CA1148952A - Alkylated diaza-spirodecanes, their preparation and use as light stabilizers - Google Patents
Alkylated diaza-spirodecanes, their preparation and use as light stabilizersInfo
- Publication number
- CA1148952A CA1148952A CA000358634A CA358634A CA1148952A CA 1148952 A CA1148952 A CA 1148952A CA 000358634 A CA000358634 A CA 000358634A CA 358634 A CA358634 A CA 358634A CA 1148952 A CA1148952 A CA 1148952A
- Authority
- CA
- Canada
- Prior art keywords
- diaza
- oxa
- oxo
- spiro
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
Abstract
Abstract of the disclosure:
The invention provides derivatives of polyalkyl-1-oxa-diaza-spirodecanes prepared from compounds of the formula in which X is or and mono- or dihalo-hydrocarbons by alkylation at the ni-trogen atom of the 5-membered ring, and the salts thereof.
The novel compounds are migration-resistant light stabili-zers of low volatility for synthetic polymers.
The invention provides derivatives of polyalkyl-1-oxa-diaza-spirodecanes prepared from compounds of the formula in which X is or and mono- or dihalo-hydrocarbons by alkylation at the ni-trogen atom of the 5-membered ring, and the salts thereof.
The novel compounds are migration-resistant light stabili-zers of low volatility for synthetic polymers.
Description
ll~B~52
- 2 - HOE 79/F 817 The inventior3 provides novel polyalkyl-diaza-spiro-decanes, a process for the preparation thereof, and use thereof for stabilizing organic polymers against degrada-tion induced by light and heat.
The novel polyalkyl-diaza-spirodecanes correspond to the formula (I) ~ ~ i in which X stands for a group of the formulae (II) or (III) ~~~ ~ N ~ (II) ~ O
the indices 3 and 4 indicating the ring positions in the diaza-spirodecane system, and the free valency of the ni-.
trogen atom producing the linkage with R ;
R1 is hydrogen, oxygen or C1-C12-alkyl, preferably hydro-gen, oxygen or C1-C4-alkyl, especially hydrogen;
R2 and R3 either are identical and represent hydrogen or a C1-C4-alkyl group, preferably hydrogen or a methyl group, especially hydrogen; in which case R is a methyl group; or .
R is hydrogen or C1-C5-alkyl; and R3 and R4, together with the carbon atoms to which they are linked, form a C5- or C6-cycloalkyl group or a group of M t`n~:~`~rr~
, . ..
.~
- . ",:.:
:.
~dt8.~52
The novel polyalkyl-diaza-spirodecanes correspond to the formula (I) ~ ~ i in which X stands for a group of the formulae (II) or (III) ~~~ ~ N ~ (II) ~ O
the indices 3 and 4 indicating the ring positions in the diaza-spirodecane system, and the free valency of the ni-.
trogen atom producing the linkage with R ;
R1 is hydrogen, oxygen or C1-C12-alkyl, preferably hydro-gen, oxygen or C1-C4-alkyl, especially hydrogen;
R2 and R3 either are identical and represent hydrogen or a C1-C4-alkyl group, preferably hydrogen or a methyl group, especially hydrogen; in which case R is a methyl group; or .
R is hydrogen or C1-C5-alkyl; and R3 and R4, together with the carbon atoms to which they are linked, form a C5- or C6-cycloalkyl group or a group of M t`n~:~`~rr~
, . ..
.~
- . ",:.:
:.
~dt8.~52
- 3 - HOE 79/F 817 H C CH
~ ~ < 3 h NH
~< .
R5 is hydrogen, C1-C30-alkyl, preferably C1-C18-alkyl, es-pecially C1-C5-alkyl, unsubstituted phenyl or naphthyl, or phenyl or naphthyl substituted by chlorine or C1-C4-alkyl, preferably the first cited group, or an unsubsti-tuted C7-C12-phenylalkyl group or a C7-C12-phenylalkyl group substituted by C1-C4-alkyl, preferably a benzyl group;
R is hydrogell, C1-C30-alkyl, preferably C1-C18-alkyl, es- -pecially C1-C13-alkyl, an unsubstituted phenyl or naph-thyl or a phenyl or naphthyl group substituted by chlo-rine or C1-C4-alkyl, preferably a phenyl group, an unsub- f stituted C7-C12-phenylalkyl group or such a phenylalkyl .
group substituted by C1-C4-alkyl, preferably a benzyl group, .
R5 and R , together with the carbon atom l~nking them, form an unsubstituted C5-C18-, pr0ferably C5-C12-cyoloalkyl group or such a cycloalkyl group substituted by up to four C1-C4-alkyl groups, preferably methyl groups, or a group of the formula H3C~CH3 2 5 ~N~ H
H3C C~3 : n is 1 or 2, and R7, in the case where n is 1, is an alkyl group having from 1 to 30, pre~erably 1 to 18, especially 1 to 6, carbon atoms, an alkenyl group having from 2 to 18, preferably 3 to 12, especially 3 to 6, carbon atoms, a phenylalkyl group having from 7 to 18, preferably 7 to 10, espe-~ cially 7, carbon atoms optionally substituted by a C1-C4-alkyl group, or a cycloalkyl group having from 5 to 12 carbon atoms; and in the case where n is 2, it is an .~ .
.
82S'~
~ ~ < 3 h NH
~< .
R5 is hydrogen, C1-C30-alkyl, preferably C1-C18-alkyl, es-pecially C1-C5-alkyl, unsubstituted phenyl or naphthyl, or phenyl or naphthyl substituted by chlorine or C1-C4-alkyl, preferably the first cited group, or an unsubsti-tuted C7-C12-phenylalkyl group or a C7-C12-phenylalkyl group substituted by C1-C4-alkyl, preferably a benzyl group;
R is hydrogell, C1-C30-alkyl, preferably C1-C18-alkyl, es- -pecially C1-C13-alkyl, an unsubstituted phenyl or naph-thyl or a phenyl or naphthyl group substituted by chlo-rine or C1-C4-alkyl, preferably a phenyl group, an unsub- f stituted C7-C12-phenylalkyl group or such a phenylalkyl .
group substituted by C1-C4-alkyl, preferably a benzyl group, .
R5 and R , together with the carbon atom l~nking them, form an unsubstituted C5-C18-, pr0ferably C5-C12-cyoloalkyl group or such a cycloalkyl group substituted by up to four C1-C4-alkyl groups, preferably methyl groups, or a group of the formula H3C~CH3 2 5 ~N~ H
H3C C~3 : n is 1 or 2, and R7, in the case where n is 1, is an alkyl group having from 1 to 30, pre~erably 1 to 18, especially 1 to 6, carbon atoms, an alkenyl group having from 2 to 18, preferably 3 to 12, especially 3 to 6, carbon atoms, a phenylalkyl group having from 7 to 18, preferably 7 to 10, espe-~ cially 7, carbon atoms optionally substituted by a C1-C4-alkyl group, or a cycloalkyl group having from 5 to 12 carbon atoms; and in the case where n is 2, it is an .~ .
.
82S'~
- 4 - HOE 79/F 817 alkylene group having from 2 to 30, preferably 2 to 18, especially 4 to 12, carbon atoms, an alkenylene group having from 2 to 3-preferably 2 to 18, especially 2 t;o 6, carbon atoms, or a phenylene-dialkylene group hav~ng from 8 to 18, preferably 8 to 10, especially 8, carbon atoms.
Furthermore included are the salts with non-oxidizing mineral acids, aliphatic sulfonic or phosphonic acids hav-ing from 1 to 30, preferably 1 to 18, carbon atoms, optio-nally alkylated aromatic sulfonic or phosphonic acids hav-ing from 6 to 25, preferably 6 to 18, carbon atoms; 1 to 3 alkyl groups having from 1 to 16 carbon atoms optionally being present; furthermore aliphatic mono- or dicarboxylic acids having from 2 to 34, preferably 2 to 18, carbon atoms, or aliphatic polycarboxylic acids having up to 4 carboxyl groups and a total of 16 carbon atoms, or aromatic carboxy-lic acids having up to 4 carboxyl groups and up to 25 car-bon atoms, preferably up to 2 carboxyl groups and up to 19 carbon atoms.
Examples o~ polyalkyl-diaza-spirodecanes of the inven-tion are:
(1) ~,2,3,7,7,9,9-hexamethyl-1-oxa-3,8-diaza-4-oxo-sPiro-(4,5)-decane 25 (2) 2~2~7~?~9~9--hexamethyl-3-othyl-l-oxa-3~8-diaza 9 pi ro-(4,5)-decane (3) 2,2~7~7~9~9-hexamethyl-3-propyl-1-oxa-3~8-diaza-4-oxo-spiro-(4,5)-decane (4) 2~2~7~7~9~9~hexamethyl-3-butyl-1-oxa-3~8-diaza-4 spiro-(4,5)-decane - (5) 2,2,7,7,9,9-hexamethyl-3--pentyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-dscane ~6) 2,2,7,7,9,9.hexamethyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane 35 (7) 2~217~7~9~9-~examethyl-3-nonyl-1-oxa-3~8-diaza-4 spiro-(4,5)-decane (8) 2,2,7,7,9,9-hexamethyl-3-dodscyl-1-oxa-3,8-diaza-4-oxo-spiro-t4~5)-decane . .
;`~ , I
.
~ ' :
31 ~ 52
Furthermore included are the salts with non-oxidizing mineral acids, aliphatic sulfonic or phosphonic acids hav-ing from 1 to 30, preferably 1 to 18, carbon atoms, optio-nally alkylated aromatic sulfonic or phosphonic acids hav-ing from 6 to 25, preferably 6 to 18, carbon atoms; 1 to 3 alkyl groups having from 1 to 16 carbon atoms optionally being present; furthermore aliphatic mono- or dicarboxylic acids having from 2 to 34, preferably 2 to 18, carbon atoms, or aliphatic polycarboxylic acids having up to 4 carboxyl groups and a total of 16 carbon atoms, or aromatic carboxy-lic acids having up to 4 carboxyl groups and up to 25 car-bon atoms, preferably up to 2 carboxyl groups and up to 19 carbon atoms.
Examples o~ polyalkyl-diaza-spirodecanes of the inven-tion are:
(1) ~,2,3,7,7,9,9-hexamethyl-1-oxa-3,8-diaza-4-oxo-sPiro-(4,5)-decane 25 (2) 2~2~7~?~9~9--hexamethyl-3-othyl-l-oxa-3~8-diaza 9 pi ro-(4,5)-decane (3) 2,2~7~7~9~9-hexamethyl-3-propyl-1-oxa-3~8-diaza-4-oxo-spiro-(4,5)-decane (4) 2~2~7~7~9~9~hexamethyl-3-butyl-1-oxa-3~8-diaza-4 spiro-(4,5)-decane - (5) 2,2,7,7,9,9-hexamethyl-3--pentyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-dscane ~6) 2,2,7,7,9,9.hexamethyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane 35 (7) 2~217~7~9~9-~examethyl-3-nonyl-1-oxa-3~8-diaza-4 spiro-(4,5)-decane (8) 2,2,7,7,9,9-hexamethyl-3-dodscyl-1-oxa-3,8-diaza-4-oxo-spiro-t4~5)-decane . .
;`~ , I
.
~ ' :
31 ~ 52
- 5 - HOE 79/F 817 (9) 2,2,7,7,9,9-^hexamethyl-3-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane ~10) 2,2,7,7,9,9-hexamethyl-3-benzyl-1-oxa-3,B-diaza-4-oxD-spiro-(4,5)-decsne (11) 1~h~-bis-[2~2~7~7~9~9-hsxamethy~ oxa-3~-diazs-4 ~piro-~4,5)-d~cyl-3-]-butane .
(12) 1l~6~-bis-[2~2~7~7~9~9-hexamethyl-i-oxa-3~B-diaza-4 spiro-(4,5)-dscyl-3-]-hexana (13) 1~1ol-bi~s-[2~2~7~7~9~9-hexamethy~ oxa-3~8-diaza-4-oxo- .
spiro-(4,5)-decyl-3-~-decans (14) 2,2,4,7,7,9,9-hsptamethyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane (15) 2,2,7,7,8,9,9-heptamethyl-4-butyl-1-oxa-3-oxo-4,B-diaza-~piro-(4~5)-decane 15 (16) 2,2,7,7,9,9-hsxamsthyl-4-ethyl-1-oxa-3-oxo-4,8-diaza- .
spiro-(4,5)-decane (17) 2,2,7,7,9,9-hexamethyl-4-butyl-1-oxa-3-oxo-h,a-diaza-spiro-(4,5)-dscane (18) 2,2~7,7,9,9-~examethyl-4-hexyl-1-oxa-3-oxo-4~B-diaza-spiro-(4,5)-decane (19) 2,2,7,7,9,9-haxamethyl-4-dodscyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-dscane .
(20) 2,2,7,7,9,9-hexamethyl-4-octadecyl-1-oxa-3-oxo-4,B-diaza-.
spiro-(4,5)-decans (21) 2,2,7,7,9,9-hexamethyl-4-benzyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decan B
(22) 1',6'-kis-[2,2,7,7,9,9-hexamethyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-]-hexane (23) 1',10'-bis-[2,2,7,7,9,9-hexamathyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-]-dscan B
(24) 2,3,7,7,9,9-hexamethyl-2-sthyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (25) 2,7,7,9,9-pentamethyl-2-ethyl-3-hexyl-1-oxa-3,8-diaza-4-3 oxo-spiro-(4,5)-decane (26) 2,7,7,9,9-pentamethyl-2-ethyl-3-octadscyl-1-oxa-3~a-diaza 4-oxo-spiro-(4,5)-decana ;,~ . I
!
.... .. .... . ............. ..
~8~52
(12) 1l~6~-bis-[2~2~7~7~9~9-hexamethyl-i-oxa-3~B-diaza-4 spiro-(4,5)-dscyl-3-]-hexana (13) 1~1ol-bi~s-[2~2~7~7~9~9-hexamethy~ oxa-3~8-diaza-4-oxo- .
spiro-(4,5)-decyl-3-~-decans (14) 2,2,4,7,7,9,9-hsptamethyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane (15) 2,2,7,7,8,9,9-heptamethyl-4-butyl-1-oxa-3-oxo-4,B-diaza-~piro-(4~5)-decane 15 (16) 2,2,7,7,9,9-hsxamsthyl-4-ethyl-1-oxa-3-oxo-4,8-diaza- .
spiro-(4,5)-decane (17) 2,2,7,7,9,9-hexamethyl-4-butyl-1-oxa-3-oxo-h,a-diaza-spiro-(4,5)-dscane (18) 2,2~7,7,9,9-~examethyl-4-hexyl-1-oxa-3-oxo-4~B-diaza-spiro-(4,5)-decane (19) 2,2,7,7,9,9-haxamethyl-4-dodscyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-dscane .
(20) 2,2,7,7,9,9-hexamethyl-4-octadecyl-1-oxa-3-oxo-4,B-diaza-.
spiro-(4,5)-decans (21) 2,2,7,7,9,9-hexamethyl-4-benzyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decan B
(22) 1',6'-kis-[2,2,7,7,9,9-hexamethyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-]-hexane (23) 1',10'-bis-[2,2,7,7,9,9-hexamathyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-]-dscan B
(24) 2,3,7,7,9,9-hexamethyl-2-sthyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (25) 2,7,7,9,9-pentamethyl-2-ethyl-3-hexyl-1-oxa-3,8-diaza-4-3 oxo-spiro-(4,5)-decane (26) 2,7,7,9,9-pentamethyl-2-ethyl-3-octadscyl-1-oxa-3~a-diaza 4-oxo-spiro-(4,5)-decana ;,~ . I
!
.... .. .... . ............. ..
~8~52
- 6 - :
_E 79/F 817 .
(27) 1',6'-hie~,7,7,9,9-pentamethyl 2-ethyl-1-oxa 3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]^hexans (2B) 2,4,7,7,9,9-hexamsthyl-2-ethyl-1-oxa-3-oxo-4,~-diaza-~.plrD-(4,5)-d~cane (29) 2,7,7,9,9-pentam~thyl-2-ethyl-4-hexyl-1-oxa-3-oxo-4,8-diaza spiro-(4,5)-decane (30) 2,7,7,9,9-pentame'hyl-2-ethyl-4-benzyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane (31) 1',4'-bis-~2,7,7,9,9-pentamethyl-2-ethyl-1-oxa-3-oxo-4 9 8-diaza-spiro-(4,5)-decyl-4-~-butans (32) 2,3,7,7,9,9-haxamethyl-2-iso-propyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-dscane (33) 2,7,7,9,9-pentamethyl-2-propyl-3-ethyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane 15 (34) 1~4l-bis-[2~7~7~9~9-psntamethyl-2-propyl-1-oxa-3~8-diaza 4-oxo-spiro-(4,5)-decyl-3-]-butane (35) 1',10'-~is-[2,7,7,9,9-pentamethyl-2-prnpyl-1-oxe-3,8-di2za-4-oxo-spiro-(4,~)-decyl-3-]-decane (36) 2,7,7,9,9-psntamethyl-2-~so-prapyl-4-hexyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane (37) 2l4,7,7,9,9-hexamethyl-2-iso-pro~yl-1-oxa-3-oxo-4,8-diaz~-spiro-(4,5)-decane (38) 2~7,7,9,9-pentamethyl-2-iso-propyl-4-ethyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane 25 (39) 2,3,7,7,9,9-hsxamethyl-2-iso-butyl-3,8-diaza-1-oxa-4-oxo-spiro-(4 ~ 5 )-dPcan 8 (40) 2,7,7,9,9-pentamethyl-2-iso-butyl-3-ethyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane . (41) 2,7,7,9,9-pentamethyl-2-iso-butyl-3-butyl-1-oxa-3,8-diaza-4-oxo-spiro-t4,5)-decane (42) 2,7,7,9,9-~Hntamsthyl-2-iso-butyl-3-hexyl-1-oxa-3,5-diaza-4-oxo-spiro-(4,5)-decane (43) 2,7,7~9,9-pentamethyl-2-iso-butyl-3-nonyl-1-oxa-3~8-diaza 4-oxo-spiro-(4,5)-decane 35 (44) 2,7,7,9,9-pPntamethyl-2-iso-butyl-3-octadecyl-1-oxa-3,8-diaza-4-axo-spiro-(4,5)-decane . "' " . ' ~
:
:' " ~ ' :
.'. . :, ' s~
(45) 1',6'-~is-[2,7,7,9,9-pentamethyl--2-iso-butyl-1-oxa-3,8-diaza-4-uxo-apiro (b,5)-decyl-3-~-hexane (46) 1',10'-bls--~2,7,7,9,9-pentamsthyl-2-iso-butyl-1-oxa-3,8-d1aza~4--oxo-~piro-(Lt,5)-decyl-3-]-dacans (47) 2,7,7,9,9-pentamethyl-2-butyl--S-~thyl-1-oxa-3-oxo-4,~-diaza-spiro-(4,5)-dccans ( 4a ) 2,7,7,8,9,9-hexamethyl-2-iso-butyl-4-hexyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5) decans (49) 2~7~7~8~9~9-hexamsthyl-2-iso-butyl-4-octadecyl-1-oxa-3 4,8-diaza-spiro-(4,5)-decane (50) 2,7,7,9,9~1?antamethyl-2-pentyl-3-bsnzyl~-1-oxa-3,8-diaza-4-ox~-spiro-(4,5)-decane (51) 2,4~7,7,9,9-}lexamethyl-2-pentyl-1-o%a-3-oxo-4,8-diaza-spiro-(4,5)-decans 15 (52) 2,7,7,9,9-1?entamethyl-2-pantyl-4-hexyl-1-oxa-3-Gxo-4,8-diaza-3piro-(4,5)-decane (53) 2,7,7,9,9-pent~methyl-2-pentyl-4-hen~yl-1-oxa-3-oxù-4,8-diaza-spiro-(4~5)-decane (54) 2,7,7,9,9-pentamethyl-2-pentyl-4-octadecyl-1-oxa-3-oxo-4,~-diaza-spiro-(4,5)-decane 5ss) 1 ',4'-bis-[2,7,7,9,9-pentamethyl-2-Pentyl-1-ox2-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-]-butane (56) 2,7,7,9,9~?entamsthyl-2-hexyl-3-nonyl-1-oxa-3,B-diaza-4-o X0-5 pi ro-(4,5)-decan e 25 (57) 2,4,7,7,9,9-~examethyl-2-hexyl-1-oxa-3-oxo-4,~-diaza-spiro-~4,5)-decan e (58) 2,7,7,9,9-l3entamethyl-2-haxyl-4-ethyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decan e (S9) 2,7,7,9,9~entamethyl-2-hexyl-4-butyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane t60) 2,7,7,9,9-pantamethyl-2,4-dihexyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decan e (61) 1',4'-bi~-[2,7,7,9,9-psntam~thyl-2-hexyl-1-oxa-3-Dxo-4,8-diaza-spiro-(4,5)-decyl-4-]-butan e .
~8~5;;~
(62) 1',6'~ [2,7,7,9,9-pentamethyl-2-hexyl-1-oxa-3-qxo 4,8-diaza-epiro-(4,5)-decyl-4-]-hexane ~63) 2,7,7,9,9-pentamethyl-2-hsxyl-4-octadecyl-1-oxa-3-oxo-4,8-diuza-spiro-(4,5)-dscans (64) 2,7,7,9,9-pentamethyl-2-iso-llexyl-4-benzyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-dscane (65) 2,7,7,9,9-p~ntamsthyl-2-nonyl-3-ethyl-1-oxa-3,~-diaza-4-OX0-5 piro-(4,5)-decans (66) 2,7,7,9,9-~entamethyl-2-nonyl-3-butyl-1-oxa-3,8-diaza-4-1D oxo-spiro-(4,5)-decane (67) 2,7,759,9-pentamethyl-2-nonyl-3-hexyl-1-oxa-3~8-diaza-4 ox~-spiro-(4,5)-decane (68) 2,7,7,9,9-Fenta~ethyl-2-nonyl-3-octadscyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decans 15 ~69) 1',6'-bis-r2,7,7,9,9-pentamethyl-2-nonyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-~-hexans (70) 2,3,7,7,9,9-hexamethyl-2-undecyl-1-oxa-3,8-dieza-4~ xo-spiro~(4,5)-decane (71) 2~7~7~9~9-pentamethyl-2-undecyl-3-ethyl-1-oxa-3~8-diaza-4 oxo-spiro-(4,5)-deca'ne (72) 2,7,?,9,9-pentamethyl-2-undecyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (73) 2,7,7,9;9-pentamsthyl-2-undecyl-3-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4~5)-decane 25 (7~) 2,7,7,9,9-pentamethyl-2-undecyl-3-benzyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (75) 2,7,7,9,9-Pentamethyl-2-undecyl-3-cumylyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (76) 1~6'-bls-[2~7~7~9~9-pentamethyl-2-undecyl-1-oxa-3~8-diaza 4-oxo-spiro-(4,5)-decy~-3-3-hexane (77) 1',10'-ais-[2,7,7,9,9-pentamethyl-2-undecyl-1-o%a-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-decane (78) 2,7,7l9,9-Fentamethyl-2-undecyl-1-oxa-3-oxo-4-ethyl-4,8-diaza-spiro-(4,5)-decane .~ .
.
B~52 9 .
~E~ , .
(7~) 2~7,7,9,9-~antamethyl-2-undecyl-1-oxa-3-oxo-4-benzyl-4,8-diaza-spiro-(4,5)-decane (B0) 2~7~7~9~9-pentamethyl-2-undecyl-1-oxs-3-oxo-4-octade ~J,B-dia2a-spiro-(4,5)-decane (~7) 1',6'-bis-[2,7,7,9,9-p~ntomethyl-2-undecyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-~-hsxane (B2) 2~3,7~7~9,9-hPxamethyl-2-octadscyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (83) 2,7,7,9,9-pentamethyl-2-octadecyl-3-ethyl-1-oxa-3,B-diaza-4-oxo-spiro-(4,5)-decane (84) 2,7~7,9~9-Pentamsthyl-2-octadeoyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (as) 2,7,7,9,9-Pentamethyl-2,3-dioctadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane 15(86) 1',6'-bis-~2,7~7,9,9-pentamethyl-2-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-~-hexane (87) 1',10'-bis-[2-7,7,9,9-pentamethyl-2-octadscyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-decane (8B) 3,7,7,9,9-pentamethyl-2~2-diethyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-dscane (~9) 7~7~9~9_tetramethyl-2~2~3-triethyl-1-oxa-3~8-diaZa-4-oxo-spiro-(4~5)-decane (90) 7~7~9~9-tetramethyl-2~2-diethyl-3-butyl-1-oxa-3sB-diaza 4-oxo-qpiro-t4,5)-decane 25(91) 7,7,9,9-tetramethyl-2,2-diethyl-3-hexyl-1-oxa-3,B-diaza-4-oxo-spiro-(4,5)-decane (92) 7,7,9,9-tetramethyl-2,2-diethyl-3-benzyl-1-oxa-3,8-diaza-4-oxo-spiro-(4~5)-decane (93) 1',6'- ~s-~7,7,9,9-tetramethyl-2,2-diethyl-1-oxa-3,~-diaza-4-oxo-spiro-(4,5)-decyl-3-]-hexane (94) 3,?,7,9,9-~entamethyl-2-ethyl-2-iso-butyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (95) 7,7,9,9-tetramethyl-2-ethyl-2-iso-butyl-3-hexyl-1-oxa-3,a-diaza-4-oxo-spiro-(4,5)-decane ' .
s~
~ 10 ~
HOE 79/~ 817 t (96) 7~7~9~9-tetramethyl-2-othyl-2-1so-outyl-3-benzy~ oxa 3,8-diaza-4-oxo-spiro-(4,5)-~ecane (97) 7~7~9~9-tetramethyl-2-ethyl-2-butyl-l-oxa-3-oxo-4-benzy 4,8 diaza-spiro-(4,5)-decane (9B) 1',4'- ~s-[7,7,9,9-tetramethyl-2-ethyl-2-butyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-~-butane (99) 7,7,9,9-~entamethyl-2,2-dibutyl-4-benzyl-1-oxa-4,8-diaza-3-oxo-spiro-(4,5)-decane (1ûO) 7~7~9~9-tetramethyl-2~2-dipentyl-3-hexyl-1-oxa-3~a-diaza 4-oxo-spirD-(4,5)-decane (101) 7,7,9,9-tetramethyl-2,2-dipentyl-3-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (102) 7,7,9,9-tetramethyl-2,2-dipentyl-3-benzyl-1-oxa-3,B-diaza-4-oxo-spiro-(4,5)-decane 15 (103) 1',4'-kls-[7,7,9,9-tstramethyl-2,2-dipentyl-1-Dxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-butane (1û4) 1',6'- W s-~7,7,9,9-tetramethyl-2,2-dipentyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-hexane (105) 1',10'-bis-~7,7,9,9-tetramsthyl-2,2-dipentyl-1-oxa-3,8-diaza-4-oxo-s~iro-(4,5)-decyl-3-]-dec3ne (106) 7,7,9,9-~etramethyl-2,2-ditetradecyl-3-hsxyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decana (107) 1',6'-~is-[7,7,9,9-tetramsthyl-2,2-ditetradecyl-1-oxa-3~8-diaza-4-oxo-spiro-(4~5)-decyl-3-]-heXans 25 (108) 7,7,9,9-tetra~cthyl-2,2-dioctadecyl-3-benzyl-1-oxa-3,~-diaza-4-oxo-spiro-(4,5)-dPcans (109) 7,7,9,9-tetramethyl-2,2-dioctadecyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-docane (110) 7,7,9,9-tetramethyl-2,2,3-trioctadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (111) 1',6'- ~s-[7,7,9,9-tetramethyl-2,2-dioctadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-hexane (112) 3,7~7,9,9-pentamethyl-2-phenyl-l-oxa-3~a-diaza-4-oxo-spir S )-d~cane , -8~ 2 11 _ (113) 7,7,9,9-tetramethyl-2-iso-propyl-4-ethyl-1-oxa-4,8-diaza-3-oxo-spiro-~4~5)-dccana (114) 7,7,9,9-tetramethyl-2-iso-hexyl-3-ethyl-1-axa-3,a-diaza-4--oxo--spiro--(4,5)--dccsn8 (115) 3~7~7~9~9-t~entamethyl-2-nonyl-1-oxa-3~-diaza-4-oxo-spiro-(4,5)-decane (116) 7,7,9,9-tE?tramethyl-2-isn-nonyl-3-hexyl-1-oxa-3,a-diaza-4-oxo-spiro-(4~5)-decane (117) 7,7,9,9-tetramethyl-2-iso-heptyl-3-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (118) 7,7,9,9-tetramsthyl-2-undscyl-3-benzyl-1-oxa-3,8-diaza-4 oxo-spiro-(~,5)-decane (119) 1',4'-~is-[7,7,9,9-tetramethyl-2-iso-nonyl-1-oxy-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-~-butane (120) 4,7,7,9,9-~3entamethyl-2-iso-butyl-~-oxa-3-oxo-4,8-diaza-spiro~(4,5)-decan e (121) 7,7,9,9-tstramethyl-2-iso-hsptyl-1-oxa-4-ethyl-3-oxo-4,~-diaz~-spiro-(h,5)-decan e ~122) 1'~5'-~ls-[7~7,9,9-t~tr2methyl-2-iso-pentyl-1-oxa-3-oxo-2n 4,8-diaza-spiro-(4,5)-decyl-4-]-pentane (123) 2,2,4,4- tetramsthyl-13-hexyl-?-oxa-3,13-diaza-14-oxo-di.-spiro-(5~1,4,2)-tetradecan e (124) 2,2,4,4-tstramethyl-13-sthyl-7-oxa-3,13-diaza-24-oxo-di-spiro-(5,1,4,2)-tetradecan e (125) 2,2,4,4- t~tramethyl-13-butyl-7-oxa-3,13-diaza-14-oxo-dispiro-(5,1,4,2)-tetradecan e (126) 2,2,4,4-t~tramethyl-14-ethyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentadocan e (127) 2,2,4,4-.tetramethyi-14-butyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentadecan e (128) 2,2,4,4-t~tramethyl-14-hexyl-7-oxa-3,14-diaza-15-oxo-di~piro-~5,1,5,2)-pentadecan e (129) 2,2,4,4-t}3tramethyl-14-benzyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentadscan e .
~; ' i !
8~S2 - 12 _ HOE ~
(13CI) 1',4'-bis-[2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5~l~5~2)-pentadecyl-14~-butane (131) 1',4'-bis-[2,2,4,4-tetramethyl-1-oxa-3,14-diaza-15-oxo-disp~ro-(5~1~5~2)-pentadecyl-l4]-butane (132) 1',6'-bis-[2,2~4,4-tetramethyl-7-oxa-3,14-d~aza-15-oxo-dispiro-(5,1,5,2)-pentadecyl-14]-hexane (133) 2,2,4,4,10,12-~?examethyl-14-ethyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentadecane (134) 2,2,4,4,10,10,12,12--ootamethyl-14-ethyl-7-oxa-3,14-dia~a-15-oxo-dispiro-(5,1,5,2)-pentadecane (135) 2,2,4,4,15-pentamethyl-7-oxa-3~15-diaza-14-oxo-dispir (5~1~5~2)-psntadecen e (136) 2,2,4,4-tetra0ethyl-15-hexyl-7-oxa-3,15~diaza-14-oxo-di-spiro-(5,1,5,2)-pentad~can e (137) 2,2,4,4,20-pentamathyl-7-oxa-3,20-diaza-21-oxo-dispiro-(5~ ?2)-hensicosan e (138) 2,2,4,4-tetramethyl-20-ethyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11~2)-heneicosan e (139) 2~2~4,b-tetramethyl-20-iso-propyl-7-oxa-3,20-diaza-21-oxo-dispiro-(5,1,11~2)-heneicosane (140) 2,2,4,4-tetramethyl-20-butyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11,2)-hsneicosan e (141) 2,2,4,4-tetramethyl-20-iso-butyl-7-oxa-3,20-diaz2-21-oxo-dispiro-(5,1,11,2)-heneicosane (142) 2,2,4,4-tetramethyl-20-Pentyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11,2)-heneicocane (143) 2,2,4,4-tetramethyl-20-hexyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11,2)-heneicosan e (144) 2,2,4,4-tetramethyl-20-octyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11,2)-heneicosan B
(145) 2,2,4,4-~tetramethyl-20-heptyl-7-oxa-3,20-diaza-21-o%o-di-spiro-(5,1,11,2)-heneicosan e (146) 2~2~4,4- tetramethyl-20-octadecyl-7-oxa-3,20-diaza-21-oxo-dispiro-(5,1,11,2)-heneicosan e :~.
, ...,, . " ~ .
s~
(147) 2,2,4,4-~ ~tramathyl-20-bcnzyl-7-oxa-3,20-diaza-21-oxo--di-spiro-(5,1,11,2)-heneirosans (148) 1~4~-bis-~7~2~4~4-totramethyl-7-oxa-3~2o-diaza-2l-oxo -dispiro-(5,1,11,2)-heneicosyl-20-]-butane (149) 1',5'-~is-[2,2,~,4-totramsthyl-7-oxa-3,20-diaza-21-oxo-di~piro-(5,1,11,2)-heneit:o3yl-20-]-pentane (150) 1',6'-bi~-[2,2,~,4-tstramethyl-7-oxa-3,20-diaza-21-oxo-dispirc)-(5,1,11,2)-hsneicosyl-20-]-hexane (151) 1l~1o~-bis-[2~2~4~4-tetramethyl-7-oxa-3~2o-diaza-21 dispiro-(5,1,11,2)-heneicosyl-20-]dscane ~152) 2,2,4,4,21-Pentamethyl-7-oxa-3,21-diaza-20-oxo-dispiro-(5,1,11,2)-heneicosan e (153) 7,7,9,9-tetramethyl-2,2-dibenzyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decan~
(154) 7,7,9,9~totramethyl-2,2-dibenzyl-3-octadecyl-1-oxa-3,û-diaza-4-oxo-spiro-(4,5)-decano (155) 7,7,9,9- tstramethyl-2, 2t 3-tribenzyl-1 oxa-3,8-diaza-4-oxn-spiro-(4,5)-decan e ~156) 1,2-}~is-[2,2,7,7,9,9-hexam~thyl-1-oxa-3,8-diaza-~-o~o-di~piro-(4,5)-decan-3-methyl-]-benz ene, The novel compounds are prepared according to the fol-.lowing reaction scheme from polyalkyl-1-oxa-diaza-spirode-canes of the formula (IV), which for their part are obtain-25 ed according to German Patents Nos. 2,606,026; 2,634,957 and 2,834,962, and halogen compounds of the formula (V), while hydrogen halide is split off:
- ~ . .
5;2 - 14 - HOE 79tF 817 ~H2R
H ~C y ~2 (IV) (V) ~/ Base -n Base~ HHal 20 ~ X~ 7 (1) The radicals R1 through R7 and X are as defined above, Hal is chlorine, bromine or iodine, n is 1 or 2.
In detail, the following radicals are suitable:
30 R1 = hydrogen, oxygen, methyl, butyl, hexyl, octyl, : dodecyl R2 = hydrogen, methyl, ethyl, butyl R3 = hydrogen, methyl, ethyl, butyl . R4 = methyl R3 and'~4~ -to`get~er with the carbon atom 9 = cyclohexyl, 2,2,6,6-tetramethylpiperidyl - R5 and R6 = ~lydrogen, ethyl, propyl, iso-propyl, butyl, .
, ~
~, `
.
~ . . . - .
. .
35;~
i.so-butyl, pentyl, iso-pentyl, hexyl, iso~-hex~-yl, heptyl, iso-heptyl, octyl, nonyl, iso-nonyl, decyl, undecyl, tridecyl, octadecyl, phenyl, 2,4-dichloropher1yl R5 and R6 together with the carbon atom 2 = cyclohexy-lidelle, 3,5-dimethylcyclohexyli.dene, 3,3,5,5-tetramethylcyclohexylidene, cycloheptylidene, cyclododecylidene, 2,2,6,6~tetramethylpiperi-dylene 10 R7 = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, dodecyl, tetradecyl, oc-tadecyl, benzyl, ethylene, propylene, butylene, pentylene, hexylene, decylene, butenylene, xylylene .
The synthesis is carried out as follows: In the case where n is 1, the compounds (IV) and (V) are reacted with each other in a molar ratio of from 1:1 to 1:10, preferab-ly 1:1.2 to 1:5, especially 1:1.5 to 1:3; and in the case where n is 2, in a molar ratio of from 2.5:1 to 2:1, pre-ferably 2.1:1 to 2:1, especially 2:1. The reactiGn is per-rormed in an organic solvent in the presence Or an 3quimo-lar to 20-fold amount of solid alkali metal hydroxide? or a 20 % to, preferably, 50 ~, aqueous alkali metal hydroxide solution in the presence of a phase transfer catalyst. The reaction temperature is in the range of from 20 to 120C, preferably 20 to 70C, especially 40 to 60C. As organic solvents, there are used aliphatic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, gasoline frac-tiOI1S, toluene, cyclohexane etc., or an excess of alkyl halide. By phase transfer catalysts, there are to be un-derstood compounds selected from the group Or quaternary ammonium halides, which are employed in an amount of from -~.1 to 5 weight %, relative to compound (IV); tricapryl-methylammonium chloride being especially suitable. The reaction is generally `complete after 1 to 20 hours, depend-ing on the reactivity Or the halogen component~
For work-up, the phases are separated, optionally after ., , ~, :
.
additiol1 of a small amount of water. The organic phase is repeatedl.y washed with water, dried over Na2SO4 or MgSO4, concentrated, and the residue is recrystallized In some cases, the final products crystallize already in the reac-tion solutions and are then isolated by filtration.
It was surprising and not to be expected that especial-ly those compounds in which X1 is H could be prepared ac-cording to the above method. In contrast to the course ofreaction actually observed and proved by 13C-NMR examina-tion, a subskitution at the piperidine nitrogen was ratherto be calculated on, because due to its higher basicity its nucleophilic power is considerably greater than that of amide nitrogen in the atom group X.
As to properties and efficiency of the novel compounds, it should have been expected that there are no differences at all or to an insignificant extent only as compared to 1-oxa-diaza-spirodecanes of similar structure described in the patent literature and recommended as plastics stabili-zers (German Offenlegul1gsschriften Nos. 1,770,68g and 2,227,6~9). Surprisingly, however, the novel c~mpounds are highly superior to even the best of the compounds listed in the above German Offenlegungsschriften, that is, that of Ex-ample 58 of German Offenlegungsschrift No. 1,770,689. This compound, namely 7,7,8,9,9-pentamethyl-3-epoxypropyl-1,3,8-triaza-spiro-(4,5)-decane-2,4-dione, although distinguished by a very good stabilizing action, is highly volatile on processing. This is valid, too, for the compounds of Ger-man Offenlegungsschriften Nos. 2,606,026 and 2,634,957, - and they can be easily washed off from the thermoplastic materials containing them.
High-quality stabilizers, however, have to meet severe requirements in addition to their stabilizing action, espe-ci.ally with respect to the above physical properties. For, a too high volatility results in considerable stabilizer losses on processing of the polymers, and the activity of the stabilizer is reduced when it is too readily washed off, for example on sprinkling with water.
.
.
.
.
. ; ' ~, : .
- ~ - HOE 79/F 817 It was therefore not to be expeced at all that, des-pite their relationship with the compounds of the cited Offetllegungsschriften, the compounds of the invention are not only more effective as stabili~ers, but also excel by an especially low volatility and increased resistance to being washed Gff (these advantageous properties being pre-sent above all in the compounds where n is 2), so that this must be considered as an essential technical progress.
As already mentioned, the novel compounds are used as stabilizers for plastic materials against damage thereo~
by influence of oxygen, heat and light. Examples of those plastics are the follo~ing:
Polymers which are derived from hydrocarbons with one or two unsaturated olefinic bonds, for example polyolefins such as polyethylene, optionally cross-linked, polypropy-lene, polybutene-1, polyisobutene, polymethylbutene-1, polymethylpentene-1, polyisoprene, polybutadiene, polysty-rene, copolymers of the monomers on which the abovemention-ed homopolymers are based, such as ethylene/propylene copo-lymers, propyleneJbutene-1 copolymers, propylene/isobutene copolymers, styrene/butadiene copolymers, as well as ter-polymers of ethylene and propylene with a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene, mix-tures of the abovementioned homopolymers, for example mix-tures of polypropylene and polyethylene, polypropylene andpo].ybutene-1, polypropylene and polyisobutylene, or of a butadiene/acrylonitrile copolymer with a styrene/butadiene copolymer.
Vinyl polymers containing halogen, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, po-lychloroprene and chlorinated rubber, as well as copolymers of vinyl chloride and vinylidene chloride with one another and with other olefinically unsaturated monomers.
Polymers derived from oC,~-unsaturated acids and their derivatives, such as polyacrylates, poplymethacrylates, po-lyacrylamides and polyacrylonitrile, as well as their copo-lymers with one another and with other vinyl compounds, for .
- 18 - HOE 79/F ~17 example acrylonitrile/butadiene/styrene, acrylonitrile/sty-~rene and acrylonitrile/styrene/acrylic ester copolymers.
Polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as 5 polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvi.nyl butyral, polyallyl phthalate, po~yallyl melamine and their copoly-mers with other vinyl compounds, such as ethylene/vinyl acetate copolymers.
Homopolymers and copolymers which are derived from ep-oxides, such as polyethylene oxide or polymers derived from bisglycidyl ethers.
Polyacetals, such as polyoxymethylene and polyoxy-ethylene, as well as those polyoxymethylenes which contain ethylene oxide as comonomer.
Polyurethane and polyureas.
Polycarbonates.
Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic aolds or the correspondin~ lactatms, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12.
Polyesters derived from dicarboxylic acids and diols and/or ~rom hydroxy carboxylic acids or from the correspond-ing lactones, such as polyethylene glycol terephthalate, polybutyleneterephthalate, poly-1,4 dimethylol-cyclohexane-terephthalate.
Cross-linked polymers which on the one hand are de-rived from aldehydes and on the other hand from phenols, ureas and melamines, such as phenol/formaldehyde, urea/form-aldehyde and melamine/formaldehyde resins.
Of special importance is the stabilization of polyole-fins, styrene polymers, polyamides, poly-(meth-)acrylates and of polyurethanes, for which the novel compounds are especially suitable. Examples thereof are polyethylene of 35 '~'i~her an'd'-'lower density, polypropylene, ethylene/propylene copolymers, polystyrene, styrene/butadiene/acrylonitrile terpolymers, mixtures of polyolefins or of styrene poly-~ . . .
, , - , , - ~ .
.
~ 8~3~2 mers, polyurethar~es on the basis of polyether or polyester in the form of lacquers, fibers, sheets, plates, films, elastomers or foam plastics.
The new stabilizers are incorporated i.nto the polymer masses according to the methods generally used. The incor-poratiol~ can be carried out, for example, by intermixing the compounds ar3d optionally other additives with the melt accordlng to the methods usual in the industrial practice, before or during shaping, or also by applying the dissolv-ed or dispersed compounds directly to the polymer, or byintermixing them with a solution, suspension or emulsion of same, optionally with subsequently allowing the solvent to evaporate. The amounts are from 0.01 to 5, preferably 0.05 to 2.5, and especially 0.1 to 1.0 % by weight, rela tive to the material to be stabilized. The new compounds can also be added to the plastics to be stabilized in the form of a masterbatch containing these compounds, for example in a concentration of from 2.5 to 50, preferably 5.0 to 20, % by weight.
The plastics stabllized by addition of substances of formula (I) may contain other known and usual additives, such as antioxidants based on phenol and sulfide, UV absor-bers and light protecting agents, phosphite stabilizers, metal compounds, epoxy stabilizers and polyalcohols.
Examples of antioxidants are those of the type of ste-rically hindered phenols, such as 4,4'-butylidene-bis-(2,6-di-t.-butyl-phenol), 4,4'-thio-bis-(2-t.-butyl-5-methyl-phenol), phenolic triazine compounds, thiodipropionic acid esters of fatty alcohols, dioctadecyl sulfide and -disul-fide.
The UV-absorbers and light protecting agel1ts include, for example, 2-(2'-hydroxyphenyl)~benzotriazoles, such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-hyd.oxy-benzophenones, such as 2-hydroxy-4-octoxy-benzophenone, sta~,bilizers of the group of the salicylates, such as oc-tylphenyl salicylate, nickel chelates, oxalic acid diami-;~ des and sterically hindered piperidine compounds.
. .
?.~ 3S;Z
~ 20 - HnE 79~F 817 Qs phos~hites there are to be mentioned trisnonylphe-nyl phosphite, trislauryl phosphite and esters of pentaery-thritol phosphite.
By metal compounds known as stabilizers there are to be understood: ~alcium, barium, strontium, zinc, cadmium, ma~;nesium, aluminum and lead soaps of aliphatic carboxylic acids or hydroxycarboxylic acids hav.ing about 12 to 32 car-bon atoms, salts of the aforesaid metals with aromatic carb-oxylic acids, such as benzoates or salicylates, and (al-kyl-)phenolates of these metals, and also organo-tin com-pounds such as, for example, dialkyltin thioglycolates and carboxylates.
Known epoxy stabilizers are, for example, epoxidized higher fatty acids, such as epoxidized soybean oil, tall oil, linseed oil or epoxidized butyl oleate, and also ep-oxides of long-chain olefins.
Polyols may be, for example, pentaerythritol, trime-thylolpropane, sorbitol or mannitol, i.e. preferably alco-hols having 5 or 6 carbon atoms and 3 to 6 OH-groups.
An effective stabilizer combination for poly- ~-ole-flns such as, for exmpl~, high, medium and low pressure polymers of C2- to C4- ~-olefins, especially polyethylene and polypropylene or copolymers of such ~ -olefins, COII-sists, calculated on 100 parts by weight of polymer, for example, Or from 0.01 to 5 parts by weight of one of the compounds to be used in accordance with the invention, of from 0.05 to 5 parts by weight of a phenolic stabilizer, optionally of from 0.01 to 5 parts by weight of a sulfur-containing costabilizer, and optionally of from G.01 to 3 parts by weight of a basic or neutral metal soap such as, for example, calci~lm stearate or zinc stearate, and optio-nally of from 0.1 to 5 parts by weight of a phosphite and optionally Or from 0.01 to 5 parts by weight of a known UV-stabilizer of the group of alkoxy-hydroxybenzophenones, 4-hydroxyphenyl-benzotriazoles, benzylidene-malonic acid-mononitrile esters or the so-called quenchers, such as nickel chelates.
.i .
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.
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- 21 - ~.OE 79/F 817 The plastics stabilized according to the inYentioo can be used in most different shapes, for example as sheets, fibers, ribbons, profiles, or as binders for laquers, ad- -hesives or cements.
The following examples illustrate the invention.
_ X A M P L E 1:
2t2,4,4,7,7,9,9-heptamethyl-1-oxa-4,8-diaza-3-oxo-spiro-(4,5)-decane (Compound No. 14) _ _ 6.8 g of 2,2,7,7,9,9-hexamethyl-1-oxa-4,8-diaza-3-oxo-spiro-(4,5)-decane and 20 g of methyl iodide were introdu~
ced into the reactor in-50 ml of tcluene. After having ad-ded three drops of the phase transfer catalyst tricapryl-methylammonium chloride, 20 ml of 50 % sodium hydroxide so-lution were added to the reaction mixture, and it was agi-tated for 5 hours at 45C. During the reaction, the batch becomes first jelly and then transparent. The phases are subsequently separated and the organic phase is shaken twice with 30 ml each of water, filtered and concentrated. The residue is recrystallized from petroleum ether. 5.4 g of white crystals/m.p. 128-130C.
The same results are obtained when operating in hexane, heptane and cyclohexane as solvent.
E X A M P L E S 2 to 71:
Operations were as described in Example 1 with the use o~ other educts.
Test conditions and characteristics of the products are listed in the following Table. Column 2 (Compound No.) indicates the compounds cited pages 4 to 13.
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(27) 1',6'-hie~,7,7,9,9-pentamethyl 2-ethyl-1-oxa 3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]^hexans (2B) 2,4,7,7,9,9-hexamsthyl-2-ethyl-1-oxa-3-oxo-4,~-diaza-~.plrD-(4,5)-d~cane (29) 2,7,7,9,9-pentam~thyl-2-ethyl-4-hexyl-1-oxa-3-oxo-4,8-diaza spiro-(4,5)-decane (30) 2,7,7,9,9-pentame'hyl-2-ethyl-4-benzyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane (31) 1',4'-bis-~2,7,7,9,9-pentamethyl-2-ethyl-1-oxa-3-oxo-4 9 8-diaza-spiro-(4,5)-decyl-4-~-butans (32) 2,3,7,7,9,9-haxamethyl-2-iso-propyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-dscane (33) 2,7,7,9,9-pentamethyl-2-propyl-3-ethyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane 15 (34) 1~4l-bis-[2~7~7~9~9-psntamethyl-2-propyl-1-oxa-3~8-diaza 4-oxo-spiro-(4,5)-decyl-3-]-butane (35) 1',10'-~is-[2,7,7,9,9-pentamethyl-2-prnpyl-1-oxe-3,8-di2za-4-oxo-spiro-(4,~)-decyl-3-]-decane (36) 2,7,7,9,9-psntamethyl-2-~so-prapyl-4-hexyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane (37) 2l4,7,7,9,9-hexamethyl-2-iso-pro~yl-1-oxa-3-oxo-4,8-diaz~-spiro-(4,5)-decane (38) 2~7,7,9,9-pentamethyl-2-iso-propyl-4-ethyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane 25 (39) 2,3,7,7,9,9-hsxamethyl-2-iso-butyl-3,8-diaza-1-oxa-4-oxo-spiro-(4 ~ 5 )-dPcan 8 (40) 2,7,7,9,9-pentamethyl-2-iso-butyl-3-ethyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane . (41) 2,7,7,9,9-pentamethyl-2-iso-butyl-3-butyl-1-oxa-3,8-diaza-4-oxo-spiro-t4,5)-decane (42) 2,7,7,9,9-~Hntamsthyl-2-iso-butyl-3-hexyl-1-oxa-3,5-diaza-4-oxo-spiro-(4,5)-decane (43) 2,7,7~9,9-pentamethyl-2-iso-butyl-3-nonyl-1-oxa-3~8-diaza 4-oxo-spiro-(4,5)-decane 35 (44) 2,7,7,9,9-pPntamethyl-2-iso-butyl-3-octadecyl-1-oxa-3,8-diaza-4-axo-spiro-(4,5)-decane . "' " . ' ~
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(45) 1',6'-~is-[2,7,7,9,9-pentamethyl--2-iso-butyl-1-oxa-3,8-diaza-4-uxo-apiro (b,5)-decyl-3-~-hexane (46) 1',10'-bls--~2,7,7,9,9-pentamsthyl-2-iso-butyl-1-oxa-3,8-d1aza~4--oxo-~piro-(Lt,5)-decyl-3-]-dacans (47) 2,7,7,9,9-pentamethyl-2-butyl--S-~thyl-1-oxa-3-oxo-4,~-diaza-spiro-(4,5)-dccans ( 4a ) 2,7,7,8,9,9-hexamethyl-2-iso-butyl-4-hexyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5) decans (49) 2~7~7~8~9~9-hexamsthyl-2-iso-butyl-4-octadecyl-1-oxa-3 4,8-diaza-spiro-(4,5)-decane (50) 2,7,7,9,9~1?antamethyl-2-pentyl-3-bsnzyl~-1-oxa-3,8-diaza-4-ox~-spiro-(4,5)-decane (51) 2,4~7,7,9,9-}lexamethyl-2-pentyl-1-o%a-3-oxo-4,8-diaza-spiro-(4,5)-decans 15 (52) 2,7,7,9,9-1?entamethyl-2-pantyl-4-hexyl-1-oxa-3-Gxo-4,8-diaza-3piro-(4,5)-decane (53) 2,7,7,9,9-pent~methyl-2-pentyl-4-hen~yl-1-oxa-3-oxù-4,8-diaza-spiro-(4~5)-decane (54) 2,7,7,9,9-pentamethyl-2-pentyl-4-octadecyl-1-oxa-3-oxo-4,~-diaza-spiro-(4,5)-decane 5ss) 1 ',4'-bis-[2,7,7,9,9-pentamethyl-2-Pentyl-1-ox2-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-]-butane (56) 2,7,7,9,9~?entamsthyl-2-hexyl-3-nonyl-1-oxa-3,B-diaza-4-o X0-5 pi ro-(4,5)-decan e 25 (57) 2,4,7,7,9,9-~examethyl-2-hexyl-1-oxa-3-oxo-4,~-diaza-spiro-~4,5)-decan e (58) 2,7,7,9,9-l3entamethyl-2-haxyl-4-ethyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decan e (S9) 2,7,7,9,9~entamethyl-2-hexyl-4-butyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decane t60) 2,7,7,9,9-pantamethyl-2,4-dihexyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decan e (61) 1',4'-bi~-[2,7,7,9,9-psntam~thyl-2-hexyl-1-oxa-3-Dxo-4,8-diaza-spiro-(4,5)-decyl-4-]-butan e .
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(62) 1',6'~ [2,7,7,9,9-pentamethyl-2-hexyl-1-oxa-3-qxo 4,8-diaza-epiro-(4,5)-decyl-4-]-hexane ~63) 2,7,7,9,9-pentamethyl-2-hsxyl-4-octadecyl-1-oxa-3-oxo-4,8-diuza-spiro-(4,5)-dscans (64) 2,7,7,9,9-pentamethyl-2-iso-llexyl-4-benzyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-dscane (65) 2,7,7,9,9-p~ntamsthyl-2-nonyl-3-ethyl-1-oxa-3,~-diaza-4-OX0-5 piro-(4,5)-decans (66) 2,7,7,9,9-~entamethyl-2-nonyl-3-butyl-1-oxa-3,8-diaza-4-1D oxo-spiro-(4,5)-decane (67) 2,7,759,9-pentamethyl-2-nonyl-3-hexyl-1-oxa-3~8-diaza-4 ox~-spiro-(4,5)-decane (68) 2,7,7,9,9-Fenta~ethyl-2-nonyl-3-octadscyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decans 15 ~69) 1',6'-bis-r2,7,7,9,9-pentamethyl-2-nonyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-~-hexans (70) 2,3,7,7,9,9-hexamethyl-2-undecyl-1-oxa-3,8-dieza-4~ xo-spiro~(4,5)-decane (71) 2~7~7~9~9-pentamethyl-2-undecyl-3-ethyl-1-oxa-3~8-diaza-4 oxo-spiro-(4,5)-deca'ne (72) 2,7,?,9,9-pentamethyl-2-undecyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (73) 2,7,7,9;9-pentamsthyl-2-undecyl-3-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4~5)-decane 25 (7~) 2,7,7,9,9-pentamethyl-2-undecyl-3-benzyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (75) 2,7,7,9,9-Pentamethyl-2-undecyl-3-cumylyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (76) 1~6'-bls-[2~7~7~9~9-pentamethyl-2-undecyl-1-oxa-3~8-diaza 4-oxo-spiro-(4,5)-decy~-3-3-hexane (77) 1',10'-ais-[2,7,7,9,9-pentamethyl-2-undecyl-1-o%a-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-decane (78) 2,7,7l9,9-Fentamethyl-2-undecyl-1-oxa-3-oxo-4-ethyl-4,8-diaza-spiro-(4,5)-decane .~ .
.
B~52 9 .
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(7~) 2~7,7,9,9-~antamethyl-2-undecyl-1-oxa-3-oxo-4-benzyl-4,8-diaza-spiro-(4,5)-decane (B0) 2~7~7~9~9-pentamethyl-2-undecyl-1-oxs-3-oxo-4-octade ~J,B-dia2a-spiro-(4,5)-decane (~7) 1',6'-bis-[2,7,7,9,9-p~ntomethyl-2-undecyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-~-hsxane (B2) 2~3,7~7~9,9-hPxamethyl-2-octadscyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (83) 2,7,7,9,9-pentamethyl-2-octadecyl-3-ethyl-1-oxa-3,B-diaza-4-oxo-spiro-(4,5)-decane (84) 2,7~7,9~9-Pentamsthyl-2-octadeoyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (as) 2,7,7,9,9-Pentamethyl-2,3-dioctadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane 15(86) 1',6'-bis-~2,7~7,9,9-pentamethyl-2-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-~-hexane (87) 1',10'-bis-[2-7,7,9,9-pentamethyl-2-octadscyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-decane (8B) 3,7,7,9,9-pentamethyl-2~2-diethyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-dscane (~9) 7~7~9~9_tetramethyl-2~2~3-triethyl-1-oxa-3~8-diaZa-4-oxo-spiro-(4~5)-decane (90) 7~7~9~9-tetramethyl-2~2-diethyl-3-butyl-1-oxa-3sB-diaza 4-oxo-qpiro-t4,5)-decane 25(91) 7,7,9,9-tetramethyl-2,2-diethyl-3-hexyl-1-oxa-3,B-diaza-4-oxo-spiro-(4,5)-decane (92) 7,7,9,9-tetramethyl-2,2-diethyl-3-benzyl-1-oxa-3,8-diaza-4-oxo-spiro-(4~5)-decane (93) 1',6'- ~s-~7,7,9,9-tetramethyl-2,2-diethyl-1-oxa-3,~-diaza-4-oxo-spiro-(4,5)-decyl-3-]-hexane (94) 3,?,7,9,9-~entamethyl-2-ethyl-2-iso-butyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (95) 7,7,9,9-tetramethyl-2-ethyl-2-iso-butyl-3-hexyl-1-oxa-3,a-diaza-4-oxo-spiro-(4,5)-decane ' .
s~
~ 10 ~
HOE 79/~ 817 t (96) 7~7~9~9-tetramethyl-2-othyl-2-1so-outyl-3-benzy~ oxa 3,8-diaza-4-oxo-spiro-(4,5)-~ecane (97) 7~7~9~9-tetramethyl-2-ethyl-2-butyl-l-oxa-3-oxo-4-benzy 4,8 diaza-spiro-(4,5)-decane (9B) 1',4'- ~s-[7,7,9,9-tetramethyl-2-ethyl-2-butyl-1-oxa-3-oxo-4,8-diaza-spiro-(4,5)-decyl-4-~-butane (99) 7,7,9,9-~entamethyl-2,2-dibutyl-4-benzyl-1-oxa-4,8-diaza-3-oxo-spiro-(4,5)-decane (1ûO) 7~7~9~9-tetramethyl-2~2-dipentyl-3-hexyl-1-oxa-3~a-diaza 4-oxo-spirD-(4,5)-decane (101) 7,7,9,9-tetramethyl-2,2-dipentyl-3-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (102) 7,7,9,9-tetramethyl-2,2-dipentyl-3-benzyl-1-oxa-3,B-diaza-4-oxo-spiro-(4,5)-decane 15 (103) 1',4'-kls-[7,7,9,9-tstramethyl-2,2-dipentyl-1-Dxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-butane (1û4) 1',6'- W s-~7,7,9,9-tetramethyl-2,2-dipentyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-hexane (105) 1',10'-bis-~7,7,9,9-tetramsthyl-2,2-dipentyl-1-oxa-3,8-diaza-4-oxo-s~iro-(4,5)-decyl-3-]-dec3ne (106) 7,7,9,9-~etramethyl-2,2-ditetradecyl-3-hsxyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decana (107) 1',6'-~is-[7,7,9,9-tetramsthyl-2,2-ditetradecyl-1-oxa-3~8-diaza-4-oxo-spiro-(4~5)-decyl-3-]-heXans 25 (108) 7,7,9,9-tetra~cthyl-2,2-dioctadecyl-3-benzyl-1-oxa-3,~-diaza-4-oxo-spiro-(4,5)-dPcans (109) 7,7,9,9-tetramethyl-2,2-dioctadecyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-docane (110) 7,7,9,9-tetramethyl-2,2,3-trioctadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (111) 1',6'- ~s-[7,7,9,9-tetramethyl-2,2-dioctadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-]-hexane (112) 3,7~7,9,9-pentamethyl-2-phenyl-l-oxa-3~a-diaza-4-oxo-spir S )-d~cane , -8~ 2 11 _ (113) 7,7,9,9-tetramethyl-2-iso-propyl-4-ethyl-1-oxa-4,8-diaza-3-oxo-spiro-~4~5)-dccana (114) 7,7,9,9-tetramethyl-2-iso-hexyl-3-ethyl-1-axa-3,a-diaza-4--oxo--spiro--(4,5)--dccsn8 (115) 3~7~7~9~9-t~entamethyl-2-nonyl-1-oxa-3~-diaza-4-oxo-spiro-(4,5)-decane (116) 7,7,9,9-tE?tramethyl-2-isn-nonyl-3-hexyl-1-oxa-3,a-diaza-4-oxo-spiro-(4~5)-decane (117) 7,7,9,9-tetramethyl-2-iso-heptyl-3-octadecyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decane (118) 7,7,9,9-tetramsthyl-2-undscyl-3-benzyl-1-oxa-3,8-diaza-4 oxo-spiro-(~,5)-decane (119) 1',4'-~is-[7,7,9,9-tetramethyl-2-iso-nonyl-1-oxy-3,8-diaza-4-oxo-spiro-(4,5)-decyl-3-~-butane (120) 4,7,7,9,9-~3entamethyl-2-iso-butyl-~-oxa-3-oxo-4,8-diaza-spiro~(4,5)-decan e (121) 7,7,9,9-tstramethyl-2-iso-hsptyl-1-oxa-4-ethyl-3-oxo-4,~-diaz~-spiro-(h,5)-decan e ~122) 1'~5'-~ls-[7~7,9,9-t~tr2methyl-2-iso-pentyl-1-oxa-3-oxo-2n 4,8-diaza-spiro-(4,5)-decyl-4-]-pentane (123) 2,2,4,4- tetramsthyl-13-hexyl-?-oxa-3,13-diaza-14-oxo-di.-spiro-(5~1,4,2)-tetradecan e (124) 2,2,4,4-tstramethyl-13-sthyl-7-oxa-3,13-diaza-24-oxo-di-spiro-(5,1,4,2)-tetradecan e (125) 2,2,4,4- t~tramethyl-13-butyl-7-oxa-3,13-diaza-14-oxo-dispiro-(5,1,4,2)-tetradecan e (126) 2,2,4,4-t~tramethyl-14-ethyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentadocan e (127) 2,2,4,4-.tetramethyi-14-butyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentadecan e (128) 2,2,4,4-t~tramethyl-14-hexyl-7-oxa-3,14-diaza-15-oxo-di~piro-~5,1,5,2)-pentadecan e (129) 2,2,4,4-t}3tramethyl-14-benzyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentadscan e .
~; ' i !
8~S2 - 12 _ HOE ~
(13CI) 1',4'-bis-[2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5~l~5~2)-pentadecyl-14~-butane (131) 1',4'-bis-[2,2,4,4-tetramethyl-1-oxa-3,14-diaza-15-oxo-disp~ro-(5~1~5~2)-pentadecyl-l4]-butane (132) 1',6'-bis-[2,2~4,4-tetramethyl-7-oxa-3,14-d~aza-15-oxo-dispiro-(5,1,5,2)-pentadecyl-14]-hexane (133) 2,2,4,4,10,12-~?examethyl-14-ethyl-7-oxa-3,14-diaza-15-oxo-dispiro-(5,1,5,2)-pentadecane (134) 2,2,4,4,10,10,12,12--ootamethyl-14-ethyl-7-oxa-3,14-dia~a-15-oxo-dispiro-(5,1,5,2)-pentadecane (135) 2,2,4,4,15-pentamethyl-7-oxa-3~15-diaza-14-oxo-dispir (5~1~5~2)-psntadecen e (136) 2,2,4,4-tetra0ethyl-15-hexyl-7-oxa-3,15~diaza-14-oxo-di-spiro-(5,1,5,2)-pentad~can e (137) 2,2,4,4,20-pentamathyl-7-oxa-3,20-diaza-21-oxo-dispiro-(5~ ?2)-hensicosan e (138) 2,2,4,4-tetramethyl-20-ethyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11~2)-heneicosan e (139) 2~2~4,b-tetramethyl-20-iso-propyl-7-oxa-3,20-diaza-21-oxo-dispiro-(5,1,11~2)-heneicosane (140) 2,2,4,4-tetramethyl-20-butyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11,2)-hsneicosan e (141) 2,2,4,4-tetramethyl-20-iso-butyl-7-oxa-3,20-diaz2-21-oxo-dispiro-(5,1,11,2)-heneicosane (142) 2,2,4,4-tetramethyl-20-Pentyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11,2)-heneicocane (143) 2,2,4,4-tetramethyl-20-hexyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11,2)-heneicosan e (144) 2,2,4,4-tetramethyl-20-octyl-7-oxa-3,20-diaza-21-oxo-di-spiro-(5,1,11,2)-heneicosan B
(145) 2,2,4,4-~tetramethyl-20-heptyl-7-oxa-3,20-diaza-21-o%o-di-spiro-(5,1,11,2)-heneicosan e (146) 2~2~4,4- tetramethyl-20-octadecyl-7-oxa-3,20-diaza-21-oxo-dispiro-(5,1,11,2)-heneicosan e :~.
, ...,, . " ~ .
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(147) 2,2,4,4-~ ~tramathyl-20-bcnzyl-7-oxa-3,20-diaza-21-oxo--di-spiro-(5,1,11,2)-heneirosans (148) 1~4~-bis-~7~2~4~4-totramethyl-7-oxa-3~2o-diaza-2l-oxo -dispiro-(5,1,11,2)-heneicosyl-20-]-butane (149) 1',5'-~is-[2,2,~,4-totramsthyl-7-oxa-3,20-diaza-21-oxo-di~piro-(5,1,11,2)-heneit:o3yl-20-]-pentane (150) 1',6'-bi~-[2,2,~,4-tstramethyl-7-oxa-3,20-diaza-21-oxo-dispirc)-(5,1,11,2)-hsneicosyl-20-]-hexane (151) 1l~1o~-bis-[2~2~4~4-tetramethyl-7-oxa-3~2o-diaza-21 dispiro-(5,1,11,2)-heneicosyl-20-]dscane ~152) 2,2,4,4,21-Pentamethyl-7-oxa-3,21-diaza-20-oxo-dispiro-(5,1,11,2)-heneicosan e (153) 7,7,9,9-tetramethyl-2,2-dibenzyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro-(4,5)-decan~
(154) 7,7,9,9~totramethyl-2,2-dibenzyl-3-octadecyl-1-oxa-3,û-diaza-4-oxo-spiro-(4,5)-decano (155) 7,7,9,9- tstramethyl-2, 2t 3-tribenzyl-1 oxa-3,8-diaza-4-oxn-spiro-(4,5)-decan e ~156) 1,2-}~is-[2,2,7,7,9,9-hexam~thyl-1-oxa-3,8-diaza-~-o~o-di~piro-(4,5)-decan-3-methyl-]-benz ene, The novel compounds are prepared according to the fol-.lowing reaction scheme from polyalkyl-1-oxa-diaza-spirode-canes of the formula (IV), which for their part are obtain-25 ed according to German Patents Nos. 2,606,026; 2,634,957 and 2,834,962, and halogen compounds of the formula (V), while hydrogen halide is split off:
- ~ . .
5;2 - 14 - HOE 79tF 817 ~H2R
H ~C y ~2 (IV) (V) ~/ Base -n Base~ HHal 20 ~ X~ 7 (1) The radicals R1 through R7 and X are as defined above, Hal is chlorine, bromine or iodine, n is 1 or 2.
In detail, the following radicals are suitable:
30 R1 = hydrogen, oxygen, methyl, butyl, hexyl, octyl, : dodecyl R2 = hydrogen, methyl, ethyl, butyl R3 = hydrogen, methyl, ethyl, butyl . R4 = methyl R3 and'~4~ -to`get~er with the carbon atom 9 = cyclohexyl, 2,2,6,6-tetramethylpiperidyl - R5 and R6 = ~lydrogen, ethyl, propyl, iso-propyl, butyl, .
, ~
~, `
.
~ . . . - .
. .
35;~
i.so-butyl, pentyl, iso-pentyl, hexyl, iso~-hex~-yl, heptyl, iso-heptyl, octyl, nonyl, iso-nonyl, decyl, undecyl, tridecyl, octadecyl, phenyl, 2,4-dichloropher1yl R5 and R6 together with the carbon atom 2 = cyclohexy-lidelle, 3,5-dimethylcyclohexyli.dene, 3,3,5,5-tetramethylcyclohexylidene, cycloheptylidene, cyclododecylidene, 2,2,6,6~tetramethylpiperi-dylene 10 R7 = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, dodecyl, tetradecyl, oc-tadecyl, benzyl, ethylene, propylene, butylene, pentylene, hexylene, decylene, butenylene, xylylene .
The synthesis is carried out as follows: In the case where n is 1, the compounds (IV) and (V) are reacted with each other in a molar ratio of from 1:1 to 1:10, preferab-ly 1:1.2 to 1:5, especially 1:1.5 to 1:3; and in the case where n is 2, in a molar ratio of from 2.5:1 to 2:1, pre-ferably 2.1:1 to 2:1, especially 2:1. The reactiGn is per-rormed in an organic solvent in the presence Or an 3quimo-lar to 20-fold amount of solid alkali metal hydroxide? or a 20 % to, preferably, 50 ~, aqueous alkali metal hydroxide solution in the presence of a phase transfer catalyst. The reaction temperature is in the range of from 20 to 120C, preferably 20 to 70C, especially 40 to 60C. As organic solvents, there are used aliphatic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, gasoline frac-tiOI1S, toluene, cyclohexane etc., or an excess of alkyl halide. By phase transfer catalysts, there are to be un-derstood compounds selected from the group Or quaternary ammonium halides, which are employed in an amount of from -~.1 to 5 weight %, relative to compound (IV); tricapryl-methylammonium chloride being especially suitable. The reaction is generally `complete after 1 to 20 hours, depend-ing on the reactivity Or the halogen component~
For work-up, the phases are separated, optionally after ., , ~, :
.
additiol1 of a small amount of water. The organic phase is repeatedl.y washed with water, dried over Na2SO4 or MgSO4, concentrated, and the residue is recrystallized In some cases, the final products crystallize already in the reac-tion solutions and are then isolated by filtration.
It was surprising and not to be expected that especial-ly those compounds in which X1 is H could be prepared ac-cording to the above method. In contrast to the course ofreaction actually observed and proved by 13C-NMR examina-tion, a subskitution at the piperidine nitrogen was ratherto be calculated on, because due to its higher basicity its nucleophilic power is considerably greater than that of amide nitrogen in the atom group X.
As to properties and efficiency of the novel compounds, it should have been expected that there are no differences at all or to an insignificant extent only as compared to 1-oxa-diaza-spirodecanes of similar structure described in the patent literature and recommended as plastics stabili-zers (German Offenlegul1gsschriften Nos. 1,770,68g and 2,227,6~9). Surprisingly, however, the novel c~mpounds are highly superior to even the best of the compounds listed in the above German Offenlegungsschriften, that is, that of Ex-ample 58 of German Offenlegungsschrift No. 1,770,689. This compound, namely 7,7,8,9,9-pentamethyl-3-epoxypropyl-1,3,8-triaza-spiro-(4,5)-decane-2,4-dione, although distinguished by a very good stabilizing action, is highly volatile on processing. This is valid, too, for the compounds of Ger-man Offenlegungsschriften Nos. 2,606,026 and 2,634,957, - and they can be easily washed off from the thermoplastic materials containing them.
High-quality stabilizers, however, have to meet severe requirements in addition to their stabilizing action, espe-ci.ally with respect to the above physical properties. For, a too high volatility results in considerable stabilizer losses on processing of the polymers, and the activity of the stabilizer is reduced when it is too readily washed off, for example on sprinkling with water.
.
.
.
.
. ; ' ~, : .
- ~ - HOE 79/F 817 It was therefore not to be expeced at all that, des-pite their relationship with the compounds of the cited Offetllegungsschriften, the compounds of the invention are not only more effective as stabili~ers, but also excel by an especially low volatility and increased resistance to being washed Gff (these advantageous properties being pre-sent above all in the compounds where n is 2), so that this must be considered as an essential technical progress.
As already mentioned, the novel compounds are used as stabilizers for plastic materials against damage thereo~
by influence of oxygen, heat and light. Examples of those plastics are the follo~ing:
Polymers which are derived from hydrocarbons with one or two unsaturated olefinic bonds, for example polyolefins such as polyethylene, optionally cross-linked, polypropy-lene, polybutene-1, polyisobutene, polymethylbutene-1, polymethylpentene-1, polyisoprene, polybutadiene, polysty-rene, copolymers of the monomers on which the abovemention-ed homopolymers are based, such as ethylene/propylene copo-lymers, propyleneJbutene-1 copolymers, propylene/isobutene copolymers, styrene/butadiene copolymers, as well as ter-polymers of ethylene and propylene with a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene, mix-tures of the abovementioned homopolymers, for example mix-tures of polypropylene and polyethylene, polypropylene andpo].ybutene-1, polypropylene and polyisobutylene, or of a butadiene/acrylonitrile copolymer with a styrene/butadiene copolymer.
Vinyl polymers containing halogen, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, po-lychloroprene and chlorinated rubber, as well as copolymers of vinyl chloride and vinylidene chloride with one another and with other olefinically unsaturated monomers.
Polymers derived from oC,~-unsaturated acids and their derivatives, such as polyacrylates, poplymethacrylates, po-lyacrylamides and polyacrylonitrile, as well as their copo-lymers with one another and with other vinyl compounds, for .
- 18 - HOE 79/F ~17 example acrylonitrile/butadiene/styrene, acrylonitrile/sty-~rene and acrylonitrile/styrene/acrylic ester copolymers.
Polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as 5 polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvi.nyl butyral, polyallyl phthalate, po~yallyl melamine and their copoly-mers with other vinyl compounds, such as ethylene/vinyl acetate copolymers.
Homopolymers and copolymers which are derived from ep-oxides, such as polyethylene oxide or polymers derived from bisglycidyl ethers.
Polyacetals, such as polyoxymethylene and polyoxy-ethylene, as well as those polyoxymethylenes which contain ethylene oxide as comonomer.
Polyurethane and polyureas.
Polycarbonates.
Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic aolds or the correspondin~ lactatms, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12.
Polyesters derived from dicarboxylic acids and diols and/or ~rom hydroxy carboxylic acids or from the correspond-ing lactones, such as polyethylene glycol terephthalate, polybutyleneterephthalate, poly-1,4 dimethylol-cyclohexane-terephthalate.
Cross-linked polymers which on the one hand are de-rived from aldehydes and on the other hand from phenols, ureas and melamines, such as phenol/formaldehyde, urea/form-aldehyde and melamine/formaldehyde resins.
Of special importance is the stabilization of polyole-fins, styrene polymers, polyamides, poly-(meth-)acrylates and of polyurethanes, for which the novel compounds are especially suitable. Examples thereof are polyethylene of 35 '~'i~her an'd'-'lower density, polypropylene, ethylene/propylene copolymers, polystyrene, styrene/butadiene/acrylonitrile terpolymers, mixtures of polyolefins or of styrene poly-~ . . .
, , - , , - ~ .
.
~ 8~3~2 mers, polyurethar~es on the basis of polyether or polyester in the form of lacquers, fibers, sheets, plates, films, elastomers or foam plastics.
The new stabilizers are incorporated i.nto the polymer masses according to the methods generally used. The incor-poratiol~ can be carried out, for example, by intermixing the compounds ar3d optionally other additives with the melt accordlng to the methods usual in the industrial practice, before or during shaping, or also by applying the dissolv-ed or dispersed compounds directly to the polymer, or byintermixing them with a solution, suspension or emulsion of same, optionally with subsequently allowing the solvent to evaporate. The amounts are from 0.01 to 5, preferably 0.05 to 2.5, and especially 0.1 to 1.0 % by weight, rela tive to the material to be stabilized. The new compounds can also be added to the plastics to be stabilized in the form of a masterbatch containing these compounds, for example in a concentration of from 2.5 to 50, preferably 5.0 to 20, % by weight.
The plastics stabllized by addition of substances of formula (I) may contain other known and usual additives, such as antioxidants based on phenol and sulfide, UV absor-bers and light protecting agents, phosphite stabilizers, metal compounds, epoxy stabilizers and polyalcohols.
Examples of antioxidants are those of the type of ste-rically hindered phenols, such as 4,4'-butylidene-bis-(2,6-di-t.-butyl-phenol), 4,4'-thio-bis-(2-t.-butyl-5-methyl-phenol), phenolic triazine compounds, thiodipropionic acid esters of fatty alcohols, dioctadecyl sulfide and -disul-fide.
The UV-absorbers and light protecting agel1ts include, for example, 2-(2'-hydroxyphenyl)~benzotriazoles, such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-hyd.oxy-benzophenones, such as 2-hydroxy-4-octoxy-benzophenone, sta~,bilizers of the group of the salicylates, such as oc-tylphenyl salicylate, nickel chelates, oxalic acid diami-;~ des and sterically hindered piperidine compounds.
. .
?.~ 3S;Z
~ 20 - HnE 79~F 817 Qs phos~hites there are to be mentioned trisnonylphe-nyl phosphite, trislauryl phosphite and esters of pentaery-thritol phosphite.
By metal compounds known as stabilizers there are to be understood: ~alcium, barium, strontium, zinc, cadmium, ma~;nesium, aluminum and lead soaps of aliphatic carboxylic acids or hydroxycarboxylic acids hav.ing about 12 to 32 car-bon atoms, salts of the aforesaid metals with aromatic carb-oxylic acids, such as benzoates or salicylates, and (al-kyl-)phenolates of these metals, and also organo-tin com-pounds such as, for example, dialkyltin thioglycolates and carboxylates.
Known epoxy stabilizers are, for example, epoxidized higher fatty acids, such as epoxidized soybean oil, tall oil, linseed oil or epoxidized butyl oleate, and also ep-oxides of long-chain olefins.
Polyols may be, for example, pentaerythritol, trime-thylolpropane, sorbitol or mannitol, i.e. preferably alco-hols having 5 or 6 carbon atoms and 3 to 6 OH-groups.
An effective stabilizer combination for poly- ~-ole-flns such as, for exmpl~, high, medium and low pressure polymers of C2- to C4- ~-olefins, especially polyethylene and polypropylene or copolymers of such ~ -olefins, COII-sists, calculated on 100 parts by weight of polymer, for example, Or from 0.01 to 5 parts by weight of one of the compounds to be used in accordance with the invention, of from 0.05 to 5 parts by weight of a phenolic stabilizer, optionally of from 0.01 to 5 parts by weight of a sulfur-containing costabilizer, and optionally of from G.01 to 3 parts by weight of a basic or neutral metal soap such as, for example, calci~lm stearate or zinc stearate, and optio-nally of from 0.1 to 5 parts by weight of a phosphite and optionally Or from 0.01 to 5 parts by weight of a known UV-stabilizer of the group of alkoxy-hydroxybenzophenones, 4-hydroxyphenyl-benzotriazoles, benzylidene-malonic acid-mononitrile esters or the so-called quenchers, such as nickel chelates.
.i .
: :
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.
. .
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~84~
- 21 - ~.OE 79/F 817 The plastics stabilized according to the inYentioo can be used in most different shapes, for example as sheets, fibers, ribbons, profiles, or as binders for laquers, ad- -hesives or cements.
The following examples illustrate the invention.
_ X A M P L E 1:
2t2,4,4,7,7,9,9-heptamethyl-1-oxa-4,8-diaza-3-oxo-spiro-(4,5)-decane (Compound No. 14) _ _ 6.8 g of 2,2,7,7,9,9-hexamethyl-1-oxa-4,8-diaza-3-oxo-spiro-(4,5)-decane and 20 g of methyl iodide were introdu~
ced into the reactor in-50 ml of tcluene. After having ad-ded three drops of the phase transfer catalyst tricapryl-methylammonium chloride, 20 ml of 50 % sodium hydroxide so-lution were added to the reaction mixture, and it was agi-tated for 5 hours at 45C. During the reaction, the batch becomes first jelly and then transparent. The phases are subsequently separated and the organic phase is shaken twice with 30 ml each of water, filtered and concentrated. The residue is recrystallized from petroleum ether. 5.4 g of white crystals/m.p. 128-130C.
The same results are obtained when operating in hexane, heptane and cyclohexane as solvent.
E X A M P L E S 2 to 71:
Operations were as described in Example 1 with the use o~ other educts.
Test conditions and characteristics of the products are listed in the following Table. Column 2 (Compound No.) indicates the compounds cited pages 4 to 13.
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E X A M P L E 72:
-This example shows the volatili.ty of the stabilizersin accordance with the invelltion as compared to products of the state of the art according to German Offenlegungs-5 schrift No. 2,227,689.
The volatility values were determined in an apparatus for thermogravimetric analysis. Identical amounts (500 mg) each of the stabilizers of the inventioll and of the compa-rative substances were heated at a speed of 2 K/min to 10 300C in a nitrogen atmosphere, and the loss of substance was measured in mg/cm2. The results are indicated in the following Table:
Stabilizer weight losses in mg/cm2 acc. to Example when attaining .... C
200 260 30010 min at 300 0.63 4.11 14.85 24.33 4 0.79 3.63 13.27 20.22 2 ~.58 7.43 22.l~4 35.39 69 0.32 2.37 7.27 11.06 0.01 0.32 2.05 3.79 comparison1) 114.06 45.82148.62153.26 1) Compound according to Example 58 of German Offenlegungs~
schrift No. 2,227,689.
E X A M P L E 73:
For testing the stabilizing properties of the novel .compoullds, operations were as follows:
100 Parts by weight of polypropylene having a melt flow index i5 of about 6 g/10 min (determined accord~
~ng~o~ ~AST~ a23~-62 T) and a density of 0.90 were mixed with .
.
5i2 - 0.1 part by weight of pentaerythrityl-tetrakis-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate, 0.2 part by weight of calcium stearate, and 0.3 part by weight of the stabilize. of the invention to be examined.
In order to obtain a distribution as uniform as possible on the polymer grain, the stabilizers were dissolved ili a solvent, and the solution was added dropwise to the poly-propylene powder with agitation, while the substantial part of the solvent was evaporated by simultaneous radia-tion with an IR lamp. After about 20 minutes, the calcium stearate was added, and mixing was continued for another 10 minutes. Solvent residues were removed by drying at 50C/120 min in a drying cabinet.
On a Windsor injection molding machine type SP 50, the polypropylene was injection-molded at 240C to plates hav-ing dimensions of 60x60x1 mm, from which plates test speci-mens according to German Industrial Standard DIN 53 455, form 3, were cut in a reduced scale of 1:3. The test speci-mens required ror comparlson were manufaotured in analogous manner, but without the stabilizer to be tested or with ad-dition of the comparative stabilizers.
For determining the stability to light, the specimens were exposed to radiation with light intensity variation of a Xenotest-1200 apparatus of the company Original Hanau Quarzlampen GmbH. The radiation intensity was modulated by UV filters (special filter glass d = 1.7 mm). The stability to light was tested according to &erman Industrial Standard DIN 53 387 (17 minutes of moistening, 3 minutes of sprink-ling, blackpanel temperature 45C, atmospheric moisture70-75 ~). The time of exposure was measured in hours, and the elongatiol1 at break was determined on a tensile test-ing machine of the Instron company at a draw-off speed of 5 cm/min.
.
:
Stabilizer acc. Exposure time elongation at break to Examplehoursin % of initial value -1 100 ~ 50 4 1 100 ~50 2 1 100 ~50 69 1 100 ~50 1 100 ~50 Polypropylene260 Comparison 320 (without stabilizer) Comparison 1)1 100 2 1 ) Compound according to Example 58 of German Offenlegungs-schrift No. 2,227,689.
E X A M P L E 74:
0.26 part by weight of the stabilizers indicated below are mixed by means of a laboratory high-speed mixer with polypropylene (Hostalen PPU VP 1770 F of Hoechst AG) hav-ing a melt flow lndex MFI 190/51.9 g/10 min according to German Industrial Standard DIN 53 535. The material so stabilized was melted in a laboratory extruder under usual processing conditions, and processed via a spinning pump having a multiple spinneret to give monofilaments (87 dtex), which were subsequently after-drawn in a ratio of 1:2.5.
24 each of these filaments were texturized to give a yarn whioh was processed to test fabrics. The specimens were subjected to a light fastness test in a fadeometer and, after the time of exposure as indicated, subjected to a ~inger nail test (light rubbing with-the thumb nail over the fabric). The degree of degradation is expressed in num-bers (O = no damage, 1 to 5 = increasing destructibility).
Stabili~,er acc. Destructibility of fabric to Example after .... hours of exposure (p.b.w.) 40 80 160 _ without stab. (Comp.) 0 0 5 0 0 . O
Comparison 1) 0 0 ) Compound according to Example 58 of Germar. 0ffenlegutlgs-schrift No. 2,227,689.
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:
E X A M P L E 72:
-This example shows the volatili.ty of the stabilizersin accordance with the invelltion as compared to products of the state of the art according to German Offenlegungs-5 schrift No. 2,227,689.
The volatility values were determined in an apparatus for thermogravimetric analysis. Identical amounts (500 mg) each of the stabilizers of the inventioll and of the compa-rative substances were heated at a speed of 2 K/min to 10 300C in a nitrogen atmosphere, and the loss of substance was measured in mg/cm2. The results are indicated in the following Table:
Stabilizer weight losses in mg/cm2 acc. to Example when attaining .... C
200 260 30010 min at 300 0.63 4.11 14.85 24.33 4 0.79 3.63 13.27 20.22 2 ~.58 7.43 22.l~4 35.39 69 0.32 2.37 7.27 11.06 0.01 0.32 2.05 3.79 comparison1) 114.06 45.82148.62153.26 1) Compound according to Example 58 of German Offenlegungs~
schrift No. 2,227,689.
E X A M P L E 73:
For testing the stabilizing properties of the novel .compoullds, operations were as follows:
100 Parts by weight of polypropylene having a melt flow index i5 of about 6 g/10 min (determined accord~
~ng~o~ ~AST~ a23~-62 T) and a density of 0.90 were mixed with .
.
5i2 - 0.1 part by weight of pentaerythrityl-tetrakis-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate, 0.2 part by weight of calcium stearate, and 0.3 part by weight of the stabilize. of the invention to be examined.
In order to obtain a distribution as uniform as possible on the polymer grain, the stabilizers were dissolved ili a solvent, and the solution was added dropwise to the poly-propylene powder with agitation, while the substantial part of the solvent was evaporated by simultaneous radia-tion with an IR lamp. After about 20 minutes, the calcium stearate was added, and mixing was continued for another 10 minutes. Solvent residues were removed by drying at 50C/120 min in a drying cabinet.
On a Windsor injection molding machine type SP 50, the polypropylene was injection-molded at 240C to plates hav-ing dimensions of 60x60x1 mm, from which plates test speci-mens according to German Industrial Standard DIN 53 455, form 3, were cut in a reduced scale of 1:3. The test speci-mens required ror comparlson were manufaotured in analogous manner, but without the stabilizer to be tested or with ad-dition of the comparative stabilizers.
For determining the stability to light, the specimens were exposed to radiation with light intensity variation of a Xenotest-1200 apparatus of the company Original Hanau Quarzlampen GmbH. The radiation intensity was modulated by UV filters (special filter glass d = 1.7 mm). The stability to light was tested according to &erman Industrial Standard DIN 53 387 (17 minutes of moistening, 3 minutes of sprink-ling, blackpanel temperature 45C, atmospheric moisture70-75 ~). The time of exposure was measured in hours, and the elongatiol1 at break was determined on a tensile test-ing machine of the Instron company at a draw-off speed of 5 cm/min.
.
:
Stabilizer acc. Exposure time elongation at break to Examplehoursin % of initial value -1 100 ~ 50 4 1 100 ~50 2 1 100 ~50 69 1 100 ~50 1 100 ~50 Polypropylene260 Comparison 320 (without stabilizer) Comparison 1)1 100 2 1 ) Compound according to Example 58 of German Offenlegungs-schrift No. 2,227,689.
E X A M P L E 74:
0.26 part by weight of the stabilizers indicated below are mixed by means of a laboratory high-speed mixer with polypropylene (Hostalen PPU VP 1770 F of Hoechst AG) hav-ing a melt flow lndex MFI 190/51.9 g/10 min according to German Industrial Standard DIN 53 535. The material so stabilized was melted in a laboratory extruder under usual processing conditions, and processed via a spinning pump having a multiple spinneret to give monofilaments (87 dtex), which were subsequently after-drawn in a ratio of 1:2.5.
24 each of these filaments were texturized to give a yarn whioh was processed to test fabrics. The specimens were subjected to a light fastness test in a fadeometer and, after the time of exposure as indicated, subjected to a ~inger nail test (light rubbing with-the thumb nail over the fabric). The degree of degradation is expressed in num-bers (O = no damage, 1 to 5 = increasing destructibility).
Stabili~,er acc. Destructibility of fabric to Example after .... hours of exposure (p.b.w.) 40 80 160 _ without stab. (Comp.) 0 0 5 0 0 . O
Comparison 1) 0 0 ) Compound according to Example 58 of Germar. 0ffenlegutlgs-schrift No. 2,227,689.
.. . . -'- ' ~:
:,.
:
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polyalkyl-diaza-spirodecane of the formula (I) wherein X represents a group of the formulae (II) or (III) (II) (III) the indices 3 and 4 indicating the ring positions in the diaza-spirodecane system, and the free valency of the nitrogen atom producing the linkage with R7;
R1 is hydrogen or C1-C4-alkyl, R2 and R3 either are identical and represent hydrogen or a CH3 group, R4 is a methyl group;
R5 and R6 are identical or different and represent hydrogen, C1-C18-alkyl, a phenyl group which may be substituted by C1-C4-alkyl, or a C7-C12-phenylalkyl group, or R5 and R6, together with the carbon atom linking them, form an unsubstituted C5-C18-cycloalkyl group or such a group substituted by up to four C1-C4-alkyl groups, or a group of the formula n is 1 or 2, and R7, in the case where n is 1, is an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, a phenylalkyl group having from 7 to 10 carbon atoms; and in the case where n is 2, R7 is an alkylene group having from 2 to 12 carbon atoms, or a phenyldialkylene group having from 8 to 10 carbon atoms;
and the salts thereof with non-oxidizing mineral acids, aliphatic sulfonic or phosphonic acids, aliphatic mono-, di- or polycarboxylic acids, or aromatic mono- or polycarboxylic acids.
R1 is hydrogen or C1-C4-alkyl, R2 and R3 either are identical and represent hydrogen or a CH3 group, R4 is a methyl group;
R5 and R6 are identical or different and represent hydrogen, C1-C18-alkyl, a phenyl group which may be substituted by C1-C4-alkyl, or a C7-C12-phenylalkyl group, or R5 and R6, together with the carbon atom linking them, form an unsubstituted C5-C18-cycloalkyl group or such a group substituted by up to four C1-C4-alkyl groups, or a group of the formula n is 1 or 2, and R7, in the case where n is 1, is an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, a phenylalkyl group having from 7 to 10 carbon atoms; and in the case where n is 2, R7 is an alkylene group having from 2 to 12 carbon atoms, or a phenyldialkylene group having from 8 to 10 carbon atoms;
and the salts thereof with non-oxidizing mineral acids, aliphatic sulfonic or phosphonic acids, aliphatic mono-, di- or polycarboxylic acids, or aromatic mono- or polycarboxylic acids.
2. A process for the preparation of a compound of the formula I as defined in claim 1 in which a polyalkyl-l-oxa-diaza-spirodecane of the Formula II
(II) wherein R1 through R6 and X are as defined in claim 1, is reacted with a halogen compound of the formula III
(III) in a two-phase system, consisting substantially of (a) an organic solvent and (b) an alkali metal hydroxide, in solid form or aqueous solution, in the presence of a phase transfer catalyst at 20 - 120°C; the compounds (II) and (III) being used in a molar ratio of from 1:1 to 1:10 in the case where n is 1, and in a molar ratio of from 2.5:1 to 2:1 in the case where n is 2.
(II) wherein R1 through R6 and X are as defined in claim 1, is reacted with a halogen compound of the formula III
(III) in a two-phase system, consisting substantially of (a) an organic solvent and (b) an alkali metal hydroxide, in solid form or aqueous solution, in the presence of a phase transfer catalyst at 20 - 120°C; the compounds (II) and (III) being used in a molar ratio of from 1:1 to 1:10 in the case where n is 1, and in a molar ratio of from 2.5:1 to 2:1 in the case where n is 2.
3. A process as claimed in claim 2, in which the phase transfer catalyst is a quaternary ammonium halide.
4. A composition, stabilized against decomposition by W comprising a synthetic polymer and from 0.01 to 5 parts by weight, relative to the polymer, of a stabilizer as defined in claim 1.
5. A composition as claimed in claim 4 in which the polymer is a polyolefin.
6. A composition as claimed in claim 4 in which the polymer is a halogen-containing polymer.
7. A composition as claimed in claim 4 in which the polymer is a polyacrylate or polymethacrylate.
8. A composition as claimed in claim 4 in which the polymer is polystyrene or a copolymer of styrene with at least one monomer copolymerisable therewith.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2933732.4 | 1979-08-21 | ||
| DE19792933732 DE2933732A1 (en) | 1979-08-21 | 1979-08-21 | ALKYLATED DIAZASPIRODECANE, THEIR PRODUCTION AND USE AS A LIGHT PROTECTION AGENT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148952A true CA1148952A (en) | 1983-06-28 |
Family
ID=6078894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000358634A Expired CA1148952A (en) | 1979-08-21 | 1980-08-20 | Alkylated diaza-spirodecanes, their preparation and use as light stabilizers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4319030A (en) |
| EP (1) | EP0025867B1 (en) |
| JP (1) | JPS5630985A (en) |
| CA (1) | CA1148952A (en) |
| DE (2) | DE2933732A1 (en) |
| ZA (1) | ZA805102B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH648036A5 (en) * | 1980-12-24 | 1985-02-28 | Sandoz Ag | 1-OXA-3,8-DIAZA-4-OXO-SPIRO (4,5) -DECAN COMPOUNDS. |
| US4419512A (en) * | 1981-10-15 | 1983-12-06 | Ciba-Geigy Corporation | N-Substituted polyalkylpiperidine-4-spirooxazolones |
| DE3217734A1 (en) * | 1982-05-12 | 1983-11-17 | Hoechst Ag, 6230 Frankfurt | POLYALKYLDIAZASPIRODECANYLESSIGAIC DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS LIGHT PROTECTION AGAINST ORGANIC POLYMERS |
| DE3218172A1 (en) * | 1982-05-14 | 1983-11-17 | Hoechst Ag, 6230 Frankfurt | POLYALKYLDIAZASPIRODECAN DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS STABILIZERS |
| WO1985001734A1 (en) * | 1983-10-13 | 1985-04-25 | Ford Motor Company | Polymeric light stabilizers containing polyalkylpiperidine groups |
| DE3524543A1 (en) * | 1985-07-10 | 1987-01-22 | Hoechst Ag | METHOD FOR PRODUCING 1-OXA-3,8-DIAZA-4-OXO-SPIRO (4,5) DECAN COMPOUNDS |
| DE3524542A1 (en) * | 1985-07-10 | 1987-01-22 | Hoechst Ag | 1-OXA-3-OXO-4,8-DIAZA-SPIRO (4,5) DECAN COMPOUNDS |
| DE3524541A1 (en) * | 1985-07-10 | 1987-01-22 | Hoechst Ag | NEW 1-OXA-3,8-DIAZA-4-OXO-SPIRO- (4,5) -DECAN- CONNECTIONS AND METHOD FOR THEIR PRODUCTION |
| DE3541665A1 (en) * | 1985-11-26 | 1987-05-27 | Hoechst Ag | SUBSTITUTED DIAZASPIRODECANE, THEIR PRODUCTION AND THEIR USE AS STABILIZERS FOR POLYMERS |
| US4863918A (en) * | 1987-02-06 | 1989-09-05 | Boc, Inc. | Enamine quaternary compounds, methods of making and their use as muscle relaxants |
| DE3871855D1 (en) * | 1987-05-05 | 1992-07-16 | Ciba Geigy Ag | POLYOLEFINS STABILIZED AGAINST LIGHT DAMAGE. |
| NL8702473A (en) * | 1987-10-16 | 1989-05-16 | Gen Electric | POLYMER MIXTURE WITH POLYPHENYLENE ETHER, STERICALLY Hindered AMINE AND EPOXY COMPOUND AND ARTICLES THEREFOR. |
| DE3919691A1 (en) * | 1989-06-16 | 1990-12-20 | Hoechst Ag | POLYALKYL-1-OXA-DIAZASPIRODECANE POLYMER |
| IT1247977B (en) * | 1991-06-04 | 1995-01-05 | Ciba Geigy Spa | STABILIZATION OF POLYMERIC ORGANIC MATERIALS BY MEANS OF SYNERGIC MIXTURES CONSISTING OF STERICALLY IMPEDED CYCLIC AMINES AND DERIVATIVES OF 3-PYRAZOLIDINONE OR 1,2,4, -TRIAZOLIDIN-3,5, -DIONE |
| DE4423055A1 (en) * | 1994-07-01 | 1996-01-11 | Hoechst Ag | New spiro-poly:alkyl piperidine cpds. useful for improved properties |
| KR20010050085A (en) * | 1999-08-18 | 2001-06-15 | 잔디해머,한스루돌프하우스 | Novel sterically hindered amines |
| US6465645B1 (en) | 2001-04-17 | 2002-10-15 | Ciba Specialty Chemicals Corporation | Long chain hindered amines and compositions stabilized therewith |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3708473A (en) * | 1971-02-08 | 1973-01-02 | Sterling Drug Inc | 3,3-dichloro-2-oxopolymethylenimines |
| CA975365A (en) * | 1971-06-05 | 1975-09-30 | Eiko Mori | Piperidine derivatives and their use as stabilizers |
| DE2606026C2 (en) * | 1976-02-14 | 1982-03-25 | Hoechst Ag, 6000 Frankfurt | 1-Oxa-3,8-diaza-spiro- [4,5] -decanes, their preparation and their use as light stabilizers |
| DE2634957C3 (en) * | 1976-08-04 | 1980-10-02 | Hoechst Ag, 6000 Frankfurt | l-Oxa-4,8-diaza-spiro- [43] -decanes, their preparation and their use as light stabilizers |
| DE2738340A1 (en) * | 1977-08-25 | 1979-03-01 | Hoechst Ag | NEW UREA DERIVATIVES, THEIR PRODUCTION AND USE AS LIGHT PROTECTION AGENTS |
| DE2834455A1 (en) * | 1978-08-05 | 1980-02-28 | Hoechst Ag | NEW UREA DERIVATIVES, THEIR PRODUCTION AND THEIR USE AS LIGHT PROTECTION AGENTS FOR POLYMERS |
| DE2834962A1 (en) * | 1978-08-10 | 1980-02-21 | Hoechst Ag | METHOD FOR PRODUCING AZASPIRODECANES |
| EP0017617A3 (en) * | 1979-03-27 | 1980-10-29 | Ciba-Geigy Ag | Polyalkylpiperidine spirooxazolones, their application as light stabilisers and polymers stabilised therewith |
-
1979
- 1979-08-21 DE DE19792933732 patent/DE2933732A1/en not_active Withdrawn
-
1980
- 1980-08-16 DE DE8080104875T patent/DE3065055D1/en not_active Expired
- 1980-08-16 EP EP80104875A patent/EP0025867B1/en not_active Expired
- 1980-08-18 US US06/178,927 patent/US4319030A/en not_active Expired - Lifetime
- 1980-08-20 JP JP11354780A patent/JPS5630985A/en active Granted
- 1980-08-20 ZA ZA805102A patent/ZA805102B/en unknown
- 1980-08-20 CA CA000358634A patent/CA1148952A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4319030A (en) | 1982-03-09 |
| DE2933732A1 (en) | 1981-03-26 |
| ZA805102B (en) | 1981-09-30 |
| JPH0433796B2 (en) | 1992-06-04 |
| DE3065055D1 (en) | 1983-11-03 |
| JPS5630985A (en) | 1981-03-28 |
| EP0025867A1 (en) | 1981-04-01 |
| EP0025867B1 (en) | 1983-09-28 |
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