Sterically hindered amine light stabilizers

摘要

The disclosure concerns sterically hindered amine light stabilizers (HALS) with low basicity at the nitrogen atom and high thermal stability. They are characterized by their spiro-substitution in the 4-position of the tetramethylpiperidine ring (Spiro-NOR-HALS). These compounds are useful in stabilizing polymers, especially thermoplastic polyolefins, against the deleterious effects of oxidative, thermal and actinic radiation. The compounds are also useful in stabilizing acid catalyzed and ambient cured coatings systems. They are particularly useful when high processing temperatures are additional required.

主权项

1. A process for preparing a compound of formula (I), (II), (Id), (Id′), (Ie), (Ie′), (If), (If′), (IIa) or (IIb) wherein X and Y are independently NH or O; m is 1 or 2; n is 1; Z is C═O and Z1 is NH; or Z is NH and Z1 is C═O; R is C1-C20alkyl, C3-C20alkenyl, C3-C20alkynyl which are unsubstituted or substituted by OH, halogen, NO2, carbonyl or carboxyl; phenyl, C7-C12phenylalkyl or C3-C12cycloalkyl; if m is 1 R′ and R″ are independently H, C1-C20alkyl, C3-C20alkenyl, C3-C20alkynyl which are unsubstituted or substituted by OH, halogen, NO2, carbonyl or carboxyl; phenyl, C7-C12phenylalkyl or C3-C12cycloalkyl; with the proviso that if in formula (II) Z is C═O, R is not octyl or methylbenzyl; if m is 2 R″ is H, C1-C20alkyl, C3-C20alkenyl, C3-C20alkynyl which are unsubstituted or substituted by OH, halogen, NO2, carbonyl or carboxyl; phenyl, C7-C12phenylalkyl or C3-C12cycloalkyl; and R′ C1-C20 alkylene, C5-C12cycloalkylene, phenylene, C1-C4alkylene-C5-C12cycloalkylene-C1-C4alkylene, C1-C4alkylene-phenylene-C1-C4alkylene wherein the phenylene and the C5-C12cycloalkyne radicals are unsubstituted or substituted by 1 to 4 C1-C4alkyl groups; R′″ is H, C1-C20alkyl, C3-C12cycloalkyl, phenyl or C7-C12phenylalkyl; and if m is 1 with the proviso that in formula (IIb), R is not octyl or methylbenzyl; and in formula (If′), R′ is not H when R′″ is H, comprising at least one reaction selected from the group consisting of:
a) reacting a compound of formula (O) with HCN or a precursor of HCN or with a compound of formula to obtain a compound of formula (1) wherein R4 is H or Si(CH3)3; and
b) reacting a compound of formula (1) with an amine of formula R′″—NH2 to yield a compound of formula (2) where R′″ is H, C1-C20alkyl, C3-C12cycloalkyl, phenyl or C7-C12phenylalkyl or reacting a compound of formula (O) with HCN or a precursor of HCN in the presence of an amine or ammonia; or
c) reacting a compound of formula (O) with CH3CN and a base to obtain a compound of formula (3) or
d) reacting a compound of formula (O) with a compound of formula to obtain a compound of formula (IIa); and in a further step
e) reacting the compound of formula (1) with an aldehyde, dialdehyde, ketone, or diketone of formula to obtain a compound of formula (IIb) or
reacting the compound of formula (1) with an isocyanate or diisocyanate of formula
R′—[NCO]m to obtain a compound of formula (Id), (Id′); or
f) reacting a compound of formula (2) with an isocyanate of formula
R′—[NCO]m to obtain a compound of formula (If), (If′); and or
g) reacting a compound of formula (3) with an isocyanate of formula
R′—[NCO]m to obtain a compound of formula (Ie), (Ie′) wherein a pressure of said process is from atmospheric pressure to 100 bar.