymers
which are derived from bis-glycidylethers.
Polyacetals, such as polyoxymethylene and poly-
oxyethylene and polyoxymethylenes which contain ethylene
oxide as the comonomer.
Polyurethanes and polyureas.
Polycarbonate.
Polyamides and copolyamides derived from diamines
and dicarboxylic acids and/or from aminocarboxylic acids
or the corresponding lactams, such as polyamide 6,
polyamide 6/6, polyamide 6/10, polyamide 11 and poly-
amide 12
Polyesters derived from dicarboxylic acids and
dialcohols and/or from hydroxycarboxylic acids or the
corresponding lactones, such as polyethylene terephtha-
late, polybutylene terephthalate or poly-1,4-dimethylol-
cyclohexane terephthalate
Crosslinked polymers derived from aldehydes on
the one hand and from phenols, ureas and melamines on
the other hand, such as phenol-formaldehyde, urea-
formaldehyde and melamine-formaldehyde resins.
Finally, the new compounds can also be employed
as stabilizers in the resins and paints field. Ex-
amples of these are thermosetting and thermoplastic
acrylic resins which are used for automobile finishes
~Encyclopedia of Polymer Science and Technology, Inter-
science Publishers, New Yo~k volurne 1 (1964), pages 273-
276 and volum~ 13 (1970), pages 530-532; 'IUnderstanding
Paint" by ~ R. Fuller, American Paint Journal Co.,
1 .164~6~
- 20 -
St. Louis, 1965, pages 124-135], acrylic resin lacquers,
that is the customary stoving lacquers [described, for
example, in H Kittel's "Lehrbuch der Lacke und
Beschicht~gen" ("Textbook of Lacquers and Coatings"),
Yolume 1, part 2, pages 735 and 742 (Berlin, 1972) and
in H. Wagner and H.F. Sarx "Lackkunsthar7e" ("Synthetic
Resins for Lacquers"), pages 229-235] and, very parti-
cularly, mixtures based on an acrylic resin(which can
be crosslinked by heat)and styrene and also lacquers and
coatings based on acrylic/melamine resins and alkyd/
acrylic/melamine resins Lacquers of this type can
contain, as further additives, other customary light
stabilizers, phenolic antioxidants, pigments, dyestuffs,
metal deactivators and the like.
A particularl~J important aspect is the stabili-
zation of polyolefins, styrene polymers, polyamides,
poly-(meth)acrylates and polyurethanes, for which the
compounds are preferentially suitable Examples of -
this are polyethylene of high and low density, poly-
propylene, ethylene-propylene copolymers, polystyrene
and styrene-butadiene-acrylonitrile terpolymers; mix-
tures of polyolefins or styrene polymers and polyure-
thanes based on polyethers or polyesters
The new stabilizers are incorporated into the
polymer compositions in accordance with methods which
are generally cus-tomary. The incorporation can be
effected, for example, by mixing the compounds and
optiona]ly ~urther additives into the melt by the
methods customary in the art, before or during shaping,
1 164865
or by applying the eompounds, dissolved or dispersed,
to the polymer directly or mixing the compounds into a
solution, suspension or emulsion of the polymer, where
. appropriate with subsequent evaporation of the solvent.
The quantities are 0 01 to 5, preferably 0 05 to 2.5
and, in particular, 0.1 to 1 0, % by weight, relative
to the material to be stabilized. The new compounds
can also be added to the plastics to be stabilized in
the form of a master-batch containing these compounds,
for example, i.n a concentration of 1 to 50, preferably
2.5 to 20, % by weight
The plastics which have been stabilized by the
addition of the substances according to the invention
can, if necessary, also contain other known and custom-
ary additives, such as, ~or example, antioxidants based
on phenols and sulfides, metal deactivators and light
stabilizers, phosphite stabilizers, metal compounds,
epoxy stabilizérs and polyhydric alcohols (see also
German Offenlegungsschrift 2,427,853, pages 18-24)
Examples of antioxidants are sterically hindered
phenols, such as 2,6-di-tert -butyl-4-methylphenol, 4,4~-
butylidene-bis-(2,6-di-tert.-butylphenol), 4,4l~thio-bis-
(2-tert.-butyl-5-methylphenol), 2,5-di-tert -butyl-4-
hydroxyanisole, 2,2-bis-(3,5-di-tert.-butyl-2-hydroxy-
benzyl)-malonic acid dioctadecyl ester, 1,3,5-tris-
(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-
benzene, 2,4,6-tri-(3,5-di-tert -butyl-4-hydroxybenzyl)-
phenol, phenolic triazine compounds, such as 1,3,5-
tris-(3,5-di-tert --butyl~4-hydroxybenzyl) i.socyanurate,
1 1648~S
_ 2~ --
esters of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-
propionic acid with, for example, octadecanol, penta-
erythritol and tris-hydroxyethyl isocyanurate, esters
of 3,3-bis-(3-tert.-butyl-4-hydroxyphenyl)-butanoic acids
5 with, for example, ethylene glycol, thiodipropionic acid
esters with fatty alcohols, Ca or Ni salts of 3,5-di-
tert;-butyl-4-hydroxybenzylphosphonic acid ethyl ester,
dioctadecyl sulfide and dioctadecyl disulfide.
W Absorbers and light stabilizers include 2-
10 (2 t -hydroxyphenyl)-benztriazoles, such as, for example,
the 5-chloro-39,5 9 -di-tert.-butyl and 5-chloro-3',5'-di-
tert,-amyl derivatives, 2-hydroxybenzophenones, such as,
for example, the 4-heptoxy or 4-octoxy derivative,
salicylates, such as octylphenyl salicylate, nickel com-
plexes such as, for example, those of 2,29-thio-bis-4-
(1,1,3,3-tetramethylbutyl)-phenol with butylamine or
other amines, oxalic acid diamides and sterically hin-
dered amines,
Phosphites which should be mentioned are ali-
phatic, aro~atic or aliphatic-aromatic phosphites, such
as, for example, tris-nonylphenyl phosphite, tris-(2,4-
di-tert.-butylphenyl) phosphite, tris-(2-tert -butyl-
phenyl) phosphite or esters of pentaerythritol p~losphite.
Metal compounds which are known as stabilizers
are understood in this context as meaning calcium,
barium, strontium, zinc, cadmium, magnesium, aluminum
and lead soaps of aliphatic carboxylic acids or hydroxy-
carboxylic acids having about 12 to 32 C atoms, s21ts of
the said me~als with a.romatic carboxylic acids, such as
1164~65
-- 23 --
be.nzoat~s or salicylates and (alkyl)-phenolat~s o.~ the~e
metals, and also organotin compo~ds, such as, .t`or ex~
ample, dialkyltin thioglycolates and carbox~lates,
- . Kno~n epoxy stabilizers are, for example, epoxi-
dized higher fatty acids, such as epoxidized soyabean oil,
~all oil or linseed oil or epoxidized butyl oleate and
epoxides of long-chain olefins.
Polyhydric alcohols can, for example, be penta-
erythritol, trimethylolpropane, sorbitol or mannitol,
that is to say preferably alcohols having 5 or 6 C atoms
and 2 to 6 OH groups.
An effective combination of stabilizers for
poly-a-olefins, such as, for example, high-pressure,
medium-pressure and low-pressure polymers of ~2 to C4
a-olefins, in particular polyethylene and polypropylene
or copolymers of such a-olefins, is composed, for ex-
ample, relati.ve to 100 parts by ~7eight of polymer, of
. ..
0.01 to 5 parts by weight of one o~ the compounds to be
used in accordance with the invention, 0,05 to 5 parts
by weight of a phenolic stabilizer, if appropriate 0.01
to 5 parts by weight of a sulfur-containing co-stabilizer
and, if appropriate, 0.01 to 3 parts by weight of a
basic or neutral metal soap, such as, for example,
calciurn stearate or zinc stearate, or the corresponding
oxides and, if appropriate, 0,01 to 5 parts by ~eight of
a known W stabilizer belonging to the group comprising
alkoxyhydroxybenzophenones, 4-hydroxyphenylbenzotri.azoles,
benzylidenem210nic acid mononitrile-ester or the so-
called quenchers, such as, for example, nickel chelates,
1 1fi48~5
-- 24 --
Examples of substances which can be regarded as other
customary additives are plasticizers, slip agents,
emulsifiers, fillers, such as, for example, chalk, talc
or asbestos, pigments, optical brighteners 7 flameproof-
ing agents and antistatic agents,
The plastics which have been stabilized in
accordance with the invention can be used in a wide
variety of shapes, for example as sheets, fibers, tapes
or profiles or as binders for lacquers, adhesives or
cements.
The examples below serve to illustràte the
invention further. In this connection, Examples 1
to 13 illustrate the preparation of compounds of the
formula (III), which are then reacted in accordance with
Examples 14 to 47 with a diamine of the formula (IV) to
give the poly-bis-triazinylamines according to the inven~
tion, Neither the intermediate products nor the
oligomers have a sharp melting point, but a melting
range,
Example 1
N,N1-bis-[2-Chloro-4-((2,2,6,6-tetramethyl-4-piperidyl)-
3-methoxypropylamino)-1,3,5-triazin-6-yl]-N-(2,2,6,6-tetra--
methyl-4-piperidyl)-1,6-diaminohexane
260 g of toluene and 120 g of acetone are initially
placed in a 1 1 stirred apparatus. 36,8 g (0,2 mole) of
cyanuric chloride are added and the solution is cooled to
0C, 45 6 g (0,02 mole) of N-(2,2,6s6-tetramethyl-4-
piperidyl)-~-metho~ypropylamine (= a compound of the
formula (VI)) are then added drop~ise a-t 0 to 10C,
~ 8~5
- ~5 -
~ollowed ~y 32 g of 25% strength aqueous sodium hydr-
oxide solution addeà in the course of 3 hours at 5 to
10C After adding 25.5 g (O.l mole) of N-(2,2,6~6-
tetramethyl-4-piperidyl)-l,6-diaminohexane (=the compound
of the formula (VIII)), the mixture is warmed to 50C
and 32 g of 25% strength aqueous sodium hydroxide solu-
tion are added dropwise in the course of 2 hours at this
temperature After adding 80 ml of acetone and 60 ml
of water, the organic phase is separated off and concen-
trated to dryness in vacuo at a heating bath tempera-
ture of approx. 70C and the residue is dried in a high
vacuum at 70C. This leaves 9l.5 g = 98% of theory,
of a colorless solid of melting point approx. 100C (a
~iscous melt)
~ les 2 to 13
_, .
Further compounds (III) are prepared in accord-
ance with the instructions of Example l from cyanuric
chloride and the components listed in Table l. The
numbers recorded in column 4 of the table refer to the
list of the compounds on pages 12 and 13
1 :~&~8~5
-- ~6
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-- 27 --
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8 6
_ 2~ -
Example ~4
Poly-bis-tl~iazinylamine from compound l and hexam~thylene-
diamine
,
18 0 g (O.Ol9 mole) of the `compound obtained in
Example l, together with 2.3 g (0.02 mole) of hexa-
methylenediamine and l.6 g (0.04 mole) of NaOH powder,
are stirred in lOO ml of xylene in a 250 ml stirred
apparatus for 9 hours under reflux (132C). The mix-
ture is then filtered, the filtrate is concentrated on a
rotary evaporator in vacuo and the residue is dried at
150C in a high vacuum for 4 hours This leaves a
nearly colorless resin of melting point 115C, in a
quantitative yield. Molecular weight 3,300
Examples 15 to 47
The procedure followed is analogous to that of
Example 14, using further compounds of the formula (III).
The experimental data are listed in Table 2. Column 2
refers to the compound number recorded in Table 1,
column 4, which refers to the list on pages 12 and 13
1 1 6
-- 29 --
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1 1~4865
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1 ~6~865
-- 32 --
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1 16~865
- 33 -
Example 48
12.05 g ~1/20 mole) of N-(2,2,6,6-tetramethyl-
4-piperidyl)-3-dimethylaminopropylamine are initially
t;aken in 40 r~ of xylene in a 250 r~ stirred apparatus.
9.2 g (1/20 mole) of cyanuric chloride, dissolved in
60 ml of xylene, are then added dropwise at an internal
temperature of -5 to +5C. The mixture is warmed
to 10C, 2.0 g (1/20 mole) of NaOH powder are added and
the mixture is stirred for 3 hours at 10C. 5.0 g
(1/40 mole) of N-(2,2,6,6-tetramethyl-4-piperidyl)-
ethylenediamine are then added, after which the mixture
is warmed to 50C and, after 2.0 g (1/20 mole) of NaOH
powder have been added, is stirred at this temperature
for 5 hours. After 1.5 g (1/40 mole) of ethylene-
diamine and 2.0 g (1/20 mole) of NaOH powder have been
added, the mixture is stirred under reflux for a further
8 hours and is then filtered and the filtrate is concen-
tra~ed to dryness in vacuo The residue is dried in
a high vacuum at 150C. This leaves a pale yellow
solid resin in a virtually quantitative yield. M.p.
140C
Example 49
9 2 g (1/20 mole) of cyanuric chloride are initi-
ally taken in 40 ml of xylene in a 250 rnl stirred appa--
ratus. 12.0 g (1/20 rnole) of N-(2,2,6,6-tetramethyl-
4-piperidyl)-aminohexane, dissolved in 60 ml o~ ~ylene,
are then added dropwise at O to 10C After 2 0 g
(1/20 mole) of NaOH powder have ~een added, the mi~ture
is stirred for 3 hours at 10~ and is then processed
1 16486
- 34
further as indicated in Example 40) to give a colorless
resin~ M,p. 215C.
Examples 50 to 52
The procedure followed is as in ExamplQ 49,
using the substances listed below:
.
Ex- Starting materials Result-
ample Monoamine (VI) Diamine (VIII) Diamine (IV) ng
No M.p (~
. .
50 piperidine analogous to analogous to 230
4.2~ = 1/20 Example 35 Example 18
51 dioctadecyl- analogous to analogous to 85
amine Example 17 Example 24
22.3 = 1/10
52 diethanol- analogous to analogous to 155
amine Example 22 Example 27
5.25 = 1/20
Examp]e 53
The compound 14 is obtained, analogously to
Example 1, from 45.2 g (0.2 mole) of 2-phenyl-4,6-
dichloro-1,3,5-triazine and 48.2 g (0.1 mole) of the
diamine obtained in Example 4, Yield 67 g = 78%,
- m.p. 60C.
Example 54
This example demonstrates the volatility of the
new triazine stabilizers compared with a product of the
nearest state of the art.
The vola-tility figures were determined in an
apparatus for thermogravimetric analysis, For the
determination, equal quantities ~';00 mg) of the compounds
according to the invention and of -t~e comparison substance
were heated to 300C in a nitrogen atmosphere at a heating
1 ~64865
- 35 -
rate of 2 K¦mi~ute and the loss of substance was
measured in mg/cm2 of sample surface, The results
are shown in the table below.
. . .
Stabilizer Loss of weight in mg/cm2 on reaching ...,C
according tc 220 260 300 10 minutes at 300C
Example
.31 2.37 6. oo 7.58
14 .16 2,05 4,42 5;21
18 .31 0.95 2.84 3,-36
26 ,16 1. 58 3.48 4.42
Comparison~ ~. 47 3.48 10.59 17.38
~)substance according to Example 6 of ~erman Offenleg~ngs-
schrift 2,636,144
Example 55
This example is intended to demonstrate the light
stabilizing action of the new compounds in poly-~-
olefins.
100 parts by weight of polypropylene having a
melt index i5 (230C ) of approx. 6 g/10 minutes (deter-
mined as specified in ASTM D 1238-62 T) and a density of
O,90 were mixed with O.l part by weight of pentaerythri-
tyl tetrakis-3-(3,~-di-tert.-butyl-4-hydroxyphenyl)
propionate, 0,2 part by weight of calcium stearate and
O.l part by weight of the stabilizer according to the
invention to be.tested.
In order to achi.eve as uniform as poss~ble a
distributiorl on the polymer par-ticles, the stabilizers
were dissolved in a solvent and the so~ut;ion~as added
1 1~486~
-- 36
dropwise to the polypropylene powder, whilst stirring~
the bulk o~ the solvent being re-vaporized by simulta-
neous irradiation with an IR lamp,
After approx. 20 minutes, the calcium stearate
was added and mixing was continued for a further 10
minutes. Residues of solvent were removed by drying
at ~0C/120 minutes in a drying cabinet.
The polypropylene was injection molded at 240C
on a type SP 50 Windsor injection molding machine to
give sheets measuring 60 x 60 x 1 mm. Test speci-
mens were punched out from these sheets as specified in
DIN 53,4~5, type 3, reduced on a scale of 1:3. The
test specimens required as comparison samples were pre-
pared analogously, but omitting the stabilizer to be
tested or adding ths comparison stabilizers,
The stability to light was determined by sub-
jecting the samples to irradiation with alterna-ting
light in a Xenotest 1200 apparatus made by Original -
Hanau Quarzlampen GmbH. The intensity of radiation
was modulated by W filters (special filter glass, d -
1.7 mm), The fastness to light was tested as speci-
fied in DIN ~3,387 (17 minutes drying period, 3 minutes
sprinkling, black-body temperature 4~C and a relative
atmospheric humidity o~ 70 to '7~/ during the drying
period). The elongation at break was measured on a
tensile testing machine made by Instron at a draw-o~f
rate of 5 cm/minute after a specified period of exposure,
in hours.
1 16486
-- 37 -
_ , . . .
Stabilizer Period of e~xposure Measured elongation
according toin hours at break as % of
Example initial value
14 1,400 >50
1,400 ~ ~ 50
26 .1,400 > 50
polypropylene 260 .
comparison 1) 320 .
comparison 1,400 ..
1) with no light stabilizer
2) compound according to Example 6 of German Offenlegungs-
schrift 2,636,144
Example ~6
Using a laboratory high-speed mixer, a homogeneous
mixture is prepared from polypropylene powder
( ~ Hostalen PPU VP 1770 F of Hoechst AG) having a melt
index MFI 190/5 = 1.9 g/10 minutes, see DIN 53,53.~, and
the constituents of the formulation indicated below, and
is converted into granules. The material thus stabi-
lized is then melted in a laboratory extruder under thecustomary processing conditions and is processed via a
spinning pump having an 8-orifice spinneret to give mono-
filaments, which are then after-stretched in a ratio of
1:3, textured to give yarn of 40 dtex and processed to
give tes-t fabrics
100 parts by weigh~t of polypropylene,
0,2 part by weight of calcium stearatel
0,1 part by weight o~ 3,3-bis-(3-tert,-butyl-4-
.
1~648~5
-- 38 -
hydroxyphenyl)-butanoic acid ethylene glycol
ester,
0.1 par~ by weight of dioctadecyl disulfide and
0.3 part by weight of the stabilizer to be tested
The fabric samples are stretched oYer a perforated
piece of cardboard in such a way that a free aperture of
diameter approx. 15.5 mm remains. The test specimens
are exposed in this forrn in the Xenotest X 1200 as des-
cribed in the preceding Example. At specific intervals
of time, the fabrics are loaded centrally with a weight of
diameter 6 rmm, exerting a pressure of 0.1 N/mm2. The
breakthrough of the weight is taken as the -tirne of fail-
ure.
Stabilizer according Period of exposure
to Example in hours
~,100 4)
14 3 100 4)
26 3,100 4)
polypropylene ~ 280
20 comparison 1) 400
comparison 2) 1,400
comparison 3) 3,000
1) with no stabiliser
2) compound according to Example 1 of German Offenlegungs-
B~ 2~ schrift 2,719,131 (cornmercial product Tinuvin 622)
3) compound according to Example 6 of German Offenlegungs-
schrif-t 2,635,144
1 16~8~5
- 39 -
4) weight had not yet broken through
Example 57
The stabilized granules prepared as inthe preced-
ing example are processed on a laboratory film blowing
machine (screw diameter 25 mm, length 20 D), temperature
schedule 200, 240, 250 and 255C) to give blown fiims of
a thickness of approx, 70 ~m, These films are sub-
jected to artificial weathering in the Xenotest X 1200
as described, The carbonyl number is determined, as
a characteristic of damage, by a method based on DIN
53,383, part 2, (This is defined for PP as the ratio
of the extinction values at 1,71.5 cm 1 and 1,524 cm 1,
The disintegration of the test specimens into powder
begins at a C0 number > 2,)
Stabilizer according C=0 number after ,,, hours
to Example 500 1,000 2,000 2,500
.
< 0,1 ~ 0,1 0.3 0.4
14 ~ 0,1 < 0,1 0,3 0,5
26 C 0,1 ~ 0,1 0,3 0,5
20 polypropylene ~ 2 _ _
comparison 1) > 2 _ _
comparison _ > 2 _
comparison 3) 0,1 0,1 0,4 0,9
1)~ 2) and 3) correspond to the compari.son samples of the
previous exa~ple
