Polymers containing polyalkylpiperidines and use thereof as stabilizers

The invention entitled "Polymers containing polyalkylpiperidines and use thereof as stabilizers" provides a class of polymers in which groups containing sterically hindered polyalkylpiperidines are linked in the main chain of the polymers via bridging members containing 2-hydroxy-1,3-trimethylene groups. The polymers show superior stabilizing effects for various synthetic polymers such as polyolefins against degradation thereof induced by light and/or heat. The polymers have advantages, as compared with known stabilizer compounds, that they hardly volatile upon processing with heating or during storage of articles containing thereof, and that they are resistant to extraction with solvents from articles containing thereof.

BACKGROUND OF THE INVENTION 
The present invention relates to novel polymers containing sterically 
hindered polyalkylpiperidines which are useful as stabilizers for 
synthetic polymers. 
It has been known that polyalkylpiperidine derivatives in which 1- and/or 
4-positions are substituted are effective polymer stabilizers against 
degradation thereof induced by light and/or heat. For example, 
4-spirohydantoins of 2,2,6,6-tetramethylpiperidine or 
2,6-diethyl-2,3,6-trimethylpiperidine are disclosed in U.S. Pat. Nos. 
3,542,729; 3,705,126; 3,941,744; 4,005,094; 3,898,303; and German 
Offenlegungsschrift No. 26 23 464: amino derivatives are disclosed in U.S. 
Pat. Nos. 3,684,765; 3,904,581; and German Offenlegungsschrift No. 26 21 
870: esters, ethers and carbamates of 4-ol are disclosed in U.S. Pat. Nos. 
3,640,928; 3,840,494; 4,021,432; 3,940,363; 3,993,655; 4,075,165 and 
German Offenlegungsschrift No. 26 47 452: ketals of 4-oxo compound are 
disclosed in U.S. Pat. No. 3,899,464; 3,940,363; and German 
Offenlegungsschrift No. 26 21 855: and pinacol type derivatives are 
disclosed in U.S. Pat. Nos. 4,061,616; 4,055,536 and Japanese Patent 
Provisional Publication No. 51-145548, respectively. 
Furthermore, polymers containing 4-amino-polyalkylpiperidines as the side 
chains are proposed in German Offenlegungsschriften Nos. 26 11 208; 26 36 
144; and 26 36 130. 
DETAILED DESCRIPTION OF INVENTION 
The invention provides polymers in which groups containing 
polyalkylpiperidines represented by the general formulae: 
##STR1## 
(wherein, R.sub.1 represents hydrogen atom or methyl group) are linked in 
the main chain via bridging members containing groups having a formula 
##STR2## 
The polymers show superior stabilizing effect for various polymeric 
materials against light- and heat degradation thereof, with less 
vaporization and exudation therefrom. 
The polymers of the invention containing polyalkylpiperidines are 
represented by the following formula (I): 
##STR3## 
In the above formula, l represents an integer of from 2 to 50, preferably 
2-10, most preferably 2-6. 
Both m.sub.1 and m.sub.2 represent 0, or one of them represents 1 and 
another represents 0. 
X represents a group of formula 
##STR4## 
R.sub.0 represents hydrogen atom or methyl group, preferably hydrogen atom. 
n.sub.1 represents an integer of from 1 to 10, preferably 1. 
n.sub.2 represents 0 or an integer of from 1 to 10, preferably 0. 
W represents a group of formula 
##STR5## 
n.sub.3 represents an integer of from 1 to 10, preferably 4 to 10, most 
preferably 4. As such a group are mentioned, for example, malonyl, 
succinyl, adipoyl, suberoyl, sebacoyl or decane-1,10-dicarbonyl. 
W further represents a group of formula 
##STR6## 
e.g. isophthaloyl or terephthaloyl, preferably phthaloyl, or a group of 
formula 
##STR7## 
e.g. cyclohexane-1,2-dicarbonyl. 
Y represents, when both m.sub.1 and m.sub.2 are 0, one of the following 
formulae (II) to (IV). 
##STR8## 
in which: 
R.sub.1 represents hydrogen atom or methyl group, preferably hydrogen atom. 
R.sub.2 represents hydrogen atom or an alkyl group having from 1 to 18 
carbon atoms, e.g. methyl, ethyl, n-propyl, n-butyl, octyl, dodecyl or 
octadecyl, particularly methyl. Preferred R.sub.2 is hydrogen atom. 
##STR9## 
in which: R.sub.1 has the meaning defined above. 
##STR10## 
in which: 
R.sub.1 has the meaning defined above. 
R.sub.3 represents a group of formula 
##STR11## 
R.sub.4 represents methyl group or ethyl group. 
Y represents, when one of m.sub.1 and m.sub.2 is 1 and another is 0, a 
group of the following formulae (V) to (XI). 
##STR12## 
in which: 
R.sub.1 and R.sub.2 have the meanings defined above. 
A represents an alkylene group having from 2 to 12, preferably 2 to 6, most 
preferably 6 carbon atoms, e.g. ethylene, tetramethylene, hexamethylene, 
octamethylene, decamethylene or dodecamethylene; a xylylene group, e.g. 
o-, m- or p-xylylene, preferably p-xylylene; a group of formula 
##STR13## 
a group of formula --CH.sub.2 COO--R.sub.5 --OCOCH.sub.2 -- in which 
R.sub.5 is an alkylene group having from 2 to 8 carbon atoms, e.g. 
ethylene, tetramethylene, hexamethylene or 2-ethyl-1,6-hexylene, 
preferably ethylene; a group of formula 
##STR14## 
in which R.sub.6 represents hydrogen atom, methyl group or phenyl group, 
preferably hydrogen atom, and R.sub.7 represents an aliphatic, aromatic or 
alicyclic diacyl group having up to 12 carbon atoms, for example, an 
alkanedicarbonyl having from 4 to 12 carbon atoms and optionally 
interrupted by sulfur such as malonyl, succinyl, adipoyl, sebacoyl, 
decane-1,10-dicarbonyl or 3,3'-thiodipropionyl, phthaloyl, isophthaloyl, 
terephthaloyl or cyclohexane-1,4-dicarbonyl; or a group of formula 
##STR15## 
in which p is 0 or 1, preferably 1, R.sub.8 has the same meaning as 
above-defined X, and Z has the meaning defined below. 
##STR16## 
in which: 
R.sub.1 has the meaning defined above. 
R.sub.9 represents an alkyl group having from 1 to 18, preferably 1 to 8 
carbon atoms, e.g. methyl, ethyl, n-propyl, n-butyl, n-octyl, 
2-ethylhexyl, undecyl or octadecyl; a phenyl group; benzyl group; 
cyclohexyl group; or an aliphatic, aromatic araliphatic or alicyclic acyl 
group having up to 18 carbon atoms, for example, an alkanoyl group having 
from 2 to 18 carbon atoms such as acetyl, propionyl, hexanoyl, octanoyl, 
2-ethylhexanoyl, lauroyl or stearoyl, benzoyl, toluoyl or 
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl. The most preferred R.sub.9 
is an alkyl group having from 1 to 4 carbon atoms and acetyl. 
B represents an alkylene group having from 2 to 10, preferably 2 to 6 
carbon atoms, e.g. ethylene, tetramethylene, hexamethylene, octamethylene 
or decamethylene; a xylylene group, e.g. o-, m- or p-xylylene, preferably 
p-xylylene; a group of formula 
##STR17## 
a group of formula --CH.sub.2 COO--R.sub.5 --OCOCH.sub.2 -- in which 
R.sub.5 has the meaning defined above; a group of formula 
##STR18## 
in which R.sub.6 and R.sub.7 have the meanings defined above; or a group 
of formula 
##STR19## 
in which R.sub.8 and p have the meanings defined above and Z has the 
meaning defined below. 
##STR20## 
in which: 
R.sub.1 has the meaning defined above. 
D represents an aliphatic, aromatic, araliphatic or alicyclic diacyl group 
having up to 36 carbon atoms, for example, as described in R.sub.7, an 
alkanedicarbonyl group having from 4 to 12 carbon atoms optionally 
interrupted by sulfur, phthaloyl, isophthaloyl, terephthaloyl or 
cyclohexane-1,4-dicarbonyl, or a diacyl derived from a dimeric acid, and a 
group of formula 
##STR21## 
(in which R.sub.13 represents an alkyl group having from 1 to 4 carbon 
atoms, benzyl group or 3,5-di-tert-butyl-4-hydroxybenzyl group and 
R.sub.14 has the same meaning as above-defined R.sub.13 or represents 
hydrogen atom.); or a group of formula --CONH--R.sub.10 --NHCO-- in which 
R.sub.10 represents an alkylene group having from 2 to 10, preferably 6 
carbon atoms, e.g. ethylene, tetramethylene, hexamethylene, octamethylene 
or decamethylene, a phenylene group optionally substituted with methyl, 
e.g. o-, m- or p-phenylene, particularly 2,4-tolylene, a naphthylene 
group, e.g. 1,5-naphthylene, a xylylene group, e.g. p-xylylene, a 
cyclohexylene group optionally substituted with methyl, e.g. 
1,4-cyclohexylene or methyl-2,4-cyclohexylene, a group of formula 
##STR22## 
(in which R.sub.11 represents oxygen atom or methylene group), a group of 
formula 
##STR23## 
a group of formula 
##STR24## 
or a group of formula 
##STR25## 
in which: 
R.sub.1 and R.sub.3 have the meanings defined above. 
G has the same meaning as above-defined D, or it represents an alkylene 
group having from 3 to 10, preferably 4 to 6 carbon atoms, e.g. 
trimethylene, tetramethylene, hexamethylene, octamethylene or 
decamethylene; a xylylene group, e.g. o-, m- or p-xylylene, preferably 
p-xylylene; a group of formula 
##STR26## 
or a group of formula 
##STR27## 
in which R.sub.8 has the meaning defined above and Z has the meaning 
defind below. 
##STR28## 
in which: R.sub.1 has the meaning defined above. 
##STR29## 
in which: R.sub.1 has the meaning defined above. 
##STR30## 
in which: R.sub.1 has the meaning defined above. 
All of Z in the molecule represent hydrogen atom; an alkyl group having 
from 1 to 18 carbon atoms, e.g. methyl, ethyl, n-propyl, n-butyl, octyl, 
dodecyl or octadecyl, particularly methyl; an aliphatic, aromatic, 
araliphatic or alicyclic acyl group having up to 18 carbon atoms, for 
example as described in R.sub.9, an alkanoyl having from 2 to 18, 
preferably 2 to 4 carbon atoms, benzoyl, toluoyl or 
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl; a group of formula 
--CONHR.sub.12 in which R.sub.12 is an alkyl group having from 1 to 18, 
preferably 1 to 4 carbon atoms, phenyl group or cyclohexyl group. 
Alternatively, a part of Z in the molecule represent hydrogen atom and the 
remaining Z represent above-defined groups other than hydrogen atom. 
Preferably, all of Z in the molecule represent hydrogen atom, acetyl group 
or benzoyl group, or a part of Z in the molecule are hydrogen atom and the 
remaining Z are acetyl group or benzoyl group. 
In formula (I), the terminal groups 
##STR31## 
may be present as groups of formula 
##STR32## 
which impart similar stabilizing effect and included within the scope of 
polymer of the invention. 
Among the polymers of formula (I), preferred groups are as follows: 
(1) in formula (I), when both m.sub.1 and m.sub.2 represents 0; 
(1-a) polymers in which Y is a group of formula (II) and R.sub.1 and 
R.sub.2 are hydrogen atoms, 
(1-b) polymers in which Y is a group of formula (III) or (IV) and R.sub.1 
is hydrogen atom: 
(2) in formula (I), when one of m.sub.1 and m.sub.2 represents 1 and 
another represents O, X represents a group of formula --OCH.sub.2 CH.sub.2 
O-- or --OWO-- in which W represents a group of formula 
##STR33## 
(n.sub.3 represents an integer of from 4 to 10, preferably 4) or a group 
of formula 
##STR34## 
most preferably X is a group of formula 
##STR35## 
(2-a) polymers in which Y is a group of formula (V), R.sub.1 and R.sub.2 
are hydrogen atoms and A is an alkylene group having from 2 to 6, 
particularly 6 carbon atoms or a group of formula 
##STR36## 
(R.sub.8 has the same meaning as above-defined X), 
(2-b) polymers in which Y is a group of formula (VI), R.sub.1 is hydrogen 
atom, R.sub.9 is an alkanoyl group having from 2 to 4 carbon atoms or an 
alkyl group having from 1 to 8 carbon atoms and B is an alkylene group 
having from 2 to 6 carbon atoms; or R.sub.9 is an alkyl group having from 
1 to 8 carbon atoms and B is a group of formula 
##STR37## 
(R.sub.8 has the same meaning as above-defined X); a particularly, 
polymers in which R.sub.9 is acetyl group and B is an alkylene group 
having from 2 to 6 carbon atoms, 
(2-c) polymers in which Y is a group of formula (VII), R.sub.1 is hydrogen 
atom and D is an alkanedicarbonyl group having from 4 to 12 carbon atoms, 
particularly 10 carbon atoms or a group of formula 
##STR38## 
(2-d) polymers in which Y is a group of formula (VIII), R.sub.1 is hydrogen 
atom and G is an alkanedicarbonyl group having from 4 to 12 carbon atoms 
or a group of formula 
##STR39## 
(R.sub.8 has the same meaning as above-defined X), 
(2-e) polymers in which Y is a group of formula (IX), (X) or (XI) and 
R.sub.1 is hydrogen atom. 
The following is a non-limiting list of recurring unit of the polymers of 
the invention: 
______________________________________ 
##STR40## 
No. R.sub.1 R.sub.2 
______________________________________ 
II-1 H H 
II-2 CH.sub.3 H 
______________________________________ 
__________________________________________________________________________ 
##STR41## 
##STR42## 
No. R.sub.1 No. R.sub.1 R.sub.3 
__________________________________________________________________________ 
III-1 H IV-1 H 
##STR43## 
IV-2 H 
##STR44## 
IV-3 H 
##STR45## 
IV-4 CH.sub.3 
##STR46## 
__________________________________________________________________________ 
__________________________________________________________________________ 
##STR47## 
No. X R.sub.1 
R.sub.2 
A 
__________________________________________________________________________ 
V-1 
##STR48## H H (CH.sub.2).sub.4 
V-2 " H H (CH.sub.2).sub.6 
V-3 " H H 
##STR49## 
V-4 " H H 
##STR50## 
V-5 " H H CH.sub.2 COO(CH.sub.2).sub.2 OCOCH.sub. 
2 
V-6 " H H CH.sub.2 CH.sub.2 OCO(CH.sub.2).sub.4 
COOCH.sub.2 CH.sub.2 
V-7 " H H 
##STR51## 
V-8 " H H 
##STR52## 
V-9 
##STR53## H H 
##STR54## 
V-10 
" H H 
##STR55## 
V-11 
" H H 
##STR56## 
V-12 
##STR57## H H 
##STR58## 
##STR59## 
V-13 
##STR60## H H (CH.sub.2).sub.6 
V-14 
" H H 
##STR61## 
V-15 
OCO(CH.sub.2).sub.4 COO H H (CH.sub.2).sub.4 
V-16 
OCO(CH.sub.2).sub.4 COO H H 
##STR62## 
V-17 
OCO(CH.sub.2).sub.8 COO H H 
##STR63## 
V-18 
##STR64## H H 
##STR65## 
V-19 
##STR66## H H 
##STR67## 
V-20 
OCH.sub.2 CH.sub.2 O H H 
##STR68## 
V-21 
##STR69## H H 
##STR70## 
V-22 
##STR71## H H 
##STR72## 
V-23 
##STR73## H CH.sub.3 
(CH.sub.2).sub.4 
V-24 
" CH.sub.3 
H " 
V-25 
##STR74## H H " 
__________________________________________________________________________ 
__________________________________________________________________________ 
##STR75## 
No. X R.sub.1 
R.sub.9 B 
__________________________________________________________________________ 
VI-1 
##STR76## H COCH.sub.3 (CH.sub.2).sub.2 
VI-2 
" H " (CH.sub.2).sub.3 
VI-3 
" H " (CH.sub.2).sub.4 
VI-4 
" H " (CH.sub.2).sub.6 
VI-5 
" H COC.sub.2 H.sub.5 
" 
VI-6 
" H COC.sub.11 H.sub.23 
" 
VI-7 
" H COC.sub.17 H.sub.35 
" 
VI-8 
" H 
##STR77## " 
VI-9 
" H 
##STR78## " 
VI-10 
" H CH.sub.3 " 
VI-11 
" H C.sub.4 H.sub.9 
" 
VI-12 
" H C.sub.8 H.sub.17 
" 
VI-13 
" H COCH.sub.3 (CH.sub.2).sub.10 
VI-14 
" H C.sub.4 H.sub.9 
##STR79## 
VI-15 
" H " 
##STR80## 
VI-16 
" H " CH.sub.2 COO(CH.sub.2).sub.2 
OCOCH.sub.2 
VI-17 
" H " CH.sub.2 CH.sub.2 OCO(CH.sub.2).sub.2 
COOCH.sub.2 CH.sub.2 
VI-18 
" H " CH.sub.2 CH.sub.2 OCO(CH.sub.2).sub.8 
COOCH.sub.2 CH.sub.2 
VI-19 
" H " 
##STR81## 
VI-20 
" H CH.sub.3 
##STR82## 
VI-21 
" H C.sub.2 H.sub.5 
" 
VI-22 
" H C.sub.4 H.sub.9 
" 
VI-23 
" H C.sub.8 H.sub.17 
" 
VI-24 
" H C.sub.12 H.sub.25 
" 
VI-25 
" H C.sub.18 H.sub.37 
" 
VI-26 
##STR83## H COCH.sub.3 (CH.sub.2).sub.6 
VI-27 
" H C.sub.4 H.sub.9 
##STR84## 
VI-28 
OCO(CH.sub.2).sub.4 COO 
H COCH.sub.3 (CH.sub.2).sub.2 
VI-29 
" H " (CH.sub.2).sub.6 
VI-30 
" H C.sub.2 H.sub.5 
##STR85## 
VI-31 
" H C.sub.4 H.sub.9 
" 
VI-32 
" H C.sub.8 H.sub.17 
" 
VI-33 
##STR86## H COCH.sub.3 (CH.sub.2).sub.6 
VI-34 
" H C.sub.4 H.sub.9 
##STR87## 
VI-35 
##STR88## H COCH.sub.3 (CH.sub.2).sub.2 
VI-36 
" H " (CH.sub.2).sub.6 
VI-37 
" H C.sub.4 H.sub.9 
" 
VI-38 
" H C.sub.2 H.sub.5 
##STR89## 
VI-39 
" H C.sub.4 H.sub.9 
" 
VI-40 
" H C.sub.8 H.sub.17 
" 
VI-41 
OCH.sub.2 CH.sub.2 O 
H COCH.sub.3 (CH.sub.2).sub.6 
VI-42 
" H C.sub.4 H.sub. 9 
##STR90## 
VI-43 
##STR91## H " 
##STR92## 
VI-44 
##STR93## CH.sub.3 
COCH.sub.3 (CH.sub.2).sub.6 
VI-45 
##STR94## H " " 
VI-46 
" H C.sub.2 H.sub.5 
##STR95## 
__________________________________________________________________________ 
__________________________________________________________________________ 
##STR96## 
No. X R.sub.1 
D 
__________________________________________________________________________ 
VII-1 
##STR97## H CO(CH.sub.2).sub.2 CO 
VII-2 " H CO(CH.sub.2).sub.4 CO 
VII-3 " H CO(CH.sub.2).sub.8 CO 
VII-4 " H CO(CH.sub.2).sub.10 CO 
VII-5 " H CO(CH.sub.2).sub.2S(CH.sub.2).sub.2 
CO 
VII-6 " H 
##STR98## 
VII-7 " H 
##STR99## 
VII-8 " H 
##STR100## 
VII-9 " H 
##STR101## 
VII-10 " H 
##STR102## 
VII-11 " H 
##STR103## 
VII-12 " H COC.sub.34 H.sub.62 CO 
VII-13 " H CONH(CH.sub.2).sub.6NHCO 
VII-14 " H 
##STR104## 
VII-15 " H 
##STR105## 
VII-16 " H 
##STR106## 
VII-17 " H 
##STR107## 
VII-18 " H 
##STR108## 
VII-19 " H 
##STR109## 
VII-20 " H 
##STR110## 
VII-21 " H 
##STR111## 
VII-22 
##STR112## H 
##STR113## 
VII-23 
##STR114## H CO(CH.sub.2).sub.8 CO 
VII-24 OCO(CH.sub.2).sub.4 COO 
H CO(CH.sub.2).sub.4 CO 
VII-25 " H CO(CH.sub.2).sub.8 CO 
VII-26 OCO(CH.sub.2).sub.8 CO 
H " 
VII-27 OCO(CH.sub.2).sub.10 COO 
H " 
VII-28 
##STR115## H " 
VII-29 
##STR116## H " 
VII-30 OCH.sub.2 CH.sub.2 O H " 
VII-31 
##STR117## H " 
VII-32 
##STR118## CH.sub.3 
" 
VII-33 " H 
##STR119## 
VII-34 
##STR120## H " 
VII-35 OCO(CH.sub.2).sub.4 COO 
H " 
VII-36 OCH.sub.2 CH.sub.2 O H " 
VII-37 
##STR121## H CO(CH.sub.2).sub.4 CO 
__________________________________________________________________________ 
__________________________________________________________________________ 
##STR122## 
No. X R.sub.1 
R.sub.3 
G 
__________________________________________________________________________ 
VIII-1 
##STR123## H 
##STR124## 
CO(CH.sub.2).sub.4 CO 
VIII-2 
" H " CO(CH.sub.2).sub.8 CO 
VIII-3 
" H " 
##STR125## 
VIII-4 
" H " 
##STR126## 
VIII-5 
" H " 
##STR127## 
VIII-6 
" H " (CH.sub.2).sub.4 
VIII-7 
" H " 
##STR128## 
VIII-8 
" H " CONH(CH.sub.2).sub.6 NHCO 
VIII-9 
" H 
##STR129## 
##STR130## 
VIII-10 
" H " 
##STR131## 
VIII-11 
" H " 
##STR132## 
VIII-12 
" H " 
##STR133## 
VIII-13 
" H 
##STR134## 
CO(CH.sub.2).sub.4 CO 
VIII-14 
" H " CO(CH.sub.2).sub.2S(CH.sub.2).sub.2 CO 
VIII-15 
" H " 
##STR135## 
VIII-16 
" H " COC.sub.34 H.sub.62CO 
VIII-17 
" H " 
##STR136## 
VIII-18 
" H " 
##STR137## 
VIII-19 
" H " 
##STR138## 
VIII-20 
" H " 
##STR139## 
VIII-21 
##STR140## H 
##STR141## 
CO(CH.sub.2).sub.4 CO 
VIII-22 
" H " CO(CH.sub.2).sub.10 CO 
VIII-23 
" H " 
##STR142## 
VIII-24 
" H " 
##STR143## 
VIII-25 
" H " (CH.sub.2).sub.6 
VIII-26 
" H " 
##STR144## 
VIII-27 
" H " 
##STR145## 
VIII-28 
" H " 
##STR146## 
VIII-29 
##STR147## H 
##STR148## 
CO(CH.sub.2).sub.4 CO 
VIII-30 
##STR149## H 
##STR150## 
CO(CH.sub.2).sub.4 CO 
VIII-31 
" H 
##STR151## 
##STR152## 
VIII-32 
OCO(CH.sub.2).sub.4 COO 
H 
##STR153## 
CO(CH.sub.2).sub.4 CO 
VIII-33 
" H " 
##STR154## 
VIII-34 
##STR155## H " CO(CH.sub.2).sub.4 CO 
VIII-35 
" H " 
##STR156## 
VIII-36 
OCH.sub.2 CH.sub.2 O 
H " 
##STR157## 
VIII-37 
##STR158## CH.sub.3 
" CO(CH.sub.2).sub.4 CO 
__________________________________________________________________________ 
__________________________________________________________________________ 
##STR159## 
No. X R.sub.1 
__________________________________________________________________________ 
IX-1 
##STR160## H 
IX-2 
##STR161## H 
IX-3 
##STR162## H 
IX-4 OCO(CH.sub.2).sub.8 COO H 
IX-5 
##STR163## H 
IX-6 OCH.sub.2 CH.sub.2 O H 
IX-7 
##STR164## CH.sub.3 
__________________________________________________________________________ 
__________________________________________________________________________ 
##STR165## 
No. X R.sub.1 
__________________________________________________________________________ 
X-1 
##STR166## H 
X-2 
##STR167## H 
X-3 OCO(CH.sub.2).sub.4 COO 
H 
X-4 
##STR168## H 
X-5 OCH.sub.2 CH.sub.2 O H 
__________________________________________________________________________ 
__________________________________________________________________________ 
##STR169## 
No. X R.sub.1 
__________________________________________________________________________ 
XI-1 
##STR170## H 
XI-2 
##STR171## H 
XI-3 OCO(CH.sub.2).sub.4 COO 
H 
XI-4 
##STR172## H 
XI-5 OCH.sub.2 CH.sub.2 O H 
__________________________________________________________________________ 
The polymers of the invention having formula (I) may be either homopolymer 
or copolymer. In other words, each of the meanings W, X and Y may be all 
same, partly different, or all different in their structures. In some 
instances, copolymers give better physical and/or stabilizing properties 
than homopolymers. 
Derived polymers having the above-mentioned recurring unit and a part or 
all of hydroxy groups of the polymer are etherified, esterified or derived 
into carbamate are also representative polymers of the invention. 
As such derived polymers are preferably mentioned, e.g. methyl ethers, 
ethyl ethers, acetates, propionates, benzoates, N-methyl carbamates, 
N-ethyl carbamates, N-phenyl carbamates and N-cyclohexyl carbamates. 
The polymers of formula (I) according to the invention may be prepared by 
any one of following methods which are performed under per se known 
conditions. 
(1) Polymers in which Z is hydrogen atom and both m.sub.1 and m.sub.2 are O 
may be prepared by polymerizing an epoxy compound having the formula 
##STR173## 
(in which, Y.sub.1 is a group of formulae (II) to (IV), with proviso that 
2,3-epoxypropyl group is linked to the nitrogen atom at 3-position, the 
oxygen atom at 4-position or the oxygen atom of --CH.sub.2 O-- in formulae 
(II), (III) and (IV), respectively. 
The reaction is performed preferably by heating the starting compound (XII) 
at 60.degree.-230.degree. C. in the presence or absence of an inert 
solvent. As the solvent, there may be employed, e.g. ethers such as 
dioxane or diethyleneglycol dimethyl ether; dialkylamides such as 
dimethylformamide or dimethylacetamide; chlorinated or non-chlorinated 
aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene or 
p-dichlorobenzene; and alcohols or mixtures thereof with water such as 
methanol, ethanol, n- ot tert-butanol, n-octanol, aqueous methanol or 
aqueous ethanol. 
In performing the reaction, there may be employed a catalyst, if necessary. 
As the catalyst are mentioned known ones used for hardening of epoxy 
resins, e.g. tert-amines such as triethylamine, triethanolamine or 
1,5-diazabicyclo[5.4.0]-undecene-5 (DBU) or Lewis acids such as boron 
trifluoride or zinc borofluoride. 
The starting compounds (XII) may be prepared by reacting a compound of 
formula H-Y.sub.1 -H with 1 mole equivalent of an epihalohydrin. 
(2) Polymers of formula (I) in which Z is hydrogen atom and one of m.sub.1 
and m.sub.2 is 1 and another is 0 may be prepared by polymerizing an epoxy 
compound of formula 
##STR174## 
with a piperidine compound of formula H-Y.sub.2 -H, or by polymerizing an 
epoxy compound containing piperidine of formula 
##STR175## 
with a compound H-X-H (in which, Y.sub.2 is above-defined group of formula 
(V) to (XI) and X has the meaning defined above.). 
The reaction is performed in the similar conditions as in the 
above-mentioned (1). 
The starting compounds (XIV) may be prepared by reacting a compound of 
formula H-Y.sub.2 -H with 2 mole equivalent of an epihalohydrin. 
(3) Compounds of formula (I) in which a part or all of hydrogen atom of Z 
are substituted may be prepared by introducing a substituent to a compound 
in which Z is hydrogen atom and obtained in accordance with the 
above-mentioned (1) or (2), by the methods described below: 
(3-a) Compounds in which Z is an alkyl group may be prepared by reacting 
the corresponding compound in which Z is hydrogen atom with a strong basic 
alkali metal compound such as sodium hydride or potassium tert-butyrate 
and then with the desired alkyl halide. 
(3-b) Compounds in which Z is an acyl group may be prepared by reacting the 
corresponding compound in which Z is hydrogen atom with a reactive 
derivative of the corresponding carboxylic acid. As the reactive 
derivatives, are employed acid halides, acid lower alkyl esters or acid 
anhydrides, preferably acid anhydrides. 
(3-c) Compounds in which Z is a N-substituted carbamoyl group may be 
prepared by reacting the corresponding compound in which Z is hydrogen 
atom with the corresponding isocyanate. 
The polymers of formula (I) according to the invention can effectively 
stabilize wide varieties of synthetic polymers. 
Synthetic polymers stabilized in this way include: 
olefin and diene polymers 
including homopolymers of olefins and dienes (e.g. low-density, 
high-density and cross-linked polyethylenes, polypropylene, 
polyisobutylene, polymethylbutene-1, polymethylpentene-1, polyisoprene, 
and polybutadiene), mixtures of such homopolymers (e.g. mixtures of 
polypropylene and polyethylene, polypropylene and polybutene-1, or 
polypropylene and polyisobutylene), and copolymers of olefins and dienes 
(e.g. ethylene/propylene copolymers, propylene/butene-1 copolymers, 
propylene/isobutylene copolymers, ethylene/butene-1 copolymers, and 
terpolymers of ethylene and propylene with dienes such as hexadiene, 
dicyclopentadiene or ethylidene norbornene); 
styrene polymers 
including polystyrene, copolymers of styrene and of .alpha.-methylstyrene 
(e.g. styrene/butadiene copolymers, styrene/acrylonitrile copolymers, 
styrene/acrylonitrile/methylmethacrylate copolymers, 
styrene/acrylonitrile/acrylic ester copolymers, styrene/acrylonitrile 
copolymers modified with acrylic ester polymers to provide impact 
strength, and styrene polymers modified with ethylene/propylene/diene 
elastomers to provide impact strength), and graft copolymers of styrene 
(e.g. polymers in which styrene is grafted onto polybutadiene, and 
polymers in which styrene and acrylonitrile are grafted onto polybutadiene 
as well as mixtures thereof with the aforementioned styrene copolymers 
commonly known as acrylonitrile/butadiene/styrene or ABS plastics); 
halogenated vinyl and vinylidene polymers 
including polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, 
polychloroprene, chlorinated rubbers, vinyl chloride/vinylidene chloride 
copolymers, vinyl chloride/vinyl acetate copolymers, and vinylidene 
chloride/vinyl acetate copolymers. 
polymers derived from .alpha.,.beta.-unsaturated acids 
and derivatives thereof, including polyacrylates and polymethacrylates, 
polyacrylic amides and polyacrylonitrile; 
polymers derived from unsaturated alcohols and amines 
and from the acyl derivatives thereof or acetals, including polyvinyl 
alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, 
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, and polyallyl 
malamine, and copolymers thereof with other ethylenically unsaturated 
monomers (e.g. ethylene/vinyl acetate copolymers); 
epoxy polymers 
including homopolymers and copolymers derived from epoxides (e.g. 
polyethylene oxide), and polymers derived from bis-glycidyl ethers; 
polyacetals, polyalkylene oxides and polyphenylene oxides 
including polyoxymethylene, oxymethylene/ethylene oxide copolymers, 
polyoxyethylene, polypropylene oxide, polyisobutylene oxide and 
polyphenylene oxides; 
polyurethanes and polyureas; 
polycarbonates; 
polysulphones; 
polyamides and copolyamides 
derived from diamines and dicarboxylic acids and/or from aminocarboxylic 
acids or the corresponding lactams, including nylon-6, nylon-6,6, 
nylon-6,10, nylon-11 and nylon-12; 
polyesters 
derived from dicarboxylic acids and dialcohols and/or from 
hydroxycarboxylic acids and the corresponding lactones, e.g. polyethylene 
glycol terephthalate and poly-1,4-dimethylol-cyclohexane terephthalate; 
cross-linked polymers 
derived from aldehydes together with phenols, ureas or melamines, e.g. 
phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins; 
alkyd resins 
e.g. glycerol/phthalic acid resins and mixtures thereof with 
malamine/formaldehyde resins; 
unsaturated polyester resins 
derived from copolyesters of saturated and unsaturated dicarboxylic acids 
with polyhydric alcohols as well as from vinyl compounds as cross-linking 
agents, and also halogenated flame-resistant modifications thereof. 
The amount of the stabilizers of the invention needed for effective 
stabilization of organic polymers will depend on a variety of factors, 
such as the type and properties of the polymer concerned, its intended 
use, and the presence of other stabilizers. It is generally satisfactory 
to use from 0.01% to 5% by weight of the stabilizers of the invention, 
based on the weight of the polymer, but the most effective range will vary 
with the type of polymer: viz. 0.01% to 2.0%, preferably 0.02% to 1.0%, by 
weight for olefin, diene and styrene polymers; 0.01% to 1.0%, preferably 
0.02% to 0.5%, by weight for vinyl and vinylidene polymers; and 0.01% to 
5.0%, preferably 0.02% to 2.0%, by weight for polyurethanes and 
polyamides. If desired, two or more of the stabilizers of the invention 
may be used together. 
The polymeric stabilizers of the invention may readily be incorporated into 
synthetic polymers to be stabilized by conventional techniques at any 
convenient stage prior to the manufacture of shaped articles therefrom. 
For examples, the polymeric stabilizer may be mixed with the polymer to be 
stabilized in dry powder form, or a suspension or emulsion of the 
stabilizer may be mixed with a solution, suspension or emulsion of the 
polymer to be stabilized. 
The stabilized polymeric composition of the invention may optionally also 
contain one or more of various additives conventionally used in polymer 
technology, such as the additives listed in British Patent Specification 
No. 1 401 924, at pages 11-13.

The invention is further illustrated by the following Examples, in which 
the mean molecular weight was measured by vapor pressure depression 
method. 
EXAMPLE 1 
##STR176## 
1.4 g of 
3-(2,3-epoxypropyl)-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d 
ione were heated at 180.degree.-190.degree. C. for 20 minutes in the 
absence of a solvent. 
Ethyl acetate was added to the reaction mixture and insoluble materials 
were filtered off. Precipitate formed by addition of n-hexane to the ethyl 
acetate solution was collected by filtration and dried under reduced 
pressure, giving white powder (Compound No. 1) softening at 
205.degree.-208.degree. l C. and having a means molecular weight of 1,350. 
EXAMPLE 2 
##STR177## 
3.0 g of 4-(2,3-epoxypropoxy)-2,2,6,6-tetramethyl-piperidine were heated at 
210.degree.-220.degree. C. for 5 hours under argon stream. Upon cooling, 
the reaction product solidified, giving a vitreous solid, which was 
triturated yielding pale yellow powder (Compound No. 2) softening at 
140.degree.-145.degree. C. and having a mean molecular weight of 3,800. 
EXAMPLE 3 
Acetate of Compound No. 2 
A mixture of 1.0 g of the pale yellow powder obtained in Example 2 and 10 g 
of acetic anhydride was heated at 100.degree.-110.degree. C. for 5 hours 
under nitrogen stream. The reaction mixture was poured into ice-water, 
neutralized with aqueous ammonia and extracted with ethyl acetate. The 
organic phase was washed with water and dried over anhydrous magnesium 
sulfate. 
The ethyl acetate was removed by evaporation under reduced pressure, 
affording the desired compound (Compound No. 3) softening at 
103.degree.-106.degree. C. The results of measurements of the compound by 
infrared and NMR spectrometries revealed that all of the hydroxy groups of 
the compound were acetylated. 
EXAMPLE 4 
##STR178## 
3.0 g of 
2-(2,3-epoxypropoxymethyl)-7,7,9,9-tetramethyl-1,4-dioxa-8-azaspiro[4.5]de 
cane were heated in the similar manner as in Example 2. By treating the 
reaction mixture, there was obtained the desired compound No. 4as pale 
yellow powder softening at 128.degree.-135.degree. C. and having a mean 
molecular weight of 14,000. The above-mentioned starting material was 
heated at 210.degree.-220.degree. C. for 2 hours under argon stream and 
treated, giving pale yellow powder (Compound No. 5) softening at 
80.degree.-85.degree. C. and having a mean molecular weight of 2,200. 
EXAMPLE 5 
##STR179## 
To 6.0 g of 
2-hydroxymethyl-8-(2,3-epoxypropyl)-7,7,9,9-tetramethyl-1,4-dioxa-8-azaspi 
ro[4.5]decane were added 20 ml of 10% potassium hydroxide aqueous solution 
and the mixture was refluxed for 5 hours, under stirring. 
The reaction mixture was extracted with benzene and the benzene solution 
was washed with water and dried over potassium carbonate. The residue 
obtained by removing the solvent was purified by column chromatography 
(silica gel; ethyl acetate: triethylamine=19:1), giving the desired 
compound (Compound No. 6) as pale yellow, viscous oily product having a 
mean molecular weight of 600. 
EXAMPLE 6 
##STR180## 
5.0 g of 
3-ethyl-3-(2,3-epoxypropoxymethyl)-8,8,10,10-tetramethyl-1,5-dioxa-9-azasp 
iro[5.5]undecane were heated at 220.degree.-230.degree. C. for 10 hours 
under argon stream. 
The reaction mixture was treated in the similar manner as in Example 2, 
giving the desired compound (Compound No. 7) as pale yellow powder 
softening at 130.degree.-140.degree. C. and having a mean molecular weight 
of 14,000. 
The above-mentioned starting compound was heated at 210.degree.-220.degree. 
C. for 2 hours under argon stream and treated in the similar manner, 
giving the desired compound (Compound No. 8) as white powder softening at 
55.degree.-60.degree. C. and having a means molecular weight of 1,200. 
EXAMPLE 7 
##STR181## 
7.9 g of 
2,2-bis{p-[2-hydroxy-3-(7,7,9,9,-tetramethyl-2,4-dioxo-1,3,8-triazaspiro[4 
.5]dec-3-yl)propoxy]-phenyl}propane and 3.4 g of 2,2-bis 
[p-(2,3-epoxypropoxy)-phenyl]propane were heated at 
180.degree.-190.degree. C. for 20 minutes in the absence of solvent. The 
reaction mixture was washed with ethyl acetate and dried under reduced 
pressure, giving the desired compound (Compound No. 9) as white powder 
softening at 175.degree.-180.degree. C. and having a mean molecular weight 
of 3,200. 
EXAMPLE 8 
##STR182## 
5.0 g of 
3,3'-hexamethylenebis(7,7,9,9,-tetramethyl-1,3,8-triazaspiro[4.5]decane-2, 
4-dione) and 3.3 g of 2,2-bis [4-(2,3-epoxypropoxy)cyclohexyl]propane were 
heated at 230.degree. C. for 3 hours under argon stream. The reaction 
mixture was dissolved in chloroform and the solution was poured into 
n-hexane, separating out a precipitate. The precipitate was collected by 
filtration and dried under reduced pressure, giving the desired compound 
(Compound No. 10) as white powder softening at 139.degree.-141.degree. C. 
and having a mean molecular weight of 1,900. 
EXAMPLE 9 
Benzoate of Compound No. 10 
2.0 g of white powder obtained in Example 8 and 8.0 g of benzoic anhydride 
were heated at 150.degree. C. for 15 hours under argon stream. The 
reaction mixture was dissolved in ethyl acetate, washed with 5% potassium 
carbonate aqueous solution and water, and dried over sodium sulfate. The 
residue obtained by removing the solvent was purified by column 
chromatography. At first, elution with ethyl acetate gave white powder 
(Compound No. 11) softening at 115.degree.-120.degree. C. The NMR spectrum 
of the compound showed that the benzoylation rate was 95%. Second elution 
with ethyl acetate: ethanol: triethylamine=20: 1: 1 gave greyish white 
powder (Compound No. 12) softening at 115.degree.-118.degree. C. 
The NMR spectrum of the compound showed that the benzoylation rate was 45%. 
EXAMPLE 10 
##STR183## 
4.8 g of 
N,N'-hexamethylenebis[N-(2,2,6,6-tetramethyl-4-piperidyl)acetamide] and 
3.4 g of 2,2-bis[p-(2,3-epoxypropoxy)phenyl]propane in 25 ml of n-octanol 
were refluxed at 180.degree.-200.degree. C. for 8 hours. n-Octanol was 
removed under reduced pressure and the residue was purified by column 
chromatography (silica gel; ethyl acetate: triethylamine: methanol=8: 1: 
1), giving white powder (Compound No. 13) softening at 
108.degree.-115.degree. C. and having a mean molecular weight of 2,600 
from the first eluate, and white powder (Compound No. 14) softening at 
90.degree.-110.degree. C. and having a mean molecular weight of 1,650 from 
the second eluate. 
The above-mentioned starting compound was heated at 200.degree.-220.degree. 
C. for 3 hours in the absence of a solvent and treated and purified in the 
similar manner, giving white powder (Compound No. 15) softening at 
150.degree.-160.degree. C. and having a mean molecular weight of 6,000 
from the first eluate, and white powder (Compound No. 16) softening at 
120.degree.-130.degree. C. and having a mean molecular weight of 2,650 
from the second eluate. 
EXAMPLE 11 
##STR184## 
4.8 g of 
N,N'-hexamethylenebis[N-(2,2,6,6-tetramethyl-4-piperidyl)acetamide] and 
2.8 g of bis(2,3-epoxypropyl) 1,2-cyclohexanedicarboxylate were heated at 
200.degree. C. for 5 hours under nitrogen stream. The reaction mixture was 
purified by column chromatography (silica gel; ethyl acetate: 
triethylamine: methanol=8: 1: 1) and the crude product thus obtained was 
dissolved in benzene. The benzene solution was poured into n-hexane and 
the precipitate formed was collected by filtration, giving white powder 
(Compound No. 17) softening at 115.degree.-125.degree. C. and having a 
mean molecular weight of 2,700. 
EXAMPLE 12 
##STR185## 
3.0 g of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and 2.1 g of 
2,2-bis[p(2,3-epoxypropoxy)phenyl]propane were heated at 
190.degree.-200.degree. C. for 4 hours under argon stream. 
The reaction mixture was purified by column chromatography (silica gel; 
ethyl acetate: triethylamine=20: 1), giving pale yellow solid product 
(Compound No. 18) softening at 85.degree.-90.degree. C. and having a mean 
molecular weight of 2,500 from the first eluate, and pale yellow solid 
product (Compound No. 19) softening at 74.degree.-77.degree. C. and having 
a mean molecular weight of 1,900 from the second eluate. 
EXAMPLE 13 
##STR186## 
2.2 g of bis[1-(2,3-epoxypropyl)-2,2,6,6-tetramethyl-4-piperidyl] sebacate 
and 0.55 g of adipic acid were refluxed in 5 ml of n-butanol for 24 hours. 
The n-butanol was removed from the reaction mixture and the residue was 
washed with n-hexane and then treated with ethyl acetate. 
The ethyl acetate soluble fraction was purified by column chromatography 
(silica gel; ethyl acetate: ethanol=4: 1), giving the desired compound 
(Compound No. 20) as pale yellow oil having a mean molecular weight of 
1,600. 
EXAMPLE 14 
##STR187## 
2.7 g of bis[1-(2,3-epoxypropyl)-2,2,6,6-tetramethyl-4-piperidyl] sebacate 
and 0.95 g of 1,10-decanedicarboxylic acid were refluxed in 6 ml of n-amyl 
alcohol for 17 hours. The reaction mixture was treated in the similar 
manner as in Example 12, giving the desired compound (Compound No. 21) as 
pale yellow oil having a mean molecular weight of 1,820. 
EXAMPLE 15 
##STR188## 
3.0 g of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and 1.1 g of 
ethyleneglycol diglycidyl ether were heated at 200.degree.-220.degree. C. 
for 8 hours under argon stream. 
The reaction mixture was purified by column chromatography (silica gel; 
ethyl acetate: ethanol: triethylamine=20: 1: 1), giving pale yellow, 
viscous oil (Compound No. 22) having a mean molecular weight of 3,000 from 
the first eluate, and pale yellow viscous oil (Compound No. 23) having a 
mean molecular weight of 2,300 from the second eluate. 
EXAMPLE 16 
##STR189## 
4.4 g of 
2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tatraoxa-3,15-diazatrispiro[5.2. 
2.5.2.2.]heneicosane and 3.4 g of 
2,2-bis[p-(2,3-epoxypropoxy)phenyl]propane were heated at 180.degree. C. 
for 8 hours under nitrogen stream. 
The reaction mixture was purified by column chromatography (silica gel; 
ethyl acetate: triethylamine=9: 1), and the product was dissolved in 
benzene and precipitated with n-hexane, giving the desired compound 
(Compound No. 24) as white powder softening at 180.degree.-200.degree. C. 
and having a mean molecular weight of 3,450. 
EXAMPLE 17 
Acetate of Compound No. 24 
2 g of the white powder obtained in Example 16 and 10 g of acetic anhydride 
were refluxed in 20 ml of benzene for 5 hours. The reaction mixture was 
washed with 10% potassium carbonate aqueous solution and the benzene layer 
was dried over potassium carbonate. The residue obtained by removing the 
solvent was purified by column chromatography (silica gel; ethyl acetate) 
and the obtained crude product was dissolved in benzene. 
Precipitate formed by pouring the benzene solution to n-hexane was 
collected by filtration, giving white powder (Compound No. 25) softening 
at 155.degree.-175.degree. C. The IR and NMR spectra showed that the 
hydroxy groups have been completely acetylated. 
EXAMPLE 18 
##STR190## 
2.1 g of 
3,15-bis(2,3-epoxypropyl)-2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetrao 
xa-3,15-diaza-trispiro[5.2.2.5.2.2.]heneicosane and 0.8 g of sebacic acid 
were refluxed in a mixture of 10 ml of tert-butanol and 10 ml of toluene 
for 14 hours. After the solvent was removed under reduced pressure, the 
residue was purified by column chromatography (silica gel; ethyl acetate: 
methanol=1: 1), giving the desired compound (Compound No. 26) as white 
powder softening at 149.degree.-158.degree. C. and having a mean molecular 
weight of 5,100. 
EXAMPLE 19 
##STR191## 
4.1 g of 
2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetraoxa-3,15-diazatrispiro[5.2. 
2.5.2.2.]heneicosane and 1.74 g of ethyleneglycol diglycidyl ether was 
heated at 200.degree. C. in 4 ml of octanol for 20 hours, under stirring. 
After the octanol was removed under reduced pressure, the residue was 
purified by column chromatography (silica gel; ethyl acetate: methanol: 
triethylamine =2: 2: 1), giving the desired compound (Compound No. 27) as 
pale yellow powder softening at 140.degree.-154.degree. C. and having a 
mean molecular weight of 2,770. 
EXAMPLE 20 
##STR192## 
6.4 g of 4,4'-bis(2,2,6,6-tetramethyl-4-piperidinol) and 6.8 g of 
2,2-bis[p-(2,3-epoxypropoxy)phenyl]propane were heated at 
150.degree.-160.degree. C. in 80 ml of octanol for 8 hours, under 
stirring. After the octanol was removed under reduced pressure, the 
vitreous mass left was triturated, giving the desired compound (Compound 
No. 28) as white powder softening at 106.degree.-109.degree. C. and having 
a mean molecular weight of 1,850. 
EXAMPLE 21 
##STR193## 
1.5 g of 2,2,2,',2',6,6,6',6'-octamethyl-4,4'-bipiperidilydene and 1.8 g of 
2,2-bis[p-(2,3-epoxypropoxy) phenyl]propane was heated at 
180.degree.-220.degree. C. for 2 hours under argon stream. The reaction 
mixture was dissolved in chloroform and methanol was added thereto, 
forming precipitate. The precipitate was collected by filtration, washed 
with methanol and dried under reduced pressure, giving the desired 
compound (Compound No. 29) as white solid softening at 
170.degree.-180.degree. C. and having a mean molecular weight of 5,300. 
EXAMPLE 22 
##STR194## 
A mixture of 5.24 g of bis(2,2,6,6-tetramethyl-4-piperidyl) adipate and 4.2 
g of 2,2-bis[p-(2,3-epoxypropoxy)-phenyl]propane was heated at 
160.degree.-170.degree. C. for 6 hours under nitrogen stream. The reaction 
mixture was purified by column chromatography through silica gel eluted 
with ethyl acetate, giving the desired compound (Compound No. 30) in the 
form of a white powdersoftening at 95.degree.-115.degree. C. and having a 
mean molecular weight of 3,700. 
EXAMPLE 23 
##STR195## 
A mixture of 8.5 g of bis(2,2,6,6-tetramethyl-4-piperidyl) adipate and 5.2 
g of bis(2,3-epoxypropyl) 1,4-butanedicarboxylate was heated at 
160.degree.-170.degree. C. for 4 hours under nitrogen stream. The reaction 
mixture was dissolved in ethyl acetate and the solution was poured into 
n-hexane, affording an oily substance which is insoluble in n-hexane. The 
oily substance was dried under reduced pressure, affording the desired 
compound (Compound No. 31) in the form of a colorless solid softening at 
97.degree.-115.degree. C. and having a mean molecular weight of 3,700. 
EXAMPLE 24 
##STR196## 
A mixture of 4.8 g of 
N,N'-hexamethylenebis[N-(2,2,6,6-tetramethyl-4-piperidyl)acetamdie] and 
2.6 g of bis(2,3-epoxypropyl) 1,4-butanedicarboxylate was heated at 
200.degree. C. for 3 hours under nitrogen stream. The reaction mixture was 
washed with hot n-hexane and dried under reduced pressure, affording the 
desired compound (Compound No. 32) in the form of a pale yellow powder 
softening at 50.degree.-60.degree. C. and having a mean molecular weight 
of 2020. 
EXAMPLE 25 
##STR197## 
A mixture of 4.8 g of 
N,N'-hexamethylenebis[N-(2,2,6,6-tetramethyl-4-piperidyl)acetamide] and 
1.74 g of ethylene glycol diglycidyl ether was heated at 250.degree. C. 
for 1 hour under nitrogen stream. The reaction mixture was dissolved in 
benzene and the solution was poured into n-hexane to give a precipitate. 
The precipitate was collected by filtration and dried under reduced 
pressure, affording the desired compound (Compound No. 33) in the form of 
a pale yellow powder softening at 85.degree.-95.degree. C. and having a 
mean molecular weight of 2,360. 
EXAMPLE 26 
##STR198## 
A mixture of 4.25 g of bis(2,2,6,6-tetramethyl-4-piperidyl) adipate and 
2.84 g of bis(2,3-epoxypropyl) 1,2-cyclohexanedicarboxylate was heated at 
170.degree.-180.degree. C. for 16 hours under argon stream. The reaction 
mixture was dissolved in benzene and the solution was poured into n-hexane 
to give a precipitate. The precipitate was collected by filtration and 
dried under reduced pressure, affording the desired compound (Compound No. 
34) in the form of a colorless solid softening at 89.degree.-95.degree. C. 
and having a mean molecular weight of 4,530. 
EXAMPLE 27 
##STR199## 
A mixture of 3.0 g of bis(2,2,6,6-tetramethyl-4-piperidyl) isophthalate and 
2.3 g of bis[p-(2,3-epoxypropoxy)phenyl]-propane was heated at 180.degree. 
C. for 7 hours under nitrogen stream. The reaction mixture was dissolved 
in benzene and the solution was poured into n-hexane to give a 
precipitate. 
The precipitate was collected by filtration and dried under reduced 
pressure to give the desired compound (Compound No. 35) in the form of a 
white powder softening at 155.degree.-165.degree. C. and having a mean 
molecular weight of 4,270. 
EXAMPLE 28 
##STR200## 
A mixture of 3.5 g of bis(2,2,6,6-tetramethyl-4-piperidyl) isophthalate and 
2.2 g of bis(2,3-epoxypropyl) 1,2-cyclohexanedicarboxylate was heated at 
180.degree. C. for 7 hours under nitrogen stream. The reaction mixture was 
dissolved in benzene and the solution was poured into n-hexane to give a 
precipitate, which was collected by filtration and dried under reduced 
pressure, affording the desired compound (Compound No. 36) in the form of 
a white powder softening at 94.degree.-104.degree. C. and having a mean 
molecular weight of 1,660. 
EXAMPLE 29 
##STR201## 
A mixture of 3.5 g of bis(2,2,6,6-tetramethyl-4-piperidyl) isophthalate and 
2.0 g of bis(2,3-epoxypropoxy) adipate was heated at 180.degree. C. for 7 
hours under nitrogen stream. The reaction mixture was dissolved in benzene 
and the solution was filtered and poured into n-hexane to give a 
precipitate. 
The precipitate was collected by filtration and dried under reduced 
pressure to give the desired compound (Compound No. 37) in the form of a 
pale yellow powder softening at 90.degree.-100.degree. C. and having a 
mean molecular weight of 3,000. 
EXAMPLE 30 
##STR202## 
A mixture of 3.5 g of bis(2,2,6,6-tetramethyl-4-piperidyl) isophthalate and 
1.4 g of ethylene glycol diglycidyl ether was heated at 180.degree. C. for 
7 hours under nitrogen stream. 
The reaction mixture was dissolved in benzene and the solution was poured 
into n-hexane to give a precipitate. The precipitate was collected by 
filtration and dried under reduced pressure, affording the desired 
compound (Compound No. 38) in the form of a pale yellow powder softening 
at 98.degree.-105.degree. C. and having a mean molecular weight of 3,200. 
EXAMPLE 31 
Stabilization of polypropylene 
Mixtures were made from 100 parts of unstabilized polypropylene powder 
(MFI=18), 0.2 part of stearyl 
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as an antioxidant, and 
0.25 part of the stabilizer compounds of the invention. The mixtures were 
blended and homogenized with a Brabender Plastograph at 200.degree. C. for 
10 minutes and the formed mass was pressed to a sheet of 2-3 mm thick with 
a laboratory press. The sheet was pressed with a hydraulic press at 
260.degree. C. for 6 minutes (12 tons) and put immediately into cold water 
to form a film of 0.5 mm thick, from which a film of 0.1 mm thick was 
obtained by the same procedures. 
The film was cut into test specimens of 50.times.120 mm. The test specimens 
were exposed to light in a Sunshine Weather Meter at a black panel 
temperature of 63.degree..+-.3.degree. C. and examined periodically to 
determine the percentage of elongation at brake. The test results were 
expressed as a ratio of the time required for the test specimens to reach 
50% elongation at brake when a stabilizer was used to the time required 
for the test specimens to reach 50% elongation at brake when no stabilizer 
was used. The results are shown in Table 1. 
TABLE 1. 
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Compound No. Ratio 
______________________________________ 
1 7.8 
2 7.2 
3 7.4 
5 5.4 
8 6.1 
10 4.8 
14 7.1 
17 6.8 
19 6.0 
20 7.7 
21 6.2 
22 7.8 
27 6.4 
28 4.3 
29 4.4 
30 5.0 
31 7.1 
32 5.3 
33 5.9 
34 &gt;6.7 
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EXAMPLE 32 
Stabilization of polystyrene 
Mixtures were made from 100 parts of polystyrene ("Styron 666", trade name 
of Asahi Dow Co., Ltd.) and 0.25 part of each in turn of the stabilizers 
indicated in Table 2. 
The resulting mixtures were blended and homogenized by means of a Brabender 
Plastograph at 200.degree. C. for 5 minutes, then compression-molded at 
180.degree. C. for 2 minutes, forming sheets of thickness 1.5 mm. 
Each test sheet was exposed to light in a Xenon Weather-O-Meter (6.5 kw; 
ASTM G26-77) for 1500 hours and the yellowness index of the sheet before 
and after irradiation was determined in accordance with ASTM D1925. The 
results are shown in Table 2. 
TABLE 2. 
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Yellowness Index 
Before After 
Compound No. irradiation irradiation 
______________________________________ 
2 1.9 7.1 
8 1.8 8.7 
10 2.0 8.6 
17 2.2 10.2 
19 1.8 10.8 
20 1.7 8.3 
22 1.9 9.5 
28 2.1 10.4 
None 1.8 35.2 
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EXAMPLE 33 
Stabilization of polyurethane 
Mixtures were made from 10 g of polyurethane ("Paraprene 22S", trade name 
of Nippon Polyurethane Kogyo KK) and 0.05g of each in turn of the 
stabilizers of the invention indicated in Table 3. Each mixture was 
dissolved in 30 ml of dimethylformamide and the resulting solution was 
drawn on a glass plate to form a sheet of thickness 0.4 mm. The sheets 
were maintained at 60.degree. C. for 20 minutes and dried at 120.degree. 
C. for 15 minutes to cast films of thickness 0.1 mm. The films thus 
obtained were exposed to ultraviolet radiation in a Sunshine Carbon Arc 
Lamp Weather Meter (type "WEL-SUN-HC", trade name of Suga Test Instruments 
Co., Ltd.) for 300 hours and the yellowness index before and after 
irradiation was determined in accordance with ASTM D1925. The results are 
shown in Table 3. 
TABLE 3. 
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Yellowness Index 
Before After 
Compound No. Irradiation Irradiation 
______________________________________ 
2 1.5 23.7 
8 1.9 25.5 
10 1.7 22.8 
17 2.0 26.5 
19 1.6 23.1 
20 1.8 21.9 
22 1.6 22.8 
None 1.5 47.6 
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