Azodicarboxylic acid derivatives containing hindered amine moieties as polymer stabilizers

The instant invention relates to novel hydrazine derivatives of formula III ##STR1## where R.sub.1 is hydrogen, oxyl, hydroxyl, alkyl, of 2 to 4 carbon atoms substituted by one hydroxyl group, allyl, benzyl, benzyl substituted by one of two alkyl of 1 to 4 carbon atoms or alkanoyl of 1 to 8 carbon atoms, and X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen or alkyl. These compounds are useful as intermediates from which to prepare the corresponding azo compounds, which are useful for the stabilization of polymers, particularly unsaturated elastomers, by being grafted thereon.

The instant invention pertains to novel azodicarboxylic acid derivatives 
and to polymer compositions stabilized therewith. 
BACKGROUND OF THE INVENTION 
U.S. Pat. No. 4,255,536 teaches that selected azodicarboxylates are useful 
to modify copolymers containing residual unsaturation. 
S. S. Ivanov et at. disclose in Rubber Chem. and Tech., 30, 895 (1957) the 
reaction of azodicarboxylates with rubber to form branched and crosslinked 
derivatives. 
D. S. Campbell et al., Polymer 19, 1107 (1978) and Polymer 20, 393 (1979) 
disclose the efficient grafting of polystyrene containing reactive 
azodicarboxylate units onto polydienes both in solution and in the absence 
of a solvent. 
D. N. Schulz et al., Macromolecules 13, 1367 (1980) describe the 
azodicarboxylate modification of polybutadienes with respect to structure 
reactivity and structure property relationships. 
On the other hand, the potential use of a light stabilizer containing an 
azodicarboxylic acid derivative to modify unsaturated elastomers and 
thereby incorporating the light stabilizer into the vulnerable unsaturated 
backbone of polymers such as ABS, impact polystyrene (IPS), high impact 
polystyrene (HIPS), SBS, SIS, polybutadiene (PB), polyisoprene (PI), 
emulsion SBR, EPDM, AES and ASA is not implied in any of the above 
references. The resulting polymers containing the light stabilizer exhibit 
greatly improved light stability. 
Rubber modified polymers such as ABS and HIPS and several thermoplastics 
such as polypropylene (PP)/EPDM, PP/NBR, PP/NR and the like are 
susceptible to light induced oxidative degradation attributed mainly to 
the unsaturated diene phase. The instant invention locates the light 
stabilizer in the vulnerable diene phase through a covalent bond via the 
thermalene reaction of these polymers with compounds of the instant 
invention. The additive grafts to the polymer backbone during a reactive 
processing step. In addition to improved light stability, binding of the 
additive during processing imparts a high degree of permanence. The 
physical loss of stabilizer additive and migration of said additive is 
thus minimized during demanding end-use application. Also, non-migrating 
polymer-bound stabilizer additive can find use in medical and other 
applications requiting FDA regulation (such as in materials coming into 
contract with food). Thus, decreased volatility and diffusion and 
extraction resistance are desirable properties resulting from additives 
which are grafted onto a substrate. 
In alloys and blends such as ABS/polycarbonate (PC), the location of the 
stabilizer containing a grafted hindered amine light stabilizer moiety 
only in the ABS phase would prevent its migration to PC where it is highly 
detrimental. Similar advantages could be foreseen in other polymer blends 
containing one or more components having unsaturated double bonds present. 
Examples of such polymer blends are EPDM/PP, NBR/PP, NP/PP, 
NR/polyphenylene oxide (PPO), emulsion SBR, ABS/nylon, ABS/PVC, 
ABS/polyester and the like. 
OBJECTS OF THE INVENTION 
One object of the instant invention is to provide new azodicarboxylic acid 
derivatives. 
Another object of the invention is to provide novel asymmetrical azo 
derivatives. 
Still another object of the invention is to provide stabilized polymer 
compositions stabilized by the presence of said azodicarboxylic acid 
derivative and/or said asymmetrical azo derivative. 
Still yet another object is to provide new hydrazine derivatives useful as 
hindered amine stabilizers. 
DETAILED DISCLOSURE 
The instant invention pertains to an azodicarboxylic acid derivative of 
formula I 
##STR2## 
where 
R.sub.1 is hydrogen, oxyl, hydroxyl, alkyl of 1 to 8 carbon atoms, alkyl of 
2 to 4 carbon atoms substituted by one hydroxyl group, allyl, benzyl, 
benzyl substituted by one of two alkyl of 1 to 4 carbon atoms, alkoxy of 1 
to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or alkanoyl of 1 
to 8 carbon atoms, and 
X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen, alkyl of 1 to 18 
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 
carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one alkoxy group 
of 1 to 12 carbon atoms or a group of formula II 
##STR3## 
in which R.sub.1 is as defined above. 
Preferably, R.sub.1 is alkyl of 1 to 4 carbon atoms, alkyl of 2 or 3 carbon 
atoms substituted by one hydroxyl group, alkoxy of 1 to 12 carbon atoms, 
cycloalkoxy of 5 or 6 carbon atoms or alkanoyl of 1 to 4 carbon atoms. 
Preferably, X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen, butyl or 
dodecyl or a group of formula II. 
Most preferably, R.sub.1 is methyl, 2-hydroxyethyl, methoxy, heptyloxy, 
octyloxy, cyclohexyloxy, formyl or acetyl. 
Most preferably, X is --O--. 
When any of R.sub.1 or R.sub.2 is or is a group substituted by alkyl, such 
alkyl groups are, for example, methyl, ethyl, isopropyl, n-butyl, 
tert-butyl, tert-amyl, 2-ethylhexyl, n-octyl, lauryl, n-tetradecyl, 
n-octadecyl or eicosyl; when said radicals are cycloalkyl, they are, for 
example, cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl; when said 
radicals are phenylalkyl, they are, for example, benzyl, phenethyl, 
a-methylbenzyl, .alpha.,.alpha.-dimethylbenzyl; when said radicals are 
alkoxy or cycloalkoxy, they are, for example, methoxy, butyloxy, amyloxy, 
heptyloxy, octyloxy, nonyloxy, dodecyloxy, octadecyloxy, cyclopentyloxy or 
cyclohexyloxy; when said radicals are hydroxyalkyl or alkoxyalkyl, they 
are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 
2-ethyloxyethyl, 2-butyloxyethyl; when R.sub.1 is alkanoyl, it is, for 
example, formyl, acetyl, propionyl, butyryl, valeroyl, caproyl or 
caprylyl. 
The instant compounds are prepared in a two-step sequence. In the first 
step, an appropriate 1-substituted 4-amino-, 4-alkylamino- or 
4-hydroxy-2,2,6,6-tetramethylpiperidine is converted into the 
corresponding hydrazine dicarboxylic acid diamide or hydrazine 
dicarboxylic acid diester derivative. This conversion is accomplished 
either by a transesterification reaction of the hindered amine with 
dimethylhydrazine dicarboxylate or by the reaction of chloroformic ester 
or amide (prepared from a hindered amine derivative and phosgene) with 
hydrazine hydrate. 
In the second step, the hydrazine dicarboxylic acid diester or diamide is 
oxidized to prepare the instant compounds, namely azodicarboxylic acid 
esters and amides. Among the oxidizing agents which can be employed are 
fuming nitric acid, lead peroxide in cold dilute sulfuric acid, lead 
tetraacetate, t-butylhypochlorite, manganese dioxide, calcium 
hypochlorite, N-bromosuccinimide, nitrogen tetroxide and iodobenzene 
diacetate. 
The instant invention also pertains to a stabilized polymer composition 
which comprises 
(a) a polymer, copolymer or polymer blend which contains in at least one 
polymer or polymer component significant ethylenic unsaturation, and 
(b) an effective stabilizing amount of an azodicarboxylic acid derivative 
grafted to said polymer or polymer component, said derivative having 
before grafting the structure of formula I 
##STR4## 
where R.sub.1 is hydrogen, oxyl, hydroxyl, alkyl of 1 to 8 carbon atoms, 
alkyl of 2 to 4 carbon atoms substituted by one hydroxyl group, allyl, 
benzyl, benzyl substituted by one of two alkyl of 1 to 4 carbon atoms, 
alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or 
alkanoyl of 1 to 8 carbon atoms, and 
X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen, alkyl of 1 to 18 
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 
carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one alkoxy group 
of 1 to 12 carbon atoms or a group of formula II 
##STR5## 
in which R.sub.1 is as defined above. 
Additionally, the intermediate hydrazine derivatives of formula III 
##STR6## 
where R.sub.1 is hydrogen, oxyl, hydroxyl, alkyl of 1 to 8 carbon atoms, 
alkyl of 2 to 4 carbon atoms substituted by one hydroxyl group, allyl, 
benzyl, benzyl substituted by one or two alkyl of 1 to 4 carbon atoms or 
R.sub.1 is an alkanoyl of 1 to 8 carbon atoms, and 
X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen, alkyl of 1 to 18 
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 
carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one alkoxy group 
of 1 to 12 carbon atoms or a group of formula II 
##STR7## 
in which R.sub.1 is as defined above. 
Some compounds of general formula III are described in U.S. Pat. No. 
5,204,473 where the N-atom of the piperidine moiety is substituted by an 
alkoxy, cycloalkoxy, alkenoxy or similar group. 
Further, the instant invention relates to asymmetrical compounds which are 
azo derivatives of formula IV 
##STR8## 
where R.sub.1 is hydrogen, oxyl, hydroxyl, alkyl of 1 to 8 carbon atoms, 
alkyl of 2 to 4 carbon atoms substituted by one hydroxyl group, allyl, 
benzyl, benzyl substituted by one or two alkyl of 1 to 4 carbon atoms, 
alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or 
alkanoyl of 1 to 8 carbon atoms; 
X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen, alkyl of 1 to 18 
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 
carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one alkoxy group 
of 1 to 12 carbon atoms or a group of formula II 
##STR9## 
in which R.sub.1 is as defined above; and E is a substituted or 
unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted 
cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted aryl of 6 
to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms, or 
E is --CONHR.sub.4, --CSNHR.sub.5, --COR.sub.6 COR.sub.7, --COR.sub.8 
CONHR.sub.9, --COR.sub.10, --COOR.sub.11 or --SO.sub.2 R.sub.12, 
in which R.sub.4, R.sub.5, R.sub.7, R.sub.9, R.sub.10, R.sub.11 and 
R.sub.12 are each independently of the other hydrogen, substituted or 
unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted 
cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted aryl of 6 
to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms; and 
R.sub.6 and R.sub.8 are each independently of the other a substituted or 
unsubstituted alkylene of 1 to 12 carbons. 
Preferably in formula IV, R.sub.1 is alkyl of 1 to 4 carbon atoms, alkyl of 
2 or 3 carbon atoms substituted by one hydroxyl group, alkoxy of 1 to 12 
carbon atoms, cycloalkoxy of 5 or 6 carbon atoms or alkanoyl of 1 to 4 
carbon atoms. Most preferably in formula IV, R.sub.1 is methyl, 
2-hydroxyethyl, methoxy, heptyloxy, octyloxy, cyclohexyloxy, formyl or 
acetyl. 
Preferably, X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen, butyl or 
dodecyl or a group of formula II. Most preferably, X is --O--. 
When any of R.sub.1 or R.sub.2 is or is a group substituted by alkyl, such 
alkyl groups are, for example, methyl, ethyl, isopropyl, n-butyl, 
tert-butyl, tert-amyl, 2-ethylhexyl, n-octyl, lauryl, n-tetradecyl, 
n-octadecyl or eicosyl; when said radicals are cycloalkyl, they are, for 
example, cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl; when said 
radicals are phenylalkyl, they are, for example, benzyl, phenethyl, 
.alpha.-methylbenzyl, .alpha.,.alpha.-dimethylbenzyl; when said radicals 
are alkoxy or cycloalkoxy, they are, for example, methoxy, butyloxy, 
amyloxy, heptyloxy, octyloxy, nonyloxy, dodecyloxy, octadecyloxy, 
cyclopentyloxy or cyclohexyloxy; when said radicals are hydroxyalkyl or 
alkoxyalkyl, they are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 
3-hydroxypropyl, 2-ethyloxyethyl, 2-butyloxyethyl; when R.sub.1 is 
alkanoyl, it is, for example, formyl, acetyl, propionyl, butyryl, 
valeroyl, caproyl or caprylyl. 
Preferably, when E is alkyl, cycloalkyl, aryl or phenylalkyl, E is a 
substituted or unsubstituted alkyl of 1 to 12 carbon atoms, substituted or 
unsubstituted cycloalkyl of 5 to 8 carbon atoms, substituted or 
unsubstituted phenyl, or substituted or unsubstituted phenylalkyl of 7 to 
14 carbon atoms. Most preferably, E is a substituted or unsubstituted 
alkyl of 1 to 10 carbon atoms, substituted or unsubstituted cyclohexyl, 
substituted or unsubstituted phenyl, or phenylalkyl of 7 to 9 carbon 
atoms. 
Preferably, when E is --CONHR.sub.4 or --CSNHR.sub.5, R.sub.4 and R.sub.5 
each independently of the other are a substituted or unsubstituted alkyl 
of 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl of 5 to 8 
carbon atoms, substituted or unsubstituted phenyl, or substituted or 
unsubstituted phenylalkyl of 7 to 14 carbon atoms. Most preferably, 
R.sub.4 and R.sub.5 are each independently of the other a substituted or 
unsubstituted alkyl of 1 to 10 carbon atoms, substituted or unsubstituted 
cyclohexyl, substituted or unsubstituted phenyl, or phenylalkyl of 7 to 9 
carbon atoms. 
When E is --COR.sub.6 COR.sub.7 or --COR.sub.8 CONHR.sub.9, preferably, 
R.sub.6 and R.sub.8 are each independently of the other a substituted or 
unsubstituted alkylene of 1 to 8 carbon atoms and R.sub.7 and R.sub.9 are 
each independently of the other a substituted or unsubstituted alkyl of 1 
to 8 carbon atoms, substituted or unsubstituted cycloalkyl of 5 to 8 
carbon atoms, substituted or unsubstituted aryl of 6 to 12 carbon atoms or 
a substituted or unsubstituted phenylalkyl of 7 to 14 carbon atoms. 
When E is --COR.sub.10, preferably R.sub.10 is a substituted or 
unsubstituted alkyl of 1 to 12 carbon atoms, substituted or unsubstituted 
cycloalkyl of 5 to 8 carbon atoms, substituted or unsubstituted phenyl, or 
substituted or unsubstituted phenylalkyl of 7 to 14 carbon atoms. Most 
preferably, R.sub.10 is a substituted or unsubstituted alkyl of 1 to 10 
carbon atoms, substituted or unsubstituted cyclohexyl, substituted or 
unsubstituted phenyl, or phenylalkyl of 7 to 9 carbon atoms. 
When E is --COOR.sub.13 or --SO.sub.2 R.sub.12, preferably R.sub.11 and 
R.sub.12 are each independently of the other a substituted or 
unsubstituted alkyl of 1 to 8 carbon atoms, substituted or unsubstituted 
cycloalkyl of 5 to 8 carbon atoms, substituted or unsubstituted aryl of 6 
to 12 carbon atoms or substituted or unsubstituted phenylalkyl of 7 to 14 
carbon atoms. 
The instant asymmetrical azo compounds are prepared in several steps. 
Depending on the desired end product, it is initially necessary to prepare 
one of two intermediates: an appropriate 1-substituted 4-amino, 
4-alkylamino or 4-hydroxy-2,2,6,6-tetramethylpiperidine is converted into 
either the corresponding ester or amide derivative or the corresponding 
hydrazine ester or amide derivative. Conversion into the hindered amine 
ester or amide may be accomplished by reaction of the appropriate hindered 
amine with a halogenated ester such as methyl chloroformate. The resulting 
compound may then be converted into the corresponding hydrazine ester or 
amide derivative by reaction with hydrazine. Alternatively, to form the 
hydrazine ester or amide derivative, the 4-hydroxy, alkylamino or amino 
piperidine compound may be reacted with a carbazate compound such as ethyl 
carbazate. 
In the next step, the above ester or amide piperidine derivative or the 
hydrazine ester or amide derivative is reacted with an appropriate 
coreactant to form the corresponding intermediate asymmetrical hydrazide, 
the choice of which coreactant depends upon the desired end product. These 
possibilities and the preparative methods therefor are illustrated below 
and are intended to be non-limitative in nature. 
As a final step, the intermediate asymmetrical hydrazide compound is 
oxidized to prepare the instant asymmetrical azo compounds. The oxidizing 
agents which can be employed are fuming nitric acid, lead peroxide in cold 
dilute sulfuric acid, lead tetraacetate, t-butylhypochlorite, manganese 
dioxide, calcium hypochlorite, N-bromosuccinimide, nitrogen tetroxide and 
iodobenzene diacetate. 
The intermediate asymmetrical HALS hydrazides are prepared by reacting 
(2,2,6,6-tetramethylperidinyl)esters with a primary or secondary alkyl 
hydrazine, hydrazine or hydrazine hydrate. The reaction is illustrated by 
the following equation. 
##STR10## 
where R.sub.1 and X are as previously defined, R is an alkyl of 1 to 20 
carbons or phenyl and R' is a substituted or unsubstituted alkyl of 1 to 
20 carbon atoms, substituted or unsubstituted cycloalkyl of 5 to 12 carbon 
atoms, substituted or unsubstituted aryl of 6 to 14 carbon atoms or 
phenylalkyl of 7 to 22 carbon atoms. 
Typically the ester is dissolved in a polar solvent and convened to the 
desired hydrazide by stirring with an equivalent amount or slight excess 
of a primary or secondary alkylhydrazine, hydrazine or hydrazine hydrate. 
The reaction may go at room temperature or may require heating. Preferably 
the hydrazinolysis reaction is carried out in methanol or ethanol at 
10.degree.-30.degree. C. but other solvents such as isopropanol or 
ethylene glycol are also acceptable. In most cases the resulting 
hydrazides can be purified by recrystallization from the lower alcohols. 
The starting esters are known in the literature as described in U.S. Pat. 
Nos. 3,941,744, 3,975,462, 4,005,094, 4,241,208, 4,408,05 1, 4,526,966, 
4,562,220, 4,689,416, 4,745,192, 4,755,602 and U.S. Pat. No. DE 3,523,679. 
Examples of suitable hydrazines include hydrazine, hydrazine hydrate, 
35-85% hydrazine hydrate, methylhydrazine, ethylhydrazine, 
propylhydrazine, isopropylhydrazine, n-butylhydrazine, sec-butylhydrazine, 
n-amylhydrazine, sec-amylhydrazine, n-hexylhydrazine and n-octylhydrazine 
and sec-octylhydrazine. 
The carbamoyl and thiocarbamoyl derivatives are prepared by reacting the 
hydrazides with isocyanates or isothiocyanates in aprotic polar solvents 
such as tetrahydrofuran or dimethylformamide, as illustrated by the 
following equations. 
##STR11## 
where R.sub.1, R.sub.4, R.sub.5 and X are as previously defined. 
The reactions of hydrazides isocyanates and isothiocyanates are well known 
in the art and can occur under a wide variety of temperatures, times, 
solvents and concentrations. Generally a mole ratio of 0.9 to 1.0 to 1.1 
to 1.0 of the hydrazide to the monofunctional coreactant is employed. 
The hydrazides also react with unsubstituted or N-substituted amic acid 
esters in lower alcohol solutions to form diacyl hydrazines. 
##STR12## 
where R.sub.1, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R and X are as 
previously defined. 
The reactions are normally carried out in refluxing alcohol (i.e. methanol) 
but may be carried out in higher boiling aprotic solvents or without 
solvent by heating a mixture of the two components above their melting 
points. The methyl and ethyl esters of N-substituted oxamates and 
succinamates are the preferred coreactants. 
The acyl derivatives of the hydrazide may be prepared by reacting the 
esters (cited in the literature, as above) with acid hydrazides in 
refluxing alcohol (i.e. methanol). 
##STR13## 
where R.sub.1, R.sub.10, R and X are as previously defined. 
The acyl derivatives may also be prepared by reacting the hydrazides with 
non-cyclic carboxylic acid anhydrides: 
##STR14## 
where R.sub.1 and X are as defined above and R.sub.13 is defined as 
R.sub.10 above. The reactions are typically conducted in aprotic solvents, 
such as tetrahydrofuran, diethyl ether or t-butyl methyl ether. However, 
the reaction may also be carried out by adding the anhydride to a 
methanolic solution of the hydrazide. In addition, when R.sub.1 is 
hydrogen, alkyl, allyl, benzyl or an alkyl substituted benzyl, the 
carboxylic acid generated in the reaction may form a salt with the 
hindered amine. The free base derivatives may be regenerated from the 
carboxylic acid salt by neutralizing the salt with a stronger base than 
the hindered amine, for example, dilute sodium hydroxide, dilute potassium 
hydroxide, hydrazine or more basic amines, such as diethylamine or 
triethylamine. 
The alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl and 
aralkoxycarbonyl derivatives of the hydrazides may be prepared by reacting 
the ester, with the corresponding alkyl, cycloalkyl, aryl or aralkyl 
carbazates in refluxing alcohol (i.e. methanol). 
##STR15## 
where R.sub.1, R.sub.11, R and X are as previously defined. 
Alternatively, these derivatives may be prepared by reacting the hydrazide 
with a disubstituted carbonate or substituted haloformate. When a 
haloformate is used, an additional base may be used to react with the 
halogen acid formed. The amine group in the molecule may serve this 
purpose, but must then be released from its salt form by subsequent 
reaction with a strong base (as during workup). 
##STR16## 
where R.sub.1, R.sub.11, R and X are as previously defined and Y is 
aryloxy or halogen. 
The sulfonyl derivatives of the hydrazide may be prepared by reacting the 
esters of the literature with the corresponding sulfonyl hydrazide. 
##STR17## 
where R.sub.1, R.sub.12, R and X are as defined previously. 
Examples of suitable isocyanates include allyl isocyanate, benzyl 
isocyanate, n-butyl isocyanate, sec-butyl isocyanate, isobutyl isocyanate, 
t-butyl isocyanate, cyclohexyl isocyanate, ethyl isocyanate, isopropyl 
isocyanate, 4-methoxyphenyl isocyanate, methyl isocyanate, octadecyl 
isocyanate, 1-naphthyl isocyanate, phenyl isocyanate, o-tolyl isocyanate, 
m-tolyl isocyanate and p-tolyl isocyanate, dimethyl-m-isopropenylbenzyl 
isocyanate and 2-isocyanatoethyl methacryalate. 
Examples of suitable isothiocyanates include allyl isothiocyanate, benzyl 
isothiocyanate, 4-bromophenyl isothiocyanate, n-butyl isothiocyanate, 
sec-butyl isothiocyanate, isobutyl isothiocyanate, t-butyl isothiocyanate, 
3-chlorophenyl isothiocyanate, cyclohexyl isothiocyanate, cyclohexyl 
isothiocyanate, ethyl isothiocyanate, methyl isothiocyanate, propyl 
isothiocyanate, isopropyl isothiocyanate, 1-naphthyl isothiocyanate, 
t-octyl isothiocyanate, phenethyl isothiocyanate, phenyl isothiocyanate, 
propyl isothiocyanate, o-tolyl isothiocyanate, m-tolyl isothiocyanate and 
p-tolyl isothiocyanates. 
Examples of suitable amic acid esters include methyl oxamate, ethyl 
oxamate, propyl oxamate, isopropyl oxamate, n-butyl oxamate, phenyl 
oxamate, methyl succinamates, ethyl succinamate, propyl succinamate, 
isopropyl succinamate, n-butyl succinamate, phenyl succinamate, ethyl 
N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate, methyl 
N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate, ethyl 
N-(2,2,6,6-tetramethyl-4-piperidinyl)succinamate, methyl 
N-(2,2,6,6-tetramethyl-4-piperidynyl)succinamate, ethyl 
N-(3,5-di-t-butyl-4-hydroxyphenyl)oxamate, methyl 
N-(3,5-di-t-butyl-4-hydroxyphenyl)oxamate, ethyl 
N-(3,5-di-t-butyl-4-hydroxyphenyl)succinamate and methyl 
N-(3,5-di-t-butyl-4-hydroxyphenyl)succinamate. 
Examples of suitable acid hydrazides include acetyl hydrazide, propionic 
hydrazide, butyric hydrazide, isobutyric hydrazide, valeric hydrazide, 
isovaleric hydrazide, caproic hydrazide, decanoic hydrazide, lauric 
hydrazide, stearic hydrazide, benzhydrazide, 
3,5-di-t-butyl-4-hydroxybenzhydrazide. 
Examples of suitable carbazates include ethyl carbazate, methyl carbazate, 
propyl carbazate, isopropyl carbazate, butyl carbazate, cyclohexyl 
carbazate, cyclopentyl carbazate, cyclododecyl carbazate, phenyl 
carbazate, benzyl carbazate, 4-t-butylcyclohexyl carbazate, 2-ethylhexyl 
carbazate, 4-methylphenyl carbazate and 3-methoxyphenyl carbazate. 
Examples of suitable sulfonyl halides include benzenesulfonyl hydrazide, 
4-bromobenzenesulfonyl hydrazide, 1-butanesulfonyl hydrazide, 
4-t-butylbenzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, 
ethanesulfonyl hydrazide, methanesulfonyl hydrazide, 
4-fluorobenzenesulfonyl hydrazide, 1-hexadecanadulfonyl hydrazide, 
isopropanesulfonyl hydrazide and 1-naphthalenesulfonyl hydrazide. 
The instant invention also pertains to a stabilized polymer composition 
which comprises 
(a) a polymer, copolymer or polymer blend which contains in at least one 
polymer or polymer component significant ethylenic unsaturation, and 
(b) an effective stabilizing amount of an asymmetrical azo derivative 
grafted to said polymer or polymer component, said derivative having 
before grafting the structure of formula IV 
##STR18## 
where R.sub.1 is hydrogen, oxyl, hydroxyl, alkyl of 1 to 8 carbon atoms, 
alkyl of 2 to 4 carbon atoms substituted by one hydroxyl group, allyl, 
benzyl, benzyl substituted by one of two alkyl of 1 to 4 carbon atoms, 
alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or 
alkanoyl of 1 to 8 carbon atoms; 
X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen, alkyl of 1 to 18 
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 
carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one alkoxy group 
of 1 to 12 carbon atoms or a group of formula II 
##STR19## 
in which R.sub.1 is as defined above; and E is a substituted or 
unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted 
cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted aryl of 6 
to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms, or 
E is --CONHR.sub.4, --CSNHR.sub.5, --COR.sub.6 COR.sub.7, --COR.sub.8 
CONHR.sub.9, --COR.sub.10, --COOR.sub.11 or --SO.sub.2 R.sub.12, 
in which R.sub.4, R.sub.5, R.sub.7, R.sub.9, R.sub.10, R.sub.11 and 
R.sub.12 are each independently of the other hydrogen, substituted or 
unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted 
cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted aryl of 6 
to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms; and 
R.sub.6 and R.sub.8 are each independently of the other a substituted or 
unsubstituted alkylene of 1 to 12 carbons. 
Further, the instant invention relates to the intermediate hydrazine 
derivatives of formula V 
##STR20## 
where R.sub.1 is an unsubstituted or substituted alkoxy of 1 to 18 carbon 
atoms or cycloalkoxy of 5 to 12 carbon atoms; 
X is --O-- or --NR.sub.2 -- where R.sub.2 is hydrogen, alkyl of 1 to 18 
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 
carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one alkoxy group 
of 1 to 12 carbon atoms or a group of formula II 
##STR21## 
in which R.sub.1 is as defined above; and E is a substituted or 
unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted 
cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted aryl of 6 
to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms, or 
E is --CONHR.sub.4, --CSNHR.sub.5, --COR.sub.6 COR.sub.7, --COR.sub.8 
CONHR.sub.9, --COR.sub.10, --COOR.sub.11 or --SO.sub.2 R.sub.12, 
in which R.sub.4, R.sub.5, R.sub.7, R.sub.9, R.sub.10, R.sub.11 and 
R.sub.12 are each independently of the other hydrogen, substituted or 
unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted 
cycloalkyl of 5 to 12 carbon atoms, substituted or unsubstituted aryl of 6 
to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms; and 
R.sub.6 and R.sub.8 are each independently of the other a substituted or 
unsubstituted alkylene of 1 to 12 carbons. 
EP 0,467,344 Al describes some of the asymmetrical compounds of formula 
(V). 
The polymers, copolymers or polymer blends having significant ethylenic 
unsaturation in at least one polymer or polymer component, useful as 
component (a) in the stabilized compositions, are selected from the group 
consisting of ABS, HIPS, emulsion SBR, PP/EPDM, PP/NBR, PP/NR, ABS/PC, 
ABS/nylon, ABS/PVC, ABS/polyester, ABS/SMA, ABS/polysulfone, ASA/PC, 
acetal/elastomer, polyester/elastomer, nylon/elastomer, PPO/NR, EPDM/NBR 
and EPDM/olefin. 
Preferably component (a) is ABS or ABS/PC. 
When any of R.sub.1 or R.sub.2 is alkyl, such alkyl groups are, for 
example, methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, 
tert-amyl, 2-ethylhexyl, n-octyl, tert-octyl, lauryl, tert-dodecyl and 
octdecyl; when such radicals are cycloalkyl, they are, for example, 
cyclopentyl, cyclohexyl, cyclooctyl and cyclododecyl; when said radicals 
are phenylalkyl, they are, for example benzyl, phenethyl, a-methylbenzyl 
and .alpha.,.alpha.-dimethylbenzyl; when said radicals are alkoxy, they 
are, for example, methoxy, ethoxy, octyloxy and dodecyloxy; when said 
radicals are cycloalkoxy, they are, for example, cyclohexyloxy and 
cyclooctyloxy; and, when said radicals are alkanoyl, they are, for 
example, acetyl, propionyl, butanoyl and octanoyl. 
In general polymers which can be stabilized include 
1. Polymers of monoolefins and diolefins, for example polyethylene (which 
optionally can be crosslinked), polypropylene, polyisobutylene, 
polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well 
as polymers of cycloolefins, for instance of cyclopentene or norbornene. 
2. Mixtures of the polymers mentioned under 1), for example mixtures of 
polypropylene with polyisobutylene. 
3. Copolymers of monoolefins and diolefins with each other or with other 
vinyl monomers, such as, for example, ethylene/propylene, 
propylene/butene-1, propylene/isobutylene, ethylene/butene-1, 
propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates, 
ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylic 
acid copolymers and their salts (ionomers) and terpolymers of ethylene 
with propylene and a diene, such as hexadiene, dicyclopentadiene or 
ethylidene- norbornene. 
4. Polystyrene, poly-(p-methylstyrene). 
5. Copolymers of styrene or methylstyrene with dienes or acrylic 
derivatives, such as, for example, styrene/butadiene, 
styrene/acrylonitrile, styrene/ethyl methacrylate, styrene/butadiene/ethyl 
acrylate, styrene/acrylonitrile/methyl acrylate; mixtures of high impact 
strength from styrene copolymers and another polymer, such as, for 
example, from a polyacrylate, a diene polymer or an 
ethylene/propylene/diene terpolymer; and block polymers of styrene, such 
as, for example, styrene/butadiene/styrene, styrene/isoprene/styrene, 
styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene. 
6. Graft copolymers of styrene, such as, for example, styrene on 
polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and 
alkyl acrylates or methacrylates on polybutadiene, styrene and 
acrylonitrile on ethylene/propylene/diene terpolymers, styrene and 
acrylonitrile on polyacrylates or polymethacrylates, styrene and 
acrylonitrile on acrylate/butadiene copolymers, as well as mixtures 
thereof with the copolymers listed under 5), for instance the copolymer 
mixtures known as ABS-, MBS-, ASA- or AES-polymers. 
7. Halogen-containing polymers, such as polychloroprene, chlorinated 
rubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrin 
homo- and copolymers, polymers from halogen-containing vinyl compounds, as 
for example, polyvinylchloride, polyvinylidene chloride, polyvinyl 
fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for 
example, vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate, 
vinylidene chloride/vinyl acetate copolymers, or vinyl fluoride/vinyl 
ether copolymers. 
8. Polymers which are derived from .alpha..beta.-unsaturated acids and 
derivatives thereof, such as polyacrylates and polymethacrylates, 
polyacrylamide and polyacrylonitrile. 
9. Copolymers from the monomers mentioned under 8) with each other or with 
other unsaturated monomers, such as, for instance, 
acrylonitrile/butadiene, acrylonitrile/alkyl acrylate, 
acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenide 
copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers. 
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, polyvinyl benzoate, polyvinyl 
maleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine. 
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 those polyoxymethylenes which 
contain ethylene oxide as comonomer. 
13. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides 
with polystyrene. 
14. Polyurethanes which are derived from polyethers, polyesters or 
polybutadienes with terminal hydroxyl groups on the one side and aliphatic 
or aromatic polyisocyanates on the other side, as well as precursors 
thereof (polyisocyanates, polyols or prepolymers). 
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, 
polyamide 11, polyamide 12, poly-2,4,4-trimethylhexamethylene 
terephthalamide, poly-p-phenylene terephthalamide or poly-m-phenylene 
isophthalamide, as well as copolymers thereof with polyethers, such as for 
instance with polyethylene glycol, polypropylene glycol or 
polytetramethylene glycols. 
16. Polyureas, polyimides and polyamide-imides. 
17. Polyesters which are derived from dicarboxylic acids and diols and/or 
from hydroxycarboxylic acids or the corresponding lactones, such as 
polyethylene terephthalate, polybutylene terephthalate, 
poly-1,4-dimethylol-cyclohexane terephthalate, 
poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate and 
polyhydroxybenzoates as well as block-copolyether-esters derived from 
polyethers having hydroxyl end groups. 
18. Polycarbonates. 
19. Polysulfones, polyethersulfones and polyetherketones. 
20. Crosslinked polymers which are derived from aldehydes on the one hand 
and phenols, ureas and melamines 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 and 
vinyl compounds as crosslinking agents, and also halogen-containing 
modifications thereof of low flammability. 
23. Thermosetting acrylic resins, derived from substituted acrylic esters, 
such as epoxy-acrylates, urethane-acrylates or polyester acrylates. 
24. Alkyd resins, polyester resins or acrylate resins in admixture with 
melamine resins, urea resins, polyisocyanates or epoxide resins as 
crosslinking agents. 
25. Crosslinked epoxide 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 chemically modified in a polymer homologous manner, such 
as cellulose acetates, cellulose propionates and cellulose butyrates, or 
the cellulose ethers, such as methyl cellulose. 
27. Mixtures of polymers as mentioned above, for example PP/EPDM, Polyamide 
6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS. 
28. Naturally occurring and synthetic organic materials which are pure 
monomeric compounds or mixtures of such compounds, for example mineral 
oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes 
based on synthetic esters (e.g. phthalates, adipates, phosphates or 
trimellitates) and also mixtures of synthetic esters with mineral oils in 
any weight ratios, which materials may be used as plasticizers for 
polymers or as textile spinning oils, as well as aqueous emulsions of such 
materials. 
29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or 
latices of carboxylated styrene/butadiene copolymers. 
30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, 
for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes 
described, for example, in U.S. Pat. No. 4,355,147. 
31. Polyketimines in combination with unsaturated acrylic polyacetoacetate 
resins or with unsaturated acrylic resins. The unsaturated acrylic resins 
include the urethane acrylates, polyether acrylates, vinyl or acryl 
copolymers with pendant unsaturated groups and the acrylated melamines. 
The polyketimines are prepared from polyamines and ketones in the presence 
of an acid catalyst. 
32. Radiation curable compositions containing ethylenically unsaturated 
monomers or oligomers and a polyunsaturated aliphatic oligomer. 
33. Epoxymelamine resins such as light-stable epoxy resins crosslinked by 
an epoxy functional coetherified high solids melamine resin such as 
LSE-4103 (Monsanto). 
In general, the compounds of the present invention are employed in from 
about 0.01 to about 5% by weight of the stabilized composition, although 
this will vary with the particular substrate and application. An 
advantageous range is from about 0.5 to about 2%, and especially 0.1 to 
about 1%. 
The stabilizers of the instant invention may readily be incorporated into 
the organic polymers by conventional techniques, at any convenient stage 
prior to the manufacture of shaped articles therefrom. For example, the 
stabilizer may be mixed with the polymer in dry powder form, or a 
suspension or emulsion of the stabilizer may be mixed with a solution, 
suspension, or emulsion of the polymer. The resulting stabilized polymer 
compositions of the invention may optionally also contain from about 0.01 
to about 5%, preferably from about 0.025 to about 2%, and especially from 
about 0.1 to about 1% by weight of various conventional additives, such as 
the materials listed below, or mixtures thereof. 
1. Antioxidants 
1.1. Alkylated monophenols, for example, 
2,6-di-ten-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-i-butylphenol 
2,6-di-cyclopentyl-4-methylphenol 
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol 
2,6-di-octadecyl-4-methylphenol 
2,4,6-tri-cyclohexylphenol 
2,6-di-tert-butyl-4-methoxymethylphenol 
1.2. Alkylated hydroquinones, for example, 
2,6-di-tert-butyl-4-methoxyphenol 
2,5-di-tert-butyl-hydroquinone 
2,5-di-tert-amyl-hydroquinone 
2,6-diphenyl-4-octadecyloxyphenol 
1.3. Hydroxylated thiodiphenyl ethers, for example, 
2,2'-thio-bis-(6-tert-butyl-4-methylphenol) 
2,2'-thio-bis-(4-octylphenol) 
4,4'-thio-bis-(6-tert-butyl-3-methylphenol) 
4,4'-thio-bis-(6-tert-butyl-2-methylphenol) 
1.4. Alkylidene-bisphenols, for example, 
2,2'-methylene-bis-(6-ten-butyl-4-methylphenol) 
2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol) 
2,2'-methylene-bis-[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol] 
2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol) 
2,2'-methylene-bis-(6-nonyl-4-methylphenol) 
2,2'-methylene-bis-[6-(.alpha.-methylbenzyl)-4-nonylphenol] 
2,2'-methylene-bis-[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol] 
2,2'-methylene-bis-(4,6-di-tert-butylphenol) 
2,2'-ethylidene-bis-(4,6-di-tert-butylphenol) 
2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol) 
4,4'-methylene-bis-(2,6-di-tert-butylphenol) 
4,4'-methylene-bis-(6-tert-butyl-2-methylphenol) 
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane 
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol 
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl )-butane 
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl )-3-n-dodecylmercaptobutane 
ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate] 
di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene 
di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphen 
yl] terephthalate. 
1.5. Benzyl compounds, for example, 
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene 
di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide 
3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester 
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate 
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 
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester 
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, 
calcium-salt 
1.6. Acylaminophenols, for example, 
4-hydroxy-lauric acid anilide 
4-hydroxy-stearic acid anilide 
2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine 
octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate 
1.7. Esters of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid 
with monohydric or polyhydric alcohols, for example, 
______________________________________ 
methanol diethylene glycol 
octadecanol triethylene glycol 
1,6-hexanediol pentaerythritol 
neopentyl glycol 
tris-hydroxyethyl isocyanurate 
thiodiethylene glycol 
di-hydroxyethyl oxalic acid diamide 
______________________________________ 
1.8. Esters of .beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic 
acid with monohydric or polyhydric alcohols, for example, 
______________________________________ 
methanol diethylene glycol 
octadecanol triethylene glycol 
1,6-hexanediol pentaerythritol 
neopentyl glycol 
tris-hydroxyethyl isocyanurate 
thiodiethylene glycol 
di-hydroxyethyl oxalic acid diamide 
______________________________________ 
1.9. Amides of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid 
for example, 
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine 
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine 
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine 
1.10 Diarylamines, for example, 
diphenylamine, N-phenyl-1-naphthylamine, 
N-(4-tert-octylphenyl)-1-naphthylamine, 
4,4'-di-tert-octyl-diphenylamine, reaction product of N-phenylbenzylamine 
and 
2,4,4-trimethylpentene, reaction product of diphenylamine and 
2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and 
2,4,4-trimethylpentene. 
2. UV absorbers and light stabilizers 
2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-, 
3', 5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 
5-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-, 3', 
5'-bis-(.alpha.,.alpha.-dimethylbenzyl), 
3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-, 
3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-, and 
dodecylated-5'-methyl derivatives. 
2.2. 2-Hydroxy-benzophenones, 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 derivatives. 
2.3. Esters of optionally substituted benzoic acids for example, phenyl 
salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, 
dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, 
benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 
2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid 
hexadecyl ester. 
2.4. Acrylates, for example, .alpha.-cyano-.beta.,.beta.-diphenylacrylic 
acid ethyl ester or isooctyl ester, .alpha.-carbomethoxy-cinnamic acid 
methyl ester, .alpha.-cyano-.beta.-methyl-p-methoxy-cinnamic acid methyl 
ester or butyl ester, .alpha.-carbomethoxy-p-methoxy-cinnamic acid methyl 
ester, N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methyl-indoline. 
2.5. Nickel compounds, for example, nickel complexes of 
2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 
1:2 complex, optionally with additional ligands such as n-butylamine, 
triethanolamine or N-cyclohexyl-diethanolamine, nickel 
dibutyldithiocarbamate, nickel salts of 
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as 
of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as 
of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of 
1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands. 
2.6. Sterically hindered amines., for example 
bis-(2,2,6,6-tetramethylpiperidyl) sebacate, 
bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, 
n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid 
bis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of 
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, 
condensation product of 
N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 
4-tert-octylamino-2,6-dichloro-s-triazine, 
tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, 
tetrakis-(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 
1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone), 
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate. 
2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide, 
2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 
2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 
2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 
2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and 
para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides. 
2.8. Hydroxyphenyl-s-triazines, for example 
2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 
2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine; 
2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 
2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine 
; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethyl 
phenyl)-s-triazine; 
2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine; 
2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine 
, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine. 
3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide, 
N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, 
N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 
3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide. 
4. Phosphites and phosphonites, for example, triphenyl phosphite, 
diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl) 
phosphite, trilauryl phosphite, trioctadecyl phosphite, 
di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) 
phosphite, di-isodecylpentaerythritol diphosphite, 
di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, 
tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl) 
4,4'-diphenylylenediphosphonite. 
5. Compounds which destroy peroxide, for example, esters of 
.beta.-thiodipropionic acid, for example the lauryl, stearyl, myristyl or 
tridecyl esters, mercapto-benzimidazole or the zinc salt of 
2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl 
disulfide, pentaerythritol tetrakis-(.beta.-dodecylmercapto)-propionate. 
6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, 
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, 
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, 
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, 
N-hexadecyl-N-octadecylhydroxylamine, 
N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived 
from hydrogenated tallow amine. 
7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone, 
N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, 
N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, 
N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, 
N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl 
nitrone, N-heptadecyl-alpha-heptadecyl nitrone, 
N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from 
N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. 
8. Polyamide stabilizers, for example copper salts in combination with 
iodides and/or phosphorus compounds and salts of divalent manganese. 
9. Basic co-stabilizers, 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 Ca stearate, 
Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony 
pyrocatecholate or zinc pyrocatecholate. 
10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipic acid, 
diphenylacetic acid. 
11. Fillers and reinforcing agents, for example, calcium carbonate, 
silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, 
metal oxides and hydroxides, carbon black, graphite. 
12. Other additives, for example, plasticizers, lubricants, emulsifiers, 
pigments, optical brighteners, flameproofing agents, anti-static agents, 
blowing agents and thiosynergists such as dilauryl thiodipropionate or 
distearyl thiodipropionate. 
The phenolic antioxidant of particular interest is selected from the group 
consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 
neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), 
di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene 
bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 
3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 
2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 
1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate, 
1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 
1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanur 
ate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene 
bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 
1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, 
N,N'-hexamethylene-bis(3,5-di-tert-butyl- 4-hydroxyhydrocinnamamide), 
calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene 
bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 
3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, 
bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and 
N,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide. 
A most preferred phenolic antioxidant is neopentanetetrayl 
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 
3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 
2,6-di-tert-butyl-p-cresol or 
2,2'-ethylidene-bis(4,6-di-tert-butylphenol). 
The hindered amine compound of particular interest is selected from the 
group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 
his(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, 
di(1,2,2,6,6-pentamethylpiperidin-4-yl) 
(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, 
4-benzoyl-2,2,6,6-tetramethylpiperidine, 
4-stearyloxy-2,2,6,6-tetramethylpiperidine, 
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione, 
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 
1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane, 
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2] heneicosane, 
polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), 
polycondensation product of 
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic 
acid, polycondensation product of 
4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and 
1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 
1,2,3,4-butanetetracarboxylate, 
tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 
1,2,3,4-butanetetracarboxylate, polycondensation product of 
2,4-dichloro-6-morpholino-s-triazine and 
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine ), 
N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-am 
ino-s-triazin-2-yl]-1,10-diamino-4,7-diaza decane, mixed 
[2,2,6,6-tetramethylpiperidin-4-yl/.beta.,.beta.,.beta.',.beta.'-tetrameth 
yl-3,9-(2,4,8, 10-tetraoxaspiro[5.5]-undecane) diethyl] 
1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethyl 
piperidin-4-yl/.beta.,.beta.,.beta.',.beta.'-tetramethyl-3,9-(2,4,8, 
10-tetraoxaspiro[5.5]undecane)diethyl] 1,2,3,4-butanetetracarboxylate, 
octamethylene bis(2,2,6,6-tetramethyl-piperidin-4-carboxylate), 
4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), and 
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate. 
A most preferred hindered amine compound is 
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, the polycondensation 
product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperdine and 
succinic acid, the polycondensation product of 
2,4-dichloro-6-tert-octylamino-s-triazine and 
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), 
N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)am 
ino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane or 
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

The following examples are presented for the purpose of illustration only 
and are not to be construed to limit the nature or scope of the instant 
invention in any manner whatsoever. 
Example 1 
Bis(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) 
Hydrazine-1,2-dicarboxylate 
To a mixture of 15.8 g of 1-methoxy-2,2,6,6-tetramethylpiperidin-4-ol and 
5.9 g of dimethyl hydrazine-1,2-dicarboxylate is added 1.4 g of tetrabutyl 
titanate at room temperature. The mixture is heated at 
135.degree.-145.degree. C. for 12 hours and methanol is collected in a 
Dean-Stark trap. The reaction mixture is partitioned between toluene and 
water. The organic phase is then washed with water, brine, dried over 
anhydrous sodium sulfate and evaporated to leave 19.1 g of the crude 
desired product. Recrystallization of the crude product from acetonitrile 
affords 11.7 g of the title compound as an off-white solid; mp 
147.degree.-149.degree. C. 
Analysis: Calcd. for C.sub.22 H.sub.42 Na.sub.4 O.sub.6 : C, 57.6; H, 9.2.; 
N, 12.2. Found: C, 57.6; H, 9.4, N, 12.1. 
Example 2 
Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) 
Hydrazine-1,2-dicarboxylate 
The procedure of Example 1 is repeated using 24.1 g of 
1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ol, 6.67 g of dimethyl 
hydrazine-1,2-dicarboxylate and 1.5 g of tetrabutyl titanate to afford 
14.6 g of the title compound as a white solid; mp 150.degree.-152.degree. 
C. 
Analysis: Calcd. for C.sub.32 H.sub.58 N.sub.4 O.sub.6 : C, 64.4; H, 10.1; 
N, 9.4. Found: C, 64.4; H, 10.2; N, 9.3. 
Example 3 
Bis(1,2,2,6,6-pentamethylpiperidin-4-yl) Hydrazine-1,2-dicarboxylate 
The procedure of Example 1 is repeated using 33.9 g of 
1,2,2,6,6-pentamethyl-piperidin-4-ol, 13.3 g of dimethyl 
hydrazine-1,2-dicarboxylate and 0.31 g of tetrabutyl titanate to afford 
14.8 g of the title compound as a white solid; mp 189.degree.-191.degree. 
C. 
Analysis: Calcd. for C.sub.22 H.sub.42 N.sub.4 O.sub.4 : C, 61.9; H, 9.9; 
N. 13.1. Found: C, 61.8; H, 10.2,; N, 13.0. 
Example 4 
Bis(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) Azodicarboxylate 
To a solution of 8.2 g of bis(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) 
hydrazine-1,2-dicarboxylate, as prepared in Example 1, in 100 mL of 
methylene chloride is added 6.3 g of iodobenzene diacetate in one portion 
at room temperature. After stirring at room temperature for 50 minutes, 
the solution is washed with a 10% solution of sodium carbonate and then 
with brine, and dried over anhydrous magnesium sulfate. The dried solution 
is then evaporated to leave 9.3 g of the desired product. 
Recrystallization of the crude product from acetonitrile affords 6.5 g of 
the title compound; mp 145.degree.-147.degree. C. 
Analysis: Calcd. for C.sub.22 H.sub.40 N.sub.4 O.sub.6 : C, 57.8; H, 8.8; 
N, 12.3. Found: C, 57.3; H, 9.2; N, 11.9. 
Example 5 
Bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) 
Hydrazine-1,2-dicarboxylate 
To a solution of 29.7 g of triphosgene in 120 mL of tetrahydrofuran (THF) 
is added a solution of 85.7 g of 
1-octyloxy-2,2,6,6-tetramethylpiperidin-4-ol and 42.0 mL of triethylamine 
in 240 mL of THF over 4 hours at 5-10.degree. C., followed by 7.3 mL of 
hydrazine hydrate. After stirring the reaction mixture at room temperature 
for 18 hours, a solution of 71.0 g of sodium carbonate in 500 mL of water 
is added and the organic layer is removed, washed with water and dried 
over anhydrous magnesium sulfate. The dried solution is evaporated to 
afford 97.2 g of the title compound as an oil. 
NMR and mass spectra are consistent with the desired structure of the title 
compound. 
Example 6 
Bis(1,2,2,6,6-pentamethylpiperidin-4-yl) Hydrazine-1,2-dicarboxylate 
The procedure of Example 5 is repeated using 178.2 g of triphosgene, 308.4 
g of 1,2,2,6,6-pentamethylpiperidin-4-ol, 252 mL of triethylamine and 43.7 
mL of hydrazine hydate to afford 180 g of the title compound as a white 
solid; mp 189.degree.-191 .degree. C. 
Example 7 
Bis(1,2,2,6,6-pentamethylpiperidin-4-yl) Azodicarboxylate 
To a solution of 30.0 g bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 
hydrazine-1,2-dicarboxylate in 60 mL of methylene chloride is added 16.0 g 
(10.8 mL), of trifluoroacetic acid at 0.degree.-5.degree. C., followed the 
addition of 22.6 g of iodobenzene diacetate at room temperature. After 
stirring at room temperature for 2.5 hours, the reaction mixture is washed 
with saturated sodium bicarbonate solution and then with brine, and dried 
over anhydrous magnesium sulfate. The dried solution is evaporated to 
afford a pale yellow oil. Trituration with acetonitrile affords 7.0 g of 
the title compound as a pale yellow solid; mp 135.degree.-137.degree. C. 
NMR and IR analyses are consistent with the desired structure. 
Analysis: Calcd. for C.sub.22 H.sub.40 N.sub.4 O.sub.4 : C, 62.2; H, 9.5; 
N, 13.2 Found: C, 61.9; H, 10.0; N, 12.8. 
Example 8 
Bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Azodicarboxylate 
The procedure of Example 4 is repeated using 4.6 g of 
bis(1-octyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) 
hydrazine-1,2-dicarboxylate and 2.3 g of iodobenzene diacetate to afford 
3.3 gg of the title compound as a pale yellow oil. NMR, IR and mass 
spectra analyses are consistent with the desired structure. 
Example 9 
Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Azodicarboxylate 
The procedure of Example 4 is repeated using 12.2 g of 
bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) 
hydrazine-1,2-dicarboxylate and 7.2 g of iodobenzene diacetate to afford 
10.3 g of the title compound; mp 189.degree.-191 .degree. C. 
Analysis: Calcd. for C.sub.32 H.sub.56 N.sub.4 O.sub.6 : C, 64.6; H, 9.8; 
N, 9.4. Found: C, 64.6; H, 9.7; N, 9.4. 
Example 10 
Grafting of Stabilizers to ABS Resin 
ABS resin (342 EZ, Dow) is solvent-blended with 0.5% by weight of a test 
light stabilizer and then the blended ABS resin is extruded at zone 
temperatures in the range of 390.degree.-425.degree. F. 
(199.degree.-218.degree. C.) at an extruder speed set at 25 or 100 rpm. 
The lower affords a longer residence time for the resin in the extruder. 
The resulting pellets are divided into two portions to study the light 
stability of solvent extracted and non-extracted ABS samples. 
The extruded ABS resin is dry blended with titanium dioxide and then milled 
and compression molded at 365.degree. F. (185.degree. C.) into 4".times.4" 
(10.16 cm.times.10.16 cm) plaques and cut into 1" (2.54 cm) specimens. A 
portion of the extruded ABS resin is dissolved in xylene and the polymer 
precipitated by the addition of methanol. The polymer crumbs are dried and 
then solvent blended with 0.1% by weight of n-octadecyl 
3,5-di-tert-butyl-4-hydroxyhydrocinnamate and 1% by weight of titanium 
dioxide, followed by milling and compression molding as outlined above. 
Both samples (extracted and non-extracted) are exposed in standard 
interior automotive Xenon Arc WeatherOmeter (XAW) and ACS tests. .DELTA.E 
color measurements are made at 50 hour intervals. The amount of light 
stabilizer that is grafted onto the polymer is also determined by liquid 
chromatography (LC). 
TABLE A 
______________________________________ 
Non-Extracted Grafted ABS Resin 
.DELTA.E Values** after 
Hours of Exposure 
Conc. (Interior Automotive Xenon) 
Stabilizer* 
% by wt 50 100 150 200 275 
______________________________________ 
Base -- 1.5 4.4 7.3 10.1 13.8 
HALS A 0.5 1.1 0.5 0.8 1.5 3.3 
Compound of 
0.5 0.8 1.7 4.3 6.3 9.1 
Example 4 
______________________________________ 
*HALS A is bis(1,2,2,6,6pentamethylpiperidin-4-yl) sebacate. 
**Lower numbers indicate better color performance. 
TABLE B 
______________________________________ 
Extracted Grafted ABS Resin 
.DELTA.E Values** after 
Hours of Exposure 
Conc. (Interior Automotive Xenon) 
Stabilizer* 
% by wt 50 100 150 200 275 
______________________________________ 
Base -- 1.5 4.4 7.3 10.1 17.4 
HALS A 0.5 1.4 4.5 7.6 11.9 15.3 
Compound of 
0.5 0.8 1.7 4.3 6.3 7.6 
Example 4 
______________________________________ 
*HALS A is bis(1,2,2,6,6pentamethylpiperidin-4-yl) sebacate. 
**Lower numbers indicate better color performance. 
The above data in Tables A and B illustrate the light stabilizing activity 
of the instant compound of Example 4, which activity is maintained even 
after the ABS resin is extracted in xylene as compared to HALS A, a 
non-graftable control light stabilizer which is removed from the ABS resin 
by extraction. 
Analytical data indicating the chemical bonding of the compound of Example 
4 to the polymer substrate during the reactive extrusion processing are 
summarized in Table C. These data are the results of two replicate samples 
analyzed by liquid chromatography on the xylene solution obtained after 
the ABS resin has been extracted. 
TABLE C 
______________________________________ 
Percent 
Initial Concentration 
Extract 
Conc. (% by wt) 
(% by wt) of Init. 
Stabilizer* 
Before Extraction 
After Extraction 
Conc. 
______________________________________ 
HALS A 0.5 0.1 80 
Compound of 
0.5 0.5 0 
Example 4 
______________________________________ 
*HALS A is bis(1,2,2,6,6pentamethylpiperidin-4-yl) sebacate. 
These data show that a vast portion of the prior an hindered amine light 
stabilizer is extracted when the extruded ABS resin is extracted with 
xylene solvent, but that the instant compounds as typified by the compound 
of Exampel 4 are chemically bonded to the ABS resin substrate and are not 
removed by solvent extraction. 
Example 11 
Grafting of Stabilizers to ABS Resin 
A representative example of the instant light stabilizers is incorporated 
into polybutadiene rubber (DIENE 55, Firestone Tire and Rubber Co.) using 
a Brabender Plasticorder, at 100.degree. C. under nitrogen for seven 
minutes. Any non-grafted light stabilizer is removed from the 
polybutadiene by dissolving the polymer in xylene, followed by 
precipitation by the addition of methanol. The resulting polymer is dried 
(40.degree. C., air oven). The total nitrogen analysis of the polymer 
samples before and after extraction indicates the substantial grafting of 
the instant compound to polybutadiene rubber during the processing step. 
TABLE D 
______________________________________ 
Percent 
Initial Concentration 
Extract. 
Conc. (% by wt) 
(% by wt) of Init. 
Stabilizer* 
Before Extraction 
After Extraction 
Conc. 
______________________________________ 
Compound of 
2.0 1.51 25 
Example 9 
______________________________________ 
These data show that, when polybutadiene rubber is extracted with xylene 
solvent, the instant compounds as typified by the compound of Example 9 
are chemically bonded to the polybutadiene substrate and are not prone to 
be removed by solvent extraction in a substantial fashion. 
Example 12 
Light Stabilization of ABS/Polycarbonate Blends 
A 50/50 blend of ABS (containing a hindered amine stabilizer compound) and 
polycarbonate is prepared by compounding the mixed resin pellets in a mini 
Brabender extruder. Injection molded 125 mil (3.2 mm) Izod bars are then 
prepared for evaluation of light stability, under interior automotive 
Xenon Arc WeatherOmeter exposure and spray Xenon Arc WeatherOmeter 
exposure test as described in Example 10. The results are given in Tables 
E and F below. 
TABLE E 
______________________________________ 
Light Stability Performance during GM-XAW Exposure 
.DELTA.E Values** after 
Conc. Hours of Exposure 
Stabilizer* 
% by wt 102 200 400 600 
______________________________________ 
Base -- 9.7 17.1 26.1 26.9 
HALS A 0.5 9.1 15.7 23.5 24.2 
HALS B 0.5 8.5 14.4 22.9 23.0 
Compound of 
0.5 6.8 12.8 20.3 20.5 
Example 7 
Compound of 
0.5 5.8 11.8 19.4 20.8 
Example 4 
______________________________________ 
*HALS A is bis(1,2,2,6,6pentamethylpiperidin-4-yl) sebacate. 
HALS B is bis(2,2,6,6tetramethylpiperidin-4-yl) sebacate. 
**Lower numbers indicate better color performance. 
TABLE F 
______________________________________ 
Light Stability Performance during XAW with Spray Exposure 
.DELTA.E Values** after 
Conc. Hours of Exposure 
Stabilizer* 
% by wt 230 406 600 800 1213 
______________________________________ 
Base -- 1.2 5.9 11.2 15.0 21.1 
HALS A 0.5 0.6 3.2 6.4 9.4 15.5 
HALS B 0.5 1.1 1.8 5.0 8.3 14.4 
Compound of 
0.5 1.3 0.9 4.4 7.3 12.8 
Example 7 
Compound of 
0.5 1.0 1.3 3.4 6.6 12.6 
Example 4 
______________________________________ 
*HALS A is bis(1,2,2,6,6pentamethylpiperidin-4-yl) sebacate. 
HALS B is bis(2,2,6,6tetrainethylpiperidin-4-yl) sebacate. 
**Lower numbers indicate better color performance. 
The above data clearly demonstrate the advantages of the instant invention. 
When a hindered amine light stabilizer is located into the ABS phase of a 
ABS/polycarbonate blend, thus preventing its migration into the 
polycarbonate, the overall light stability of the blend is improved. 
Examples 13-19 
Following the general procedure of Example 1 or Example 5, the following 
compounds of formula III are prepared. 
______________________________________ 
##STR22## III 
Example R.sub.1 X 
______________________________________ 
13 methoxy NH 
14 cyclohexyloxy NH 
15 methyl NH 
16 octyloxy NH 
17 2-hydroxyethyl O 
18 benzyl O 
19 hydrogen O 
______________________________________ 
Examples 20-26 
Following the general procedure of Example 4 or Example 7, the compounds of 
formula I are prepared. 
______________________________________ 
##STR23## I 
Example R.sub.1 X 
______________________________________ 
20 methoxy NH 
21 cyclohexyloxy NH 
22 methyl NH 
23 octyloxy NH 
24 2-hydroxyethyl O 
25 benzyl O 
26 hydrogen O 
______________________________________ 
Example 27 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl Cloroformate 
The title compound is prepared by reacting 
1-methoxy-2,2,6,6-tetramethyl-piperidin-4-ol (1 mole) with 
methylchloroformate (1 mole). 
Example 28 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl Carbazate 
The title compound is prepared by reacting the compound of Example 27 (1 
mole) with hydrazine (1.1 mole), employing methanol as the solvent. 
Example 29 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl 2-Methylhydrazinecarboxylate 
The title compound is prepared by reacting the compound of Example 27 (1 
mole) with methylhydrazine (1.1 mole) in methanol. 
Example 30 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl 
2-Isobutylcarbamoylhydrazinecarboxylate 
To obtain the title compound, the compound of Example 28 (1 mole) is 
reacted with isobutyl isocyanate (1.1 mole) in tetrahydrofuran. 
Example 31 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl 
2-Allylthiocarbamoylhydrazinecarboxylate 
To obtain the title compound, the compound of Example 28 (1 mole) is 
reacted with allyl isothiocyanate (1.1 mole), employing dimethylformamide 
as the solvent. 
Example 32 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl 
2-Succinamoylhydrazinecarboxylate 
The title compound is prepared by reacting the compound of Example 28 (1 
mole) with isopropyl succinamate (1 mole), employing methanol as the 
solvent. 
Example 33 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl 
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)succinamoylhydrazinecarboxylate 
The title compound is made by the reaction of the compound of Example 28 
with ethyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)succinamate in methanol. 
Example 34 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl) 2-Acetylhydrazinecarboxylate 
The title compound is prepared by reacting the compound of Example 27 (1 
mole) with acetyl hydrazide (1 mole) in methanol. 
Example 35 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl 
2-Hydrazinocarbonylhydrazinecarboxylate 
The title compound is prepared by reacting the compound of Example 28 (1 
mole) with methyl carbazate (1 mole) by refluxing the reaction mixture in 
methanol. 
Example 36 
1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl 
2-Benzenesulfonylhydrazinecarboxylate 
The title compound is prepared by reacting the compound of Example 27 (1 
mole) with benzenesulfonyl hydrazide (1 mole). 
Example 37 
The procedure of Example 4 is repeated using the asymmetrical hydrazide 
compounds of Examples 29-36, respectively, to obtain the following 
corresponding asymmetrical azo compounds of formula IVa: 
______________________________________ 
##STR24## IVa 
Hydrazide 
Example 
Compound Azo Compound 
______________________________________ 
A 29 methyl 
B 30 CONH-isobutyl 
C 31 CSNH-allyl 
D 32 COCH.sub.2 CH.sub.2 CONH.sub.2 
E 33 
##STR25## 
F 34 acetyl 
G 35 CONHNH.sub.2 
H 36 SO.sub.2 -phenyl 
______________________________________ 
Example 38 
Grafting of Stabilizers to ABS Resin 
The procedure of Example 11 is repeated using the instant asymmetrical azo 
compounds of Example 37 A-H, respectively. 
The instant compounds are chemically bonded to the polybutadiene substrate 
and are not prone to be removed by solvent extraction to any substantial 
degree. 
Example 39 
Light Stabilization of ABS/Polycarbonate Blends 
The procedure of Example 12 is repeated using the instant asymmetrical azo 
compounds of Examples 37 A-H, respectively. 
The instant compounds, located into the ABS phase of an ABS/polycarbonate 
blend improve the overall light stability of the polymer blend. 
Examples 40-42 
Following the general procedure of Example 29, the following compounds of 
formula V are prepared. 
______________________________________ 
##STR26## (V) 
Example R.sub.1 X E 
______________________________________ 
40 methoxy NH ethyl 
41 cyclohexyloxy NH propyl 
42 octyloxy O n-amyl 
______________________________________ 
Examples 43-44 
Using the general procedure of Example 30, the following instant compounds 
of formula V are prepared. 
______________________________________ 
Example R.sub.1 X E 
______________________________________ 
43 methoxy --NH-- --CONH-benzyl 
44 ethoxy --O-- --CONH-octadecyl 
______________________________________ 
Examples 45-47 
Using the general procedure of Example 31, the following instant compounds 
of formula V are prepared. 
______________________________________ 
Example 
R.sub.1 X E 
______________________________________ 
45 methoxy --NH-- --CSNH-n-butyl 
46 cyclohexyloxy 
--NH-- --CSNH-(3-chlorophenyl) 
47 octyloxy --O-- --CSNH-cyclohexyl 
______________________________________ 
Examples 48-49 
Using the general procedure of Example 32, the following instant compounds 
of formula V are prepared. 
______________________________________ 
Example R.sub.1 X E 
______________________________________ 
48 methoxy --NH-- 
succinamoyl 
49 octyloxy --O-- 
succinamoyl 
______________________________________ 
Examples 50-51 
Using the general procedure of Example 33, the following instant compounds 
of formula V are prepared. 
______________________________________ 
Example R.sub.1 X E 
______________________________________ 
50 ethoxy --NH-- N-(3,5-di-tert- 
butyl-4-hydroxy- 
phenyl)succinamoyl 
51 benzyloxy --O-- N-(3,5-di-tert- 
butyl-4-hydroxy- 
phenyl)succinamoyl 
______________________________________ 
Examples 52-53 
Using the general procedure of Example 34, the following instant compounds 
of formula V are prepared. 
______________________________________ 
Example R.sub.1 X E 
______________________________________ 
52 propyloxy --NH-- --COC.sub.2 H.sub.5 
53 cyclohexyloxy --O-- --COC.sub.3 H.sub.7 
______________________________________ 
Examples 54-55 
Using the general procedure of Example 35, the following instant compounds 
of formula V are prepared. 
______________________________________ 
Example R.sub.1 X E 
______________________________________ 
54 benzyloxy --NH-- --COOC.sub.2 H.sub.5 
55 octyloxy --O-- --COOC.sub.3 H.sub.7 
______________________________________ 
Examples 56-57 
Using the general procedure of Example 36, the following instant compounds 
of formula V are prepared. 
______________________________________ 
Example R.sub.1 X E 
______________________________________ 
66 methoxy --NH-- 4-bromobenzenesulfonyl 
67 benzyloxy --O-- 1-butanesulfonyl 
______________________________________ 
Examples 58-84 
Using the general procedure of Example 4, the following instant compounds 
of formula IV are prepared. 
______________________________________ 
##STR27## IV 
Example 
R.sub.1 X E 
______________________________________ 
58 methoxy NH ethyl 
59 cyclohexyloxy 
NH propyl 
60 benzyl NH n-butyl 
61 hydrogen O sec-octyl 
62 octyloxy O n-amyl 
63 hydrogen O sec-octyl 
64 methoxy NH CONH-benzyl 
65 hydrogen NH CONH-allyl 
66 butyl NH CONH-cyclohexyl 
67 allyl O CONH-isobutyl 
68 ethoxy O CONH-octadecyl 
69 methoxy NH CSNH-n-butyl 
70 cyclohexyloxy 
NH CSNH-(3-chlorophenyl) 
71 2-hydroxyethyl 
NH CSNH-m-tolyl 
72 octyloxy O CSNH-cyclohexyl 
73 benzyl O CSNH-ethyl 
74 octyloxy O 
succinamoyl 
75 methyl O 
succinamoyl 
76 ethanyol NH 
succinamoyl 
77 benzyl O N-(3,5-di-tert-butyl- 
4-hydroxyphenyl)- 
succinamoyl 
78 hydrogen NH COC.sub.2 H.sub.5 
79 cyclohexyloxy 
O COC.sub.3 H.sub.7 
80 allyl NH COOC.sub.2 H.sub.5 
81 hydrogen O COOC.sub.3 H.sub.7 
82 methoxy NH 4-bromobezenesulfonyl 
83 benzyl O 1-butanesulfonyl 
______________________________________