Urea derivatives, process for their manufacture and their use as light protecting agents for polymers

The amide nitrogen of 9,9-dimethyl-2-oxa-4-oxo-3,8-diazaspiro-(4,5)-decane reacts with isocyanates or diisocyanates to give novel urea derivatives which can be used as light stabilizers for plastic materials.

This invention relates to novel urea derivatives, to a process for their 
manufacture and to their use for stabilizing synthetic polymers against 
the detrimental influence of light. 
The novel urea derivatives derive from 
9,9-dimethyl-1-oxa-4-oxo-3,8-diazaspiro(4,5)decane and correspond to the 
formula I 
##STR1## 
in which R.sup.1 and R.sup.2 denote identical or different straight chain 
or branched alkyl radicals having from 1 to 12, preferably 1 to 6, carbon 
atoms, especially methyl; or R.sup.1 and R.sup.2 together with the carbon 
atoms to which they are linked denote an optionally methylsubstituted 
cyclopentane or cyclohexane ring or a 2,2,6,6-tetramethylpiperidine ring 
carbon atoms 4 of which is identical with carbon atom 7 of the spirodecane 
system; 
R.sup.3 denotes hydrogen, alkyl or isoalkyl having from 1 to 30, preferably 
1 to 10 and more preferably 1 to 6, carbon atoms, or aralkyl having from 7 
to 10 carbon atoms with 1 to 4 carbon atoms in the aliphatic chain; 
R.sup.4 denotes hydrogen, alkyl having from 1 to 30, preferably 1 to 17 and 
more preferably 1 to 11, carbon atoms, phenyl or naphthyl optionally 
substituted by a halogen atom, preferably chlorine, or alkyl having from 1 
to 4 carbon atoms, or denotes aralkyl with 7 to 10 carbon atoms with 1 to 
4 carbon atoms being in the aliphatic chain; 
R.sup.3 and R.sup.4 may also be together with the carbon atom by which they 
are linked a cycloalkane ring having from 4 to 20, preferably 5 to 12 and 
more preferably 5 to 7, carbon atoms which may be substituted by 1 or 2 
C.sub.1 to C.sub.4 alkyl radicals; 
R.sup.5 denotes hydrogen, oxygen or C.sub.1 -C.sub.4 alkyl, preferably 
hydrogen or methyl and more preferably hydrogen; 
R.sup.6, with n being 1, denotes alkyl having from 1 to 20, preferably from 
4 to 18, carbon atoms, alkenyl having from 2 to 18 carbon atoms, 
cycloalkyl having from 5 to 12, preferably 5 to 7 and more preferably 6, 
carbon atoms which may be substituted by a C.sub.1 -C.sub.4 alkyl radical; 
phenyl or naphthyl optionally substituted by a chlorine atom or alkyl 
having from 1 to 18, preferably 1 to 4, carbon atoms; or phenylalkyl 
having from 7 to 18, preferably 7 to 10, carbon atoms, or 
R.sup.6, with n being 2, denotes a straight chain or branched alkylene 
group having from 2 to B 20, preferably 2 to 12 and more preferably 2 to 
6, carbon atoms, or phenylene or naphthylene optionally substituted by 
C.sub.1 -C.sub.4 alkyl, or a diphenylenealkane radical having from 13 to 
18 carbon atoms. 
The nitrogen atom in position 8 or the ring has basic properties when it is 
substituted by hydrogen or alkyl, and, therefore, the compounds in these 
cases may also be in the form of salts with inorganic or organic acids. 
Radicals R.sup.1 and R.sup.2 denote for example, methyl, ethyl or isobutyl 
and radicals in which R.sup.1 and R.sup.2 form a ring together with the 
carbon atom to which they are bound are, for example, cyclopentyl, 
cyclohexyl or 2,2,6,6-tetramethyl-piperididyl. 
Examples of R.sup.3 are hydrogen, methyl, ethyl, propyl, butyl, pentyl, 
hexyl, heptyl, benzyl, examples for R.sup.4 are hydrogen, methyl, ethyl, 
propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, 
heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, 
undecyl, dodecyl, tridecyl, benzyl, phenyl, chlorophenyl, phenylethyl. 
Examples for those cases in which R.sup.3 and R.sup.4, together with carbon 
atom 2 of the ring to which they are linked, form a cycloalkyl ring are 
cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl and cyclododecyl. 
R.sup.5 denotes, for example hydrogen and lower alkyl, preferably methyl. 
In compounds with n=1 (monoisocyanates) R.sup.6 denotes for example methyl, 
ethyl, propyl, butyl, isobutyl, octadecyl, cyclohexyl, phenyl, 
3-chlorophenyl, 4-chlorophenyl, 3-methylphenyl, 4-methylphenyl, 
1-naphthyl. 
In compounds with n=2 (diisocyanates) R.sup.6 denotes for example, 
ethylene, hexamethylene, diphenylene methane, 4-methyl-m-phenylene. 
Examples of possible salts of the compounds of formula I are those with 
non-oxidizing inorganic acids, such as phosphates, phosphites, chlorides, 
sulfates and salts with organic mono- and polycarboxylic acids, such as 
acetates, laurates, stearates, succinates, sebacates, maleates, citrates, 
tartrates, oxalates, benzoates, sulfonates, phosphonates. The salts are 
prepared by combining equivalent amounts of acid and base, each dissolved 
in a solvent, and evaporating the solvent. 
From among the novel urea derivatives the following are named by way of 
example: 
2,2,7,7,9,9-hexamethyl-3-propyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5) 
-decane; 
2,2,7,7,9,9-hexamethyl-3-butyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5)- 
decane; 
2,2,7,7,9,9-hexamethyl-3-tert.-butyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro- 
(4,5)-decane; 
2,2,7,7,9,9-hexamethyl-3-octadecyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4 
,5)-decane; 
2,2,7,7,9,9-hexamethyl-3-cyclohexyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro-( 
4,5)-decane; 
2,2,7,7,9,9-hexamethyl-3-phenyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5) 
-decane; 
2,2,7,7,9,9-hexamethyl-3-m-chlorophenyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spi 
ro-(4,5)-decane; 
2,2,7,7,9,9-hexamethyl-3-p-chlorophenyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spi 
ro-(4,5)-decane; 
2,2,7,7,9,9-hexamethyl-3-.alpha.-naphthyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-s 
piro-(4,5)-decane; 
2-butyl-7,7,9,9-tetramethyl-3-octadecyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spi 
ro-(4,5)-decane; 
2-iso-pentyl-7,7,9,9-tetramethyl-3-cyclohexyl-carbamoyl-1-oxa-4-oxo-3,8-dia 
za-spiro-(4,5)-decane; 
2-iso-nonyl-7,7,9,9-tetramethyl-3-butyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spi 
ro-(4,5)-decane; 
2-undecyl-7,7,9,9-tetramethyl-3-octadecyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-s 
piro-(4,5)-decane; 
2-phenyl-7,7,9,9-tetramethyl-3-phenyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro 
-(4,5)-decane; 
2-phenyl-7,7,9,9-tetramethyl-3-octadecyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-sp 
iro-(4,5)-decane; 
2-propyl-2,7,7,9,9-pentamethyl,3-propyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spi 
ro-(4,5)-decane; 
2-iso-butyl-2,7,7,9,9-pentamethyl-3-cyclohexyl-carbamoyl-1-oxa-4-oxo-3,8-di 
aza-spiro-(4,5)-decane; 
2-iso-octyl-7,7,9,9-tetramethyl-3-cyclohexyl-carbamoyl-1-oxa-4-oxo-3,8-diaz 
a-spiro-(4,5)-decane; 
2-nonyl-2,7,7,9,9-pentamethyl-3-octadecyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-s 
piro-(4,5)-decane; 
2,2-diethyl-7,7,9,9-tetramethyl-3-butyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spi 
ro-(4,5)-decane; 
2,2-diethyl-7,7,9,9-tetramethyl-3-cyclohexyl-carbamoyl-1-oxa-4-oxo-3,8-diaz 
a-spiro-(4,5)-decane; 
2,2-diethyl-7,7,9,9-tetramethyl-3-octadecyl-carbamoyl-1-oxa-4-oxo-3,8-diaza 
-spiro-(4,5)-decane; 
2,2-diethyl-7,7,9,9-tetramethyl-3-phenyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-sp 
iro-(4,5)-decane; 
2,2-dipropyl-7,7,9,9-tetramethyl-3-butyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-sp 
iro-(4,5)-decane; 
2,2-dibutyl-7,7,9,9-tetramethyl-3-octadecyl-carbamoyl-1-oxa-4-oxo-3,8-diaza 
-spiro-(4,5)-decane; 
2-ethyl-2-pentyl-7,7,9,9-tetramethyl-3-cyclohexyl-carbamoyl-1oxa-4-oxo-3,8- 
diaza-spiro-(4,5)-decane; 
2,2-dibenzyl-7,7,9,9-tetramethyl-3-phenyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-s 
piro-(4,5)-decane; 
2,2,4,4-tetramethyl-14-butyl-carbamoyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1 
,5,2)-pentadecane; 
2,2,4,4-tetramethyl-14-cyclohexyl-carbamoyl-7-oxa-3,14-diaza-15-oxo-dispiro 
-(5,1,5,2)-pentadecane; 
2,2,4,4-tetramethyl-14-phenyl-carbamoyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5, 
1,5,2)-pentadecane; 
n-hexane-1',6'-bis-[3-carbamoyl-2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8-diaz 
a-spiro-(4,5)-decane]; 
toluylene-2',4'-bis-[3-carbamoyl-2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8-dia 
za-spiro-(4,5)-decane]; 
n-hexane-1',6'-bis-[14-carbamoyl-2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15-ox 
o-dispiro-(5,1,5,2)-pentadecane]; 
toluylene-2',4'-bis-[14-carbamoyl-2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15-o 
xo-dispiro-(5,1,5,2)-pentadecyl]; 
n-hexane-1',6'-bis-[20-carbamoyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-ox 
o-dispiro-(5,1,11,2)-heneicosane]; 
toluylene-2',4'-bis-[20-carbamoyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-o 
xo-dispiro-(5,1,11,2)-heneicosane]; 
n-hexane-1',6'-bis-[3-carbamoyl-2,2-diethyl-7,7,9,9-tetramethyl-1-oxa-4-oxo 
-3,8-diaza-spiro-(4,5)-decane]; 
toluylene-2',4'-bis-[3-carbamoyl-2,2-diethyl-7,7,9,9-tetramethyl-1-oxa-4-ox 
o-3,8-diaza-spiro-(4,5)-decane]; 
n-hexane-1',6'-bis-[3-carbamoyl-2-iso-octyl-7,7,9,9-tetramethyl-1-oxa-4-oxo 
-3,8-diaza-spiro-(4,5)-decane]; 
toluylene-2',4'-bis-[3-carbamoyl-2,2-diethyl-7,7,9,9-tetramethyl-1-oxa-4-ox 
o-3,8-diaza-spiro-(4,5)-decane]; 
n-hexane-1',6'-bis-[3-carbamoyl-2-iso-octyl-7,7,9,9-tetramethyl-1-oxa-4-oxo 
-3,8-diaza-spiro-(4,5)-decane]. 
The different nomenclature of some of the compounds listed above results 
from the IU regulations (cf. Hellwinkel, "Die systematische Nomenklatur 
der organischen Chemie"; Spinger-Verlag, Heidelberg). 
The novel compounds of formula I are produced by reacting substituted 
piperidines of the formula III, obtainable by the process disclosed in 
German Offenlegungshrift No. 2,606,026, with isocyanates or diisocyanates 
of the formula II. The reaction is illustrated by the following equation: 
##STR2## 
in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 are as defined 
above and n is 1 or 2 according to the functionality of the isocyanate. It 
is especially surprising that compounds of formula III in which R.sup.5 
denotes hydrogen also react with the isocyanates in the manner indicated 
above and not at the amine nitrogen in position 8. 
To carry out the reaction the piperidine derivative is dissolved in an 
inert organic solvent, a catalytic amount of a strong base, for example 
1,4-diazabicyclooctane is added, the equivalent amount of the isocayanate, 
optionally in the same solvent, is added dropwise and the mixture is 
allowed to react at 20.degree. to 180.degree. C., preferably 20.degree. to 
140.degree. C. and more preferably 50.degree. to 120.degree. C. The 
reaction time is from 1 to 30 and preferably 4 to 20 hours. 
Suitable inert organic solvents are, for example, heptane, aliphatic 
hydrocarbon fractions having a boiling temperature of up to 180.degree. 
C., toluene, xylene, diethyl ether, dioxane, halo-hydrocarbons such as 
chloroform, carbon tetrachloride and chlorobenzene, preferably, however, 
toluene. 
Difficulty soluble reaction products are separated by filtration, while 
with dissolved products the solvent is evaporated and the remaining 
reaction product is purified by recrystallization. 
The novel urea derivatives are excellently suitable for stabilizing 
synthetic polymers against the decomposing action of light. Synthetic 
polymers in the sense of the present specification are halogen-free and 
halogen-containing homo- and copolymers, more particularly homopolymers of 
olefins, dienes and styrene, such as for example, polyethylene of low and 
high density, polypropylene, polystyrene, polybutadiene and polyisoprene; 
copolymers of olefins, dienes and styrene with one another or with other 
olefinically unsaturated monomers, such as, for example, 
ethylene-propylene copolymers, ethylene-butene copolymers, 
styrene-butadiene copolymers, ethylene-vinyl acetate copolymers and 
acrylonitrile and acrylonitrile-butadienestyrene copolymers, homopolymers 
of vinyl chloride and vinylidene chloride as well as copolymers of the 
said monomers with one another and with other olefinically unsaturated 
monomers. The term synthetic polymer is also intended to include 
polyurethanes, polyacetals, polyesters, polyamides, polyacrylates and 
epoxide resins. Especially good results are obtained with 
poly-.alpha.-olefins such as polyethylenes and preferably polypropylenes 
and with vinyl chloride polymers. 
It is surprising and could not have been foreseen that the compounds 
according to the invention are distinctly superior in their UV stabilizing 
effect to compounds as described in German Offenlungungsschrift Nos. 
2,500,313; 1,770,689 and 1,769,646 having similar structures, i.e. ureas 
or spirodecanes with similar basic skeleton. Rather, it could be supposed 
that, due to the insignificant modifications of the structure, the 
compounds would have the same effect or even a somewhat inferior effect 
and, owing to their polarity, would exhibit a poorer compatibility, 
especially with non polar polymers, for example polyolefins. 
The novel compounds with stabilizing effect are incorporated into the 
polymer mass by customary methods. Alternatively, a solution, suspension 
or emulsion of the stabilizer can be mixed with the polymer per se or with 
a solution, suspension or emulsion thereof, whereupon the solvent is 
removed. 
The stabilizers according to the invention can be used either alone or in 
admixture with one or several stabilizers generally used in plastics 
processing, for example antioxydants on phenol and sulfide basis, UV 
absorbers and light protecting agents, phosphite stabilizers, metal 
compounds, epoxide stabilizers and polyhydric alcohols. The plastics 
compositions to be stabilized may further contain flame retardants and 
pigments, dyestuffs, antistatic agents and fillers, for example glass 
fibers. 
Examples of suitable antioxydants are those of the type of sterically 
hindered phenols, for example 2,6-di-tert.butyl-p-cresol, 
2,6-dioctadecyl-p-cresol, 4,4'-butylidene-bis(2,6-di-tert.butyl-phenol), 
4,4'-thio-bis(2-tert.butyl-5-methyl-phenol), phenolic triazine compounds, 
thiodipropionic acid esters of fatty alcohols, dioctadecyl sulfide and 
disulfide. 
UV absorbers and light protecting agents to be used are, for example, 
2-(2'-hydroxyphenyl)-benztriazoles such as 
2-(2'-hydroxy-5'-methylphenyl)-benztriazole, 2-hydroxybenzophenones such 
as 2-hydroxy-4-octoxy-benzophenone, stabilizers of the salicylate group 
such as octylphenyl salicylate, nickel chelates, oxalic acid diamides and 
sterically hindered piperidine compounds. 
Suitable phosphite stabilizers are trisnonylphenyl phosphite, trislauryl 
phosphite and esters of pentaerythritol phosphite. 
Metal compounds known as stabilizers include calcium, barium, strontium, 
zinc, cadmium, magnesium, aluminum and lead soaps of aliphatic carboxylic 
acids or oxycarboxylic acids having about 12 to 32 carbon atoms, salts of 
the said metals with aromatic carboxylic acids such as benzoates or 
salicylates as well as (alkyl)phenolates of the aforesaid metals, 
organotin compounds, for example di-alkyl-tin thioglycolates and 
carboxylates. 
Known epoxide stabilizers are, for example, epoxidized higher fatty acids, 
such as epoxidized soybean oil, tall oil, linseed oil, or epoxidized butyl 
oleate, and epoxides of long chain olefins. 
Polyhydric alcohols to be used are, for example, pentaerythritol, 
trimethylolpropane, sorbitol or mannitol, i.e. preferably alcohols having 
5 or 6 carbon atoms and 3 to 6 hydroxy groups. 
An efficient stabilizer combination for poly-.alpha.-olefins, such a high, 
medium and low pressure polymers of C.sub.2 to C.sub.4 -.alpha.-olefins, 
especially polyethylene and polypropylene, or copolymers of the said 
.alpha.-olefins consists, for example of 0.01 to 5 parts by weight of a 
compound according to the invention, 0.05 to 5 parts of a phenolic 
stabilizer, optionally 0.01 to 5 parts by weight of a sulfur-containing 
costabilizer, optionally 0.01 to 3 parts by weight of a basic or neutral 
metal soap, such as calcium stearate or zinc stearate, optionally 0.1 to 5 
parts by weight of a phosphite and optionally 0.01 to 5 parts by weight of 
a known UV stabilizer from the group of alkoxyhydroxybenzophenones, 
hydroxyphenylbenztriazoles, benzylidene-malonic acid mononitrile esters, 
or so-called quenchers, for example nickel chelates, all parts being 
calculated on 100 parts by weight of polymer.

The following examples illustrate the invention. The structures of the 
compounds obtained were determined by nuclear resonance spectroscopy, 
their composition was determined by elemental analysis. 
EXAMPLE 1 
2,2,7,7,9,9-Hexamethyl-3-propyl-carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5) 
-decane 
12.0 g (0.05 mol) of 
2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5)-decane, 4.25 g 
(0.05 mol) of propyl isocyanate, 0.1 g 1,4-diazabicyclooctane and 100 ml 
of absolute toluene were refluxed for 15 hours while stirring. The toluene 
was then distilled off and the residue recrystallized from heptane; m.p. 
119.degree. C. stearate m.p. 87.degree. C.; succinate m.p. 169.degree. C.; 
p.-tert-butylbenzoate m.p. 217.degree. C. 
EXAMPLES 2 TO 22 
The compounds listed in the following table were prepared under the 
conditions of Example 1. 
TABLE 
__________________________________________________________________________ 
Examples 2 to 22 
Ex. 
starting material process product 
No. 
spiro compound isocyanate 
carbamoyl compound m.p. 
__________________________________________________________________________ 
.degree.C. 
2 2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8 
C.sub.4 H.sub.9 NCO 
2,2,7,7,9,9-hexamethyl-3-butyl-carbamoyl-1 
- 90-93 
diaza-spiro-(4,5)-decane oxa-4-oxo-3,8-diaza-spiro-(4,5)-decane 
3 2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8- 
t.-C.sub.4 H.sub.9 NCO 
2,2,7,7,9,9-hexamethyl-3-tert.-butyl-carba 
moyl- 95 
diaza-spiro-(4,5)-decane 1-oxa-4-oxo-3,8-diaza-spiro-(4,5)-decane 
4 2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8- 
C.sub.18 H.sub.37 NCO 
2,2,7,7,9,9-hexamethyl-3-octadecyl-carbamo 
yl- 51-53 
diaza-spiro-(4,5)-decane 1-oxa-4-oxo-3,8-diaza-spiro-(4,5)-decane 
5 2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8- 
C.sub.6 H.sub.11 NCO 
2,2,7,7,9,9-hexamethyl-3-cyclohexyl-carbam 
oyl- 123-125 
diaza-spiro-(4,5)-decane 1-oxa-4-oxo-3,8-diaza-spiro-(4,5)-decane 
6 2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8- 
C.sub.6 H.sub.5 NCO 
2,2,7,7,9,9-hexamethyl-3-phenyl-carbamoyl- 
1- 144-147 
diaza-spiro-(4,5)-decane oxa-4-oxo-3,8-diaza-spiro-(4,5)-decane 
7 2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8- 
(CH.sub.2).sub.6 (NCO).sub.2 
n-hexane-1',6'-bis-[3-carbamoyl-2,2,7,7,9, 
9- 191-194 
diaza-spiro-(4,5)-decane hexamethyl-1-oxa-4-oxo-3,8-diaza-spiro-(4, 
5)- 
decane] 
8 2,2,7,7,9,9-hexamethyl-1-oxa-4-oxo-3,8 
toluylene-2,4- 
toluylene-2',4'-bis-[3-carbamoyl-2,2,7,7,9 
,9- 186 
diaza-spiro-(4,5)-decane 
diisocyanate 
hexamethyl-1-oxa-4-oxo-3,8-diaza-spiro-(4, 
5)- 
decane] 
9 2,2-diethyl-7,7,9,9-tetramethyl-1-oxa- 
C.sub.4 H.sub.9 NCO 
2,2-diethyl-7,7,9,9-tetramethyl-3-butyl-ca 
rb- 105-108 
4-oxo-3,8-diaza-spiro-(4,5)-decane 
amoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5)-de 
cane 
10 2,2-diethyl-7,7,9,9-tetramethyl-1-oxa- 
C.sub.6 H.sub.11 NCO 
2,2-diethyl-7,7,9,9-tetramethyl-3-cyclohex 
yl- 
4-oxo-3,8-diaza-spiro-(4,5)-decane 
carbamoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5 
)-decane 
11 2,2-diethyl-7,7,9,9-tetramethyl-1-oxa-4- 
C.sub.6 H.sub.5 NCO 
2,2-diethyl-7,7,9,9-tetramethyl-3-phenyl-c 
arb- 110-112 
oxo-3,8-diaza-spiro-(4,5)-decane 
amoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5)-de 
cane 
12 2,2-diethyl-7,7,9,9-tetramethyl-1-oxa-4- 
(CH.sub.2).sub.6 (NCO).sub.2 
n-hexane-1',6'-bis-[3-carbamoyl-2,2-diethy 
l- 130-131 
oxo-3,8-diaza-spiro-(4,5)-decane 
7,7,9,9-tetramethyl-1-oxa-4-oxo-3,8-diaza- 
spiro- 
(4,5)-decane] 
13 2,2-diethyl-7,7,9,9-tetramethyl-1-oxa-4- 
toluylene-2,4 
toluylene-2',4'-bis-[3-carbamoyl-2,2-dieth 
yl- 190 
oxo-3,8-diaza-spiro-(4,5)-decane 
diisocyanate 
7,7,9,9-tetramethyl-1-oxa-4-oxo-3,8-diaza- 
spiro- 
(4,5)-decane] 
14 2-iso-octyl-7,7,9,9-tetramethyl-1-oxa-4- 
C.sub.6 H.sub.11 NCO 
2-iso-octyl-7,7,9,9-tetramethyl-3-cyclohex 
yl-carb- 93-97 
oxo-3,8-diaza-spiro-(4,5)-decane 
amoyl-1-oxa-4-oxo-3,8-diaza-spiro-(4,5-)-d 
ecane 
15 2-iso-octyl-7,7,9,9-tetramethyl-1-oxa-4- 
(CH.sub.2).sub.6 (NCO).sub.2 
n-hexane-1',6'-bis-[3-carbamoyl-2-iso-octy 
l- waxy 
oxo-3,8-diaza-spiro-(4,5)-decane 
7,7,9,9-tetramethyl-1-oxa-4-oxo-3,8-diaza- 
spiro- 
(4,5)-decane] 
16 2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15- 
C.sub.4 H.sub.9 NCO 
2,2,4,4-tetramethyl-14-butyl-carbamoyl-7-o 
xa- 103-106 
oxo-dispiro-(5,1,5,2)-pentadecane 
3,15-diaza-15-oxo-dispiro-(5,1,5,2)-petand 
ecane 
17 2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15- 
C.sub.6 H.sub.11 NCO 
2,2,4,4-tetramethyl-14-cyclohexyl-carbamoy 
l-7-oxa- 153 
oxo-dispiro-(5,1,5,2)-pentadecane 
3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentad 
ecane 
18 2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15- 
C.sub.6 H.sub.5 NCO 
2,2,4,4-tetramethyl-14-phenyl-carbamoyl-7- 
oxa- 156-158 
oxo-dispiro-(5,1,5,2)-pentadecane 
3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentad 
ecane 
19 2,2,4,4-tetramethyl-7-oxa-3,14-diaza- 
(CH.sub.2).sub. 6 (NCO).sub.2 
n-hexane-1',6'-bis[14-carbamoyl-2,2,4,4- 
15-oxo-dispiro-(5,1,5,2)-pentadecane 
tetramethyl-7-oxa-3,14-diaza-15-oxo-dispir 
o- 
(5,1,5,2)-pentadecane] 
20 2,2,4,4-tetramethyl-7-oxa-3,14-diaza- 
toluylene- 
toluylene-2',4'-bis-[14-carbamoyl-2,2,4,4- 
158 
15-oxo-dispiro-(5,1,5,2)-pentadecane 
2,4-diiso- 
tetramethyl-7-oxa-3,14-diaza-15-oxo-dispir 
o- 
cyanate (5,1,5,2)-pentadecane] 
21 2,2,4,4-tetramethyl-7-oxa-3,20-diaza- 
(CH.sub.2).sub.6 (NCO).sub.2 
n-hexane-1',6'-bis-[20-carbamoyl-2,2,4,4- 
21-oxo-dispiro-(5,1,11,2)-heneicosane 
tetramethyl-7-oxa-3,20-diaza-21-oxo-dispir 
o- 
(5,1,11,2)-heneicosane] 
22 2,2,4,4-tetramethyl-7-oxa-3,20-diaza- 
toluylene- 
toluylene-2',4'-bis-[20-carbamoyl-2,2,4,4- 
21-oxo-dispiro-(5,1,11,2)-heneicosane 
2,4-diiso- 
tetramethyl-7-oxa-3,20-diaza-21-oxo-dispir 
o- 
cyanate (5,1,11,2)-heneicosane] 
__________________________________________________________________________ 
EXAMPLE 23 
This example demonstrates the light stabilizing effect of the compounds 
according to the invention when used in a poly-.alpha.-olefin. 
100 parts by weight of polypropylene having a melting index i.sub.5 of 
about 6 g/10 min (determined according to ASTM D 1238-62 T) and a density 
of 0.96 g/cc were blended with 
0.1 part by weight of 
pentaerythrityl-tetrakis-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate, 
0.2 part by weight of calcium stearate and 
0.1 part by weight of the stabilizer of the invention. 
To ensure as uniform as possible a distribution on the polymer particles 
the stabilizers were dissolved in a solvent and the solution was added 
dropwise to the polypropylene powder while stirring and simultaneously 
exposing the mixture to the radiation of an IR lamp for evaporating the 
major portion of the solvent. After about 20 minutes, the calcium stearate 
was added and mixing was continued for another 10 minutes. Solvent 
residues were removed by drying for 120 minutes at 50.degree. C. in a 
drying cabinet. 
On a Windsor injection molding machine of the type SP 50 plates of the 
dimensions 60.times.60.times.1 mm were molded at 250.degree. C. and test 
specimens were cut out according to DIN 53 455, form 3, reduced scale 1:3. 
The test specimens used for comparison were made in analogous manner but 
without addition of the stabilizer of the invention (test g) and with the 
use of known stabilizers (tests e and f). 
The stability to light of the specimens was tested in a Xenotest-450 
apparatus of Original Hanau Quarzlampen GMBH with a combination of 6 IR 
and 1 UV filters according to DIN 53 387 (accelerated test of weathering 
resistance). During the exposure to light the blackpanel temperature was 
43.degree. C..+-.1.degree. C. and the relative humidity in the test 
chamber was 70.+-.1%. Every 2 hours fresh air was passed through the test 
chamber for 5 minutes. The elongation at break was determined on a tensile 
tester of Messrs. Instrom at a draw off speed of 5 cm/min after a defined 
period of radiation. The test results are listed in the following table. 
The stability factor results from the relation of the time of exposure of 
the stabilized test specimen to the time of exposure of the non stabilized 
test specimen, in each case after a time of radiation after which the 
elongation at break had dropped to one half of its initial value. 
______________________________________ 
Test stabilizer of Example 
stability factor 
______________________________________ 
(a) 5 4.5 
(b) 8 4.5 
(c) 19 5.0 
(d) 21 5.0 
(e) benzophenone stabilizer .sup.1 
2.5 
(f) benzotriazole stabilizer .sup.2 
2.5 
(g) control (without stabilizer) 
1 
______________________________________ 
.sup.1 2hydroxy-4-n-octyloxybenzophenone 
.sup.2 2(2-hydroxy-3',5di-tert.butylphenyl 5chlorobenzotriazole