CA1198437A - N-substituted polyalkylpiperidine-4-spirooxazolidones - Google Patents
N-substituted polyalkylpiperidine-4-spirooxazolidonesInfo
- Publication number
- CA1198437A CA1198437A CA000413272A CA413272A CA1198437A CA 1198437 A CA1198437 A CA 1198437A CA 000413272 A CA000413272 A CA 000413272A CA 413272 A CA413272 A CA 413272A CA 1198437 A CA1198437 A CA 1198437A
- Authority
- CA
- Canada
- Prior art keywords
- hydrogen
- alkyl
- oxa
- oxo
- diaza
- 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
- 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
- C07D498/12—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 three hetero rings
- C07D498/20—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
N-Substituted polyalkylpiperidine-4-spirooxazolidones Abstract of the Disclosure Compounds of the formulae Ia and Ib
Description
8 ~ 3 ~
Case 3-13598/S/=
N-Substituted polyalkylpiperidine-4-spirooxazolidones The invention relates to novel polyalkylpiperidine-4-spirooxalidones and to their use as stabilisers for organic polymers, in particular against the action of light, as well as to the so stabilised polymers.
In German Offenlegungsschrift specifications 26 06 026, 28 34 962 and 29 33 732, and in European patent application 17 617, there have already been disclosed polyalkylpiperidine-4-spirooxazolidones of the formulae A and B
R~i R R R"
y X- N/ .~i (A) Y (B~
as light stabilisers for organic polymers, wherein R is alkyl, R' is hydrogen or alkyl, R" is a monovalen~ hydro-carbon radical, X is hydrogen, oxygen, OH or an unsubstituted or substituted hydrocarbon radical, and Y
is hydrogen or a hydrocarbon radical. All these compounds have a basic nitrogen atom in the piperidine ring and are therefore basic compounds which can form salts with acids.
~98437 For ~pecific fields of use the basicity of these compounds can be a drawback, for example for acid catalysed lacquers or for electrostatically or electrophoretically applied lacquers. There was accordingly a need for non-basic polyalkylpiperidine-4-spirooxazolidones for such special fields of use.
It has been found that those compounds of the formulae A and B are suitable for such use in which X is an acyl, carbamoyl or cyanomethyl group. Accordingly, the invention provides compounds of the formula Ia or Ib \2/CH3~R i ~2 CH3 1 4 _; O ~ n R5 -- /O I-R LR
(Ia) (Ib) wherein n is 1 or 2;
Rl is C2-C30alkanoyl, C3-C20alkenoyl, -CH2CN, -Co-N(R6)(R7), C royl C8-C14arylalkanoyl or C8 20 R is hydrogen or Cl-C4alkyl; each of R3 and R4 independently of the other is hydrogen, Cl-C~Oalkyl, unsubstituted or chlorine- or alkyl-substituted C6-ClOaryl, unsubstituted or alkyl-substituted C7-C~laralkyl, or R3 and R4, together with the carbon atom to which they are attached, form a cycloalkane or alkylcycloalkane ring containing 5 to 18 carbon atoms,or a group of the formula ~i ~ ~1 ~8437 .
R , when n is 1, is Cl-C30alkyl, C3-C20alkenyl, unsubsti-tuted or alkyl-substituted C7-Cllaralkyl, or is c5-cl2cycloalkyl, c2-cl8alkanoyl, C3~C18alkenY
C aroyl ~ -C14arylalkanoyl or C8 C20 or ~5 when n is 2, is C2-C30alkylene, C2-C30a y C8-C18arylenedialkylene;
R is hydrogen, Cl-C18alkyl, C5-C8cycloalkyl, C7-C15aralkyl or c6-ClOaryl;
R7 is Cl-C18alkyl, C5-C8cycloalkyl, C7-C15aralkyl or 6 C67CloarYl; or R and R , together with the nitrogen atom, form a 5- to 7-membered ring which can be interrupted by further hetero-atoms, and R8 is hydrogen, Cl-C12alkyl, C3-C5a:Lkenyl, C3-C5alkynyl, unsubstituted or alkyl-substituted C7-Cllaralkyl, C2-cl8alkanoyl~ c3-C18alkenoyl, -CH2CN or -co-N(R6)(~7~.
R , R3, R4, R5, R6, R7 and R8 can be unbranched or branched alkyl. Within the scope of the defined number of carbon atoms, examples of such alkyl groups are methyl, ethyl, isopropyl, sec-butyl, tert-butyl, hexyl, octyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, docosyl or triacontyl.
'a37 .
Within the scope of the defined number of carbon atoms, R5 and R as a~enyl can be e g. allyl, methallyl, 3,3-dimethylallyl, 1-buten-4-yl, 2-hepten-1-yl or oleyl.
R8 as alkynyl can De e.g. propargyl, butynyl or pentynyl.
R5, R and R7 as cycloalkyl can be e.g. cyclopentyl, cyclohexyl or cyclooctyl. R5 can also be e.g. methylcyclo-hexyl, dimethylcyclopentyl or cyclododecyl.
R3, R4, R6 and R7 as aryl can be phenyl or naphthyl, and R3 and R4 can also be e,g. chloroaryl or alkyl-substi~
tuted aryl, in particular phenyl substituted by Cl-C4alkyl.
Examples of such groups are chlorophenyl, chloronaphthyl, mono- or dimethylphenyl, nonylphenyl or dodecylphenyl.
R3, R4, R5, R6, R and R8 as aralkyl can be e.g.
phenylethyl, phenylisopropyl and, in particular, benzyl.
Examples of R3, R4, R5 and R8 as alkylated aralkyl are methylnaphthylmethyl, octylbenzyl, nonylbenzyl, dodecyl-benzyl and, in partic~lar, benzyl substituted by Cl-C4alkyl, e.g. methylbenzyl, isopropylbenzyl or tert-butylbenzyl.
A cycloal~ane ring formed by R3 and R4 together with the carbon atom to which they are attached can be e.g~ a cyclohexane, cyclooctane or cyclododecane ring.
A 5- to 7-membered ring ~ormed by R6 and R7, together with the nitrogen atom to which they are attached, can be e.g. a pyrrolidine, piperidine, morpholine or piperazine ring.
R as alkylene can be unbranched or branched alkylene, e.g. ethylene, hexamethylene, octamethylene, dodecylmethylene, 1,2-propylene or 2,2-dimethylpropylene-1~8~37 1,3. R5 as alkylene can be e.g. 2-butylene-1,4 or 2,3-dimethyl-2-butenylene-1,4. R5 as arylene-dialkylene can be e.g. phenylenediethylene or naphthylenPdimethylene, and~
in particular m- or p-xylylene.
Rl, R5 and R as aliphatic acyl radical~ can be e.g.
acPtyl, propionyl, butyryl, hexanoyl, octanoyl, dodecanoyl or octadecanoyl (stearoyl). Rl can also be e.g. eicosanoyl, docosanoyl, tricontanoyl, acryloyl, methacryloyl, crotonoyl, hexenoyl or octadecenoyl (oleoyl), Rl and R5 as aromatic acyl radicals can be e.g.
benzoyl, naphthoyl, ~henylacetyl, phenylpropionyl, naphthylacetyl, toluyl, dimethylbenzoyl, 4-butylbenzoyl, 4-octylbenzoyl or 4-dodecylbenzoyl Preferred compounds of the formula Ia or Ib are those wherein is C2 C12alkan6oyl~7C3-Csalkenoyl~ phenylacetyl~ -CH CN
or -CO-N(R )(R );
R2 is hydrogen;
each of R3 and R4 independently of the other is hydrogen, Cl-C12-alkyl, C7-C12aralkyl or phenyl substituted by Cl-C4-alkyl, or R3 and R4, together with the carbon atom to which they are attached, form a cycloalkane or alkylcycloalkane ring containing 5 to 12 carbon atoms or a group of the formula .~./ 3 C,~3\CH3 R5, when n is 1, is Cl-C18alkyl, C3-C6alkenyl, ~5-C6cyclo-alkyl, C7-C12aralkyl, C2-C12alkanoyl or C3-C12-alkenoyl, and when n is 2, is ~2-C]8alkylenes C4-C12al~enylene or xylylene;
R is hydrogen, Cl-C12alkyl, C5-C6cycloalkyl, C7-C12aralkyl or phenyl;
R7 is C -C12alkyl, C5-C66ycloal7yl, C7 12 C6-ClOaryl, or R and R , together with the nitrogen atom to which they are attached, form a 5- to 7-mem~ered ring; and R8 is hydrogen, Cl-C6alkylg C3-C5alkenyL, benzyl, C2-C12-alkanoyl, C3-C12alkenoyl, propargyl or cyanomethyl.
Particularly preferred are compounds of the formula Ia, wherein n is l; Rl is C2-C12alkanoyl, C3-C5alkenoyl, -Co-N(R6)(R7~ or -CH2CN; R2 is hydrogen; each of R3 and R4 independently of the other is hydrogen, Cl~C4alkyl, benzyl or phenyl, or R3 and R4, together with the carbon atom to which they are attached, form a C5-C12cycloal~ane ring;
R5 is Cl-C6alkyl, C3-C5alkenyl, benzyl, C2-C12alkanoyl or C3-C5alkenoyl; R6 is hydrogen, Cl-C6alkyl, cyclohexyl, benzyl or phenyl; and R is Cl-C6alkyl, cyclohexyl, benzyl or phenyl; or R6 and R7, together with the nitrogen atom to which they are attached, form a 5- to 7-membered ring.
Examples of compounds of the formula Ia, wherein n is 1, are:
8-acetyl-2,2,7,7,9,9-hexamethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5~decane, 8-acryloyl-2,2,7,7,9,9-hexamethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]-decane, 3-methacryloyl-2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15-oxo-dispiro[5.1.5.2]pentadecane, 3-acryloyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, ~1~8~37 8-acryloyl-2~2,7,7,9,9-hexamethyl-3 benzyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, 8-acryloyl-7,7,9,9-tetramethyl-3-octadecyl-2,2-diethyl-1-oxa-398-diaza-4-oxo-spiro[4,5]decaneg~
3-acetyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 3-acryloyl-2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 3,20-diheptadecanoyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 3-acetyl-2~2,4,4-tetramethyl-20-benzyl-7-oxa-3;20-diaza-21-oxo-dispiro~5.1.11.2]heneicosane, 3-(N,N-diethyl)-carbamoyl-2,2,4,4-tetramethyl-7-oxa-3920-diaza-21-oxo-dispiro[5.1.11.2]h~neicosane, 3-(N,N-dioctyl)-carbamoyl-2,2,4,4-tetramethyl-20-octadecyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 3-phenylcarbamoyl-2,2,4,4-tetramethyl-20-octadecyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11 2]heneicosane, 8-cyclohexylcarbamoyl-2,2,7,7,9,9-hexamethyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane.
Examples of compounds of the formula Ia, wherein n is
Case 3-13598/S/=
N-Substituted polyalkylpiperidine-4-spirooxazolidones The invention relates to novel polyalkylpiperidine-4-spirooxalidones and to their use as stabilisers for organic polymers, in particular against the action of light, as well as to the so stabilised polymers.
In German Offenlegungsschrift specifications 26 06 026, 28 34 962 and 29 33 732, and in European patent application 17 617, there have already been disclosed polyalkylpiperidine-4-spirooxazolidones of the formulae A and B
R~i R R R"
y X- N/ .~i (A) Y (B~
as light stabilisers for organic polymers, wherein R is alkyl, R' is hydrogen or alkyl, R" is a monovalen~ hydro-carbon radical, X is hydrogen, oxygen, OH or an unsubstituted or substituted hydrocarbon radical, and Y
is hydrogen or a hydrocarbon radical. All these compounds have a basic nitrogen atom in the piperidine ring and are therefore basic compounds which can form salts with acids.
~98437 For ~pecific fields of use the basicity of these compounds can be a drawback, for example for acid catalysed lacquers or for electrostatically or electrophoretically applied lacquers. There was accordingly a need for non-basic polyalkylpiperidine-4-spirooxazolidones for such special fields of use.
It has been found that those compounds of the formulae A and B are suitable for such use in which X is an acyl, carbamoyl or cyanomethyl group. Accordingly, the invention provides compounds of the formula Ia or Ib \2/CH3~R i ~2 CH3 1 4 _; O ~ n R5 -- /O I-R LR
(Ia) (Ib) wherein n is 1 or 2;
Rl is C2-C30alkanoyl, C3-C20alkenoyl, -CH2CN, -Co-N(R6)(R7), C royl C8-C14arylalkanoyl or C8 20 R is hydrogen or Cl-C4alkyl; each of R3 and R4 independently of the other is hydrogen, Cl-C~Oalkyl, unsubstituted or chlorine- or alkyl-substituted C6-ClOaryl, unsubstituted or alkyl-substituted C7-C~laralkyl, or R3 and R4, together with the carbon atom to which they are attached, form a cycloalkane or alkylcycloalkane ring containing 5 to 18 carbon atoms,or a group of the formula ~i ~ ~1 ~8437 .
R , when n is 1, is Cl-C30alkyl, C3-C20alkenyl, unsubsti-tuted or alkyl-substituted C7-Cllaralkyl, or is c5-cl2cycloalkyl, c2-cl8alkanoyl, C3~C18alkenY
C aroyl ~ -C14arylalkanoyl or C8 C20 or ~5 when n is 2, is C2-C30alkylene, C2-C30a y C8-C18arylenedialkylene;
R is hydrogen, Cl-C18alkyl, C5-C8cycloalkyl, C7-C15aralkyl or c6-ClOaryl;
R7 is Cl-C18alkyl, C5-C8cycloalkyl, C7-C15aralkyl or 6 C67CloarYl; or R and R , together with the nitrogen atom, form a 5- to 7-membered ring which can be interrupted by further hetero-atoms, and R8 is hydrogen, Cl-C12alkyl, C3-C5a:Lkenyl, C3-C5alkynyl, unsubstituted or alkyl-substituted C7-Cllaralkyl, C2-cl8alkanoyl~ c3-C18alkenoyl, -CH2CN or -co-N(R6)(~7~.
R , R3, R4, R5, R6, R7 and R8 can be unbranched or branched alkyl. Within the scope of the defined number of carbon atoms, examples of such alkyl groups are methyl, ethyl, isopropyl, sec-butyl, tert-butyl, hexyl, octyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, docosyl or triacontyl.
'a37 .
Within the scope of the defined number of carbon atoms, R5 and R as a~enyl can be e g. allyl, methallyl, 3,3-dimethylallyl, 1-buten-4-yl, 2-hepten-1-yl or oleyl.
R8 as alkynyl can De e.g. propargyl, butynyl or pentynyl.
R5, R and R7 as cycloalkyl can be e.g. cyclopentyl, cyclohexyl or cyclooctyl. R5 can also be e.g. methylcyclo-hexyl, dimethylcyclopentyl or cyclododecyl.
R3, R4, R6 and R7 as aryl can be phenyl or naphthyl, and R3 and R4 can also be e,g. chloroaryl or alkyl-substi~
tuted aryl, in particular phenyl substituted by Cl-C4alkyl.
Examples of such groups are chlorophenyl, chloronaphthyl, mono- or dimethylphenyl, nonylphenyl or dodecylphenyl.
R3, R4, R5, R6, R and R8 as aralkyl can be e.g.
phenylethyl, phenylisopropyl and, in particular, benzyl.
Examples of R3, R4, R5 and R8 as alkylated aralkyl are methylnaphthylmethyl, octylbenzyl, nonylbenzyl, dodecyl-benzyl and, in partic~lar, benzyl substituted by Cl-C4alkyl, e.g. methylbenzyl, isopropylbenzyl or tert-butylbenzyl.
A cycloal~ane ring formed by R3 and R4 together with the carbon atom to which they are attached can be e.g~ a cyclohexane, cyclooctane or cyclododecane ring.
A 5- to 7-membered ring ~ormed by R6 and R7, together with the nitrogen atom to which they are attached, can be e.g. a pyrrolidine, piperidine, morpholine or piperazine ring.
R as alkylene can be unbranched or branched alkylene, e.g. ethylene, hexamethylene, octamethylene, dodecylmethylene, 1,2-propylene or 2,2-dimethylpropylene-1~8~37 1,3. R5 as alkylene can be e.g. 2-butylene-1,4 or 2,3-dimethyl-2-butenylene-1,4. R5 as arylene-dialkylene can be e.g. phenylenediethylene or naphthylenPdimethylene, and~
in particular m- or p-xylylene.
Rl, R5 and R as aliphatic acyl radical~ can be e.g.
acPtyl, propionyl, butyryl, hexanoyl, octanoyl, dodecanoyl or octadecanoyl (stearoyl). Rl can also be e.g. eicosanoyl, docosanoyl, tricontanoyl, acryloyl, methacryloyl, crotonoyl, hexenoyl or octadecenoyl (oleoyl), Rl and R5 as aromatic acyl radicals can be e.g.
benzoyl, naphthoyl, ~henylacetyl, phenylpropionyl, naphthylacetyl, toluyl, dimethylbenzoyl, 4-butylbenzoyl, 4-octylbenzoyl or 4-dodecylbenzoyl Preferred compounds of the formula Ia or Ib are those wherein is C2 C12alkan6oyl~7C3-Csalkenoyl~ phenylacetyl~ -CH CN
or -CO-N(R )(R );
R2 is hydrogen;
each of R3 and R4 independently of the other is hydrogen, Cl-C12-alkyl, C7-C12aralkyl or phenyl substituted by Cl-C4-alkyl, or R3 and R4, together with the carbon atom to which they are attached, form a cycloalkane or alkylcycloalkane ring containing 5 to 12 carbon atoms or a group of the formula .~./ 3 C,~3\CH3 R5, when n is 1, is Cl-C18alkyl, C3-C6alkenyl, ~5-C6cyclo-alkyl, C7-C12aralkyl, C2-C12alkanoyl or C3-C12-alkenoyl, and when n is 2, is ~2-C]8alkylenes C4-C12al~enylene or xylylene;
R is hydrogen, Cl-C12alkyl, C5-C6cycloalkyl, C7-C12aralkyl or phenyl;
R7 is C -C12alkyl, C5-C66ycloal7yl, C7 12 C6-ClOaryl, or R and R , together with the nitrogen atom to which they are attached, form a 5- to 7-mem~ered ring; and R8 is hydrogen, Cl-C6alkylg C3-C5alkenyL, benzyl, C2-C12-alkanoyl, C3-C12alkenoyl, propargyl or cyanomethyl.
Particularly preferred are compounds of the formula Ia, wherein n is l; Rl is C2-C12alkanoyl, C3-C5alkenoyl, -Co-N(R6)(R7~ or -CH2CN; R2 is hydrogen; each of R3 and R4 independently of the other is hydrogen, Cl~C4alkyl, benzyl or phenyl, or R3 and R4, together with the carbon atom to which they are attached, form a C5-C12cycloal~ane ring;
R5 is Cl-C6alkyl, C3-C5alkenyl, benzyl, C2-C12alkanoyl or C3-C5alkenoyl; R6 is hydrogen, Cl-C6alkyl, cyclohexyl, benzyl or phenyl; and R is Cl-C6alkyl, cyclohexyl, benzyl or phenyl; or R6 and R7, together with the nitrogen atom to which they are attached, form a 5- to 7-membered ring.
Examples of compounds of the formula Ia, wherein n is 1, are:
8-acetyl-2,2,7,7,9,9-hexamethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5~decane, 8-acryloyl-2,2,7,7,9,9-hexamethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]-decane, 3-methacryloyl-2,2,4,4-tetramethyl-7-oxa-3,14-diaza-15-oxo-dispiro[5.1.5.2]pentadecane, 3-acryloyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, ~1~8~37 8-acryloyl-2~2,7,7,9,9-hexamethyl-3 benzyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, 8-acryloyl-7,7,9,9-tetramethyl-3-octadecyl-2,2-diethyl-1-oxa-398-diaza-4-oxo-spiro[4,5]decaneg~
3-acetyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 3-acryloyl-2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 3,20-diheptadecanoyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 3-acetyl-2~2,4,4-tetramethyl-20-benzyl-7-oxa-3;20-diaza-21-oxo-dispiro~5.1.11.2]heneicosane, 3-(N,N-diethyl)-carbamoyl-2,2,4,4-tetramethyl-7-oxa-3920-diaza-21-oxo-dispiro[5.1.11.2]h~neicosane, 3-(N,N-dioctyl)-carbamoyl-2,2,4,4-tetramethyl-20-octadecyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 3-phenylcarbamoyl-2,2,4,4-tetramethyl-20-octadecyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11 2]heneicosane, 8-cyclohexylcarbamoyl-2,2,7,7,9,9-hexamethyl-3-hexyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane.
Examples of compounds of the formula Ia, wherein n is
2, are:
CH C \ / ~ ~ 3~ ca /c~3 C~3 cu3 ~ c 2 \.=./ ~ c~ \C~I
CH3-C-~) ( ~ C~ CH3 ~84~3~
~]X 3 (~H~)11~3~ \./
C~ CH3 Y, \ / ~ C~ \CH
CH -CH=CI-l-cH2 e ~ / . 3 0 ~3~ 3 C~H ) ( C~ ~3~ 3 0 CH2=CH-C ~ ,L, ` ~ 2
CH C \ / ~ ~ 3~ ca /c~3 C~3 cu3 ~ c 2 \.=./ ~ c~ \C~I
CH3-C-~) ( ~ C~ CH3 ~84~3~
~]X 3 (~H~)11~3~ \./
C~ CH3 Y, \ / ~ C~ \CH
CH -CH=CI-l-cH2 e ~ / . 3 0 ~3~ 3 C~H ) ( C~ ~3~ 3 0 CH2=CH-C ~ ,L, ` ~ 2
3 3 0 CH2--~ ~--CH2 ~ \CH
Examples of compounds of the formula Ib, wherein n is 1, are:
8-acetyl-2,2,4,7,7,9,9-heptamethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5~decane, 8-acetyl-2,2,7,7,9,9-hexamethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5]decane, 8-acetyl-7,7,9,9-tetramethyl-2-cyclohexyl-4-allyl-1-oxa-
Examples of compounds of the formula Ib, wherein n is 1, are:
8-acetyl-2,2,4,7,7,9,9-heptamethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5~decane, 8-acetyl-2,2,7,7,9,9-hexamethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5]decane, 8-acetyl-7,7,9,9-tetramethyl-2-cyclohexyl-4-allyl-1-oxa-
4,8-diaza-3-oxo- spiro [ 4 . 5]decane, 8-benzylcarbonyl-7,7,9,9-tetramethyl-2,2-dibenzyl-1-oxa-4,8-diaza-3-oxo-spiro L4. 5]decane, 8-decanoyl-2,2,7,7,9,9-hexamethyl-1-oxa-4,8-diaza-3-oxo-spiro [4~5~decane, 8-methacryloyl-2~2,4,7,7,9,9-heptamethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5]decane, ~9~37 8-acetyl-2,2,7,7,9,9-hexamethyl-4-benzyl-1-oxa-4,8-diaza-3-oxo-spiro[4.~]decane, 8-acryloyl-2,2,7,7,9,9-hexamethyl-1-oxa-4,8-diaza-3-oxo-spiro~4.5]decane, 8-[N,N-dibutyl]-carbamoyl-2,2,7,7,9,9-hexamethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5~decane, 4,8-bisacryloyl-2,2,7,7,9,9-hexamethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5]decane, 3-acetyl-2,2,4,4-tetramethyl-7-oxa-3,21-diaza-20-oxo-dispiro-[5.1.11.2]heneicosane, 3,21-diacetyl-2,2,4,4-tetramethyl-7-oxa-3,21-diaza-20-oxo-dispiro[5.1.11.2]heneicosane, 3-acryloyl-2,2,4,4-tetramethyl-7-oxa-3,21-diaza-20-oxo-dispiro[5.1.11.2]heneicosane, 3-~N,N-diethyl]-carbamoyl-2,2,4,4-tetramethyl-7-oxa-3,21-diaza-20-oxo-dispiro[5.1.11.2]heneicosane.
Examples of compounds of t~e formula Ib, wherein n is 2, are:
. . ~ 3 CH3 CH3 1 ~ 3 3 2 \.=.~ CH2 Il \-/-~ ~O - ~ 2)11 ( ~ ~3~ 3 0 CH2=CH-c - ~. ./ ~ ! ! \._.~ 2 CH3 CH3 \ ~0 ~ ~ 3 3 CH2 - CH = C~l C~2 - 10 ~
~ NH-~- < ~ 2)11 l CH2~CH2-CH
The compounds of the formula Ia can be prepared from the corresponding compounds of the formula IIa ~n R5 lla by substitution at the piperidine-nitrogen. Suitable methods are those generally employed for the N-acylation of secondary amines. Alkanoyl, alkenoyl, aroyl, aryl-alkanoyl and alkylaroyl radicals can be introduced by reaction with the corresponding carboxylic acid chlorides R Cl, in the presence of a proton acceptor, or with the carboxylic acid anhydrides (Rl)20. A carbamoyl radical -Co-N(R6)(R7) can be introduced by the stepwise reaction of IIa with a) phosgene and b) an amine R6-NH-R7, or by reaction with a carbamoyl chloride (R6)(R )N-CO-Cl.
Carbamoyl radicals, in which R6 is hydrogen, are obtained from IIa by reaction with an isocyanate R -NCO.
34~7 If a start is made from a compound IIa in which R
is hydrogen, then both nitrogen atoms can also be subs~i-tuted simultaneously in these acylation reactions to give compounds of the formula Ia, wherein R5 has the same meaning as Rl.
The introduction of a cyanomethyl radical as R can be effected by reaction of IIa with formaldehyde and hydrogen cyanide or formaldehyde and an alkali cyanideO
The compounds of the formula Ib can be prepared in analogous manner from he compounds of the formula IIb ~ R5 IIb by substitution at the piperidine-nitrogen.
Compounds of the formulaeIIa and IIb are known compounds. Their preparation is described e.g. in German Offenlegungsschrift specifications 26 06 026, 28 34 962 and 29 33 732, or can be erfected in analogous manner.
The compounds of formulae Ia and Ib are suitable as stabilisers for organic polymers against the action of light, heat and oxygen and have, in particular, an outstanding light stabilising action.
~ 3 Examples of such polymers are:
1. Polymers of mono- and diole~ins, for example polyethylene (which can be crosslinked), polypropylene, polyisobutylene, polybut~l-ene, polymethylpent-l-ene, polyisoprene or polybutadiene, and polymers of cycloolefins, e.g. of cyclopentene or norbornene.
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyethylene or with polyisobutylene.
3. Copolymers of mono- and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, propylene/but-l-ene copolymers, propylene/iso-butylene copolymers, ethylene/but-l-ene copolymers, propylene/
butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkylacrylate copolymers, ethylene/alkylmethacrylate copolymers, ethylene/v-nyl acetate copolymers, or ~thylene/
acrylic acid copolymers and salts thereof (ionomers), and also terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene.
4. Polystyrene.
S. Copolymers of styrene or ~-methylstyrene with dienes or acrylic derivatives, fGr example styrene/buta-diene, styrene/acrylonitrile, styrene/alkylmethacrylate, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength obtained from styrene copolymers and another polymer, ~or example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and also bl~c~ copolymers of styrene, for example styrene/
butadiene/styrene, styrene/isoprene/styrene, styrene/
ethylene-butylene/styrene, or styrene-ethyl~ne/propylene-styrene, 6. Graft copolymers of styrene, e~g. styrene with polybutadiene, styrene and acrylonitrile with polybutadiene, styrene and maleic anhydride with polybutadiene, styrene and alkyl acrylates or alkyl methacrylates with polybutadiene, styrene and acrylonitrile with ethylene-propylene-diene terpolymers, styrene and acrylonitrile with polyalkyl-acrylates or polyalkylmethacrylates, styrene and acrylo-nitrile with acrylate-butadiene copolymers, and mixtures thereof with the copolymers listed under 5), known e.g. as ABS, MBS, ASA or AES polymers.
7. Halogen-containing polymers, e.g. polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated poly-ethylene, especially polymers of halogenated vinyl compounds, e.~. polyvinyl chloride, polyvinylidene chLoride, polyvinyl fluoride, polyvinylidene fluoride, and their copolymers such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate.
8. Polymers which are derived from ~,~-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles.
9. Copolymers of the ~onomers listed in 8) with one another or with other unsaturated monomers, e.g. acrylo-nitrile/butadiene copolymers, acrylonit ile/alkyl acrylate copolymers, acrylonitrile/vinyl chloride copolymers, or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
10. Polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, 8~
such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleat~, polyvinyl-butyral, polyallyl phthalate, polyallylmelamine.
11. Homopolymers and copolymers of cyclic ethers such as polyethylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bis-glycidyl ethers.
12. Polyac~tals such as polyoxymethylene, and also those polyoxymethylenes w~ich contain a comonomer, e,g. ethylene oxide.
13. Polyphenylene oxides and sulfides.
14. Polyurethanes which are derived on the one hand from polyethers, polyesters and polybutadienes containing hydroxyl end groups, and from aliphatic or aromatic polyisocyanates on the other, as well as their precursors (polyisocyanates, polyols, prepolymers).
15. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, poly-2,4,4-trimethylhexamethyleneterephthal-amide, poly~m-pheny~ene-isophthalamide, and their copolymers with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
16. Polyureas, polyamides and polyamide imides.
17. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene tere-~L~9~437 phthalate, polybutylene terephthalate and poly-1,4-dimethylolcyclohexane terephthalate, poly-[2,2 bis(4-hydroxy-phenyl)propane~-terephthalate, polyhydroxybenzoates, and also block polyether esters which are derived from polyethers having hydroxyl end groups, dialcohols and dicarboxylic acids.
18. Polycarbonates.
19. Polysulfones and polyether sulfones.
20. Crosslinked polymers which are derived from alde-hydes on the one hand and from phenols, ureas and melamines on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.
Zl. Drying and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from copolyesters of saturated and un~aturated dicarboxy-lic acids with polyhydric aclcohols and vinyl compounds as crosslinking agents, and also their halogen-containing flame-resistant modifications.
23. Crosslinkable acrylic resins which are derived from substituted acrylic esters, e.g, from epoxy acrylates, urethane acrylates or polyester acrylates.
24. Alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins~
polyisocyanates or epoxy resins.
25. Crosslinked epoxy resins which are derived from polyepoxides, e.g. bis-glycidyl ethers, or from cyclo-aliphatic diepoxides.
Z6. Naturally occurring polymers, such as ce~ulose,na~ral rubber and gelatin, and also the chemically modified homo-logous derivatives thereof, such as cellulose acetates~
cellulose propionates and cellulose butyrates, and cellulose ethers such as methylcellulose.
Of particular importance is the stabilising of lacquers such as alkyd, acrylic and polyester lacquers .?
in particular the stabilising of acid catalysed stoving lacquers.
The stabilisers of this invention are incorporated in the polymers in a concentration o~ 0.01 to 5% by weight, based on the material to be stabilised. Preferably 0.1 to 2% by weight of the compounds, based on the material to be stabilised, is incorporated thereinto.
Incorporation can be effected after polymerisation, for e~ample by blending the compounds and, if desired, further additives, into the melt by methods conventionally employed in the art, before or during the manufacture of shaped articles therefrom, or also by applying the dissolved or dispersed compounds to the polymer, with or without subsequent evaporation of the solvent.
The stabilisers can also be added in the form of a master batch which contains these compounds, for example in a concentration of 2.5 to 25% by weight, to the polymers to be stabilised.
In addition to the compounds of the formulae Ia and Ib, still further known stabilisers can also be incorporated in the polymers. These stabilisers can be e.g.
antioxidants, light stabilisers or metal deactivators, or also costabilisers, for example thos of the phosphite type. Furthermore, other additives customary in plastics technology, for example flame retardants, antistatic agents, plasticisers, lubricants, blowing agents, pigments, reinforcinv materials or fillers, can also be added.
When known stabilisers are used concurr~ntly, synergistic effects can be obtained. This frequently happens especially when other light stabilisers or organic phosphites are used concurrently. The concurrent use of antioxidants when stabilising polyolefins is of particular importance.
The invention therefore also relates to the plas-tics stabilised by the addition of 0.1 to 5% by weight of a compound of the formula I, which plastics, if desired, can also contain other known and customary additives. The stabilised plastics can be used in very diverse forms, for example as films, fibres, ribbons or profiles, but especially as binders for lacquers.
The manufacture and use of the compounds of the invention is described in more detail in the following Examples. Parts and percentages are by weight.
Example 1: 51 g (0.14 mole) of 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2~heneicosane in 400 ml of acetic anhydride and 4 ml of dimethyl formamide are heated for 22 hours to 110-115C. With stirring, the reaction mixture is then cooled to room temperature and filtered.
The filtrate is worked up as described hereinbelow. The crystalline precipitate is recrystallised from dimethyl formamide, washed with water and then with acetone and vacuum dried, affording 3-acetyl-2,2,4,4-tetramethyl-7-oxa-3720-diaza-21-oxo-dispiro~5.1.11.2]heneicosane of the formula C\3/C~3 (/~ 72) 11 /4 5\ /~
\ .2 _ ./ \ 21 1H
which melts at 234-236C (stabiliser 1).
Analysis C24H42N203 calc.: c 70.89 H 10.41 N 6.~9%
(406 . 61 ) found: c 70 . 6 H 10 .5 N 7 .0 %
The acetic anhydride fîltrate obtained above is evaporated to dryness in vacuo. The residue, which crystallises after a short time, is recrystallised twice from acetonitrile, affording pure 3,20-diacetyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane of the formula -( ()2) CH CO 1~
which melts at 183-185C.
Y 26 44 2 4 calc,: C 69.60 H 9.88N 6.24%
(448.65) found: 69.6 9.8 6~4 %
The mono- and diacetyl compounds can be readily identified by thin-layer chromatography and show the expected signals in the lH-NMR spectrum.
Example 2. 27.3 g of 2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diaza-21-oxa-dispiro[5.1.11.2]heneicosane are dissolved in 130 ml of toluene. After addition of 5.4 g of paraform-aldehyde the contents of the flask are heated to 85C.
Hydrocyanic acid is then introduced at this temperature over about l~ hours into the reaction mixture (a total of 8.2 g), which is subsequently stirred for 12 hours at 85C. Then, still at the same temperature, nitrogen is passed through the yellow solution over 6 hours. The solvent is stripped off in vacuo and the residue is recrystallised from methyl ethyl ketone with the addition of activated carbon, yielding 3-cyanomethyl~2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diazo 21-oxo-dispirol5.1.11.2]heneicosane which melts at 191~192C(stabiliser 2~.
9~437 Analysis C31H47N302 calc-: C 75~41 H 9.60 N 8.51%
(493.7) found: 75.1 9.3 8.4 %
Example 3: 25 g (55mmoles) of 2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diazo-21-oxo-dispiro[5.1.11.2~heneicosane, 9.5 ml of triethylamine and 100 mg of 2,6-di-tert-butyl-4-methyl-phenol are dissolved in 70 ml of chloroform ~nd the solution is cooled to -20C. A solution of 5.23 g (58~,moles) of acryloyl chloride in 10 ml of chloroform is added dropwise at -10 to -12C over about 1 hour to the above solution.
The reaction mixture is then stirred for 4 hours at -10C
and the contents of the flask are diluted with 250 ml of hexane, clarified, and extracted with four 25 ml portions of water. The organic phase is dried over Na2S04 and then concentrated i~ vacuo. Crystallisation of the residue from acetonitrile/methyl ethyl ketone yields 3-acryloyl-2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20~diaza-21-oxo-dispiro[5.1.11.2]-heneicosane with a melting point of 174-176C (stabiliser 3).
Analysis C32H48~203 calc-: C 75.55 H 9.51 N 5.51%
(508.7) found: 75.4 9.3 5.5 %.
In corresponding manner, reaction cf 2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2~heneicosane and diethylcarbamoyl chloride gives 3-diethylcarbamoyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]-heneicosane with a melting point of 99-101C (stabiliser 4).
Analysis C30H53N303 calc.: C 71.53 H 10.60 N 8.34%
(503.8) found: 71.7 10.4 8.1 %.
Example 4- 13.6 g (30 mmoles) of 2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane and 0.03 g of 1,4-diazabicyclo[2.2.2]octane (DABC0) are dissolved in 70 ml of benzene. A solution of 2.97 g (30 mmoles) of butyl isocyanate in 10 ml of benzene is added dropwise at room temperature over about 45 minutes to the above solution and the reaction is allowed to go completion for 24 hours at room temperature. The reaction mixture is concentrated to half of its volume and diluted with diethyl ether. The colourless precipitate is filtered with suction, washed with ethyl ether and dried, affording 3-butyl-carbamoyl-2,2,4,4-tetrame~hyl-20-benzyl-7-oxa-3,20-diaza-21-oxo-dispiro~5.1.11.2~-heneicosane with a melting point of 148-150C (stabiliser 5).
Analysis C34H55N303 calc.: C 73.74 H 10.~1 N 7.59%
(553.8) found: 73.3 10.0 7.9%
The following compounds are obtained in the same manner from the corresponding starting materials:
3-cyclohexylcarbamoyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane with a melting point of 140-142C (s~abiliser 6), 3-phenylcarbamoyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane with a melting point of 124-127C (stabiliser 7).
Example 5: 19,6 g of 2,2,4,4-tetramethyl-20-allyl-7-oxa-3920-diaza-21-oxo-dispiro[5.1.11.2]heneicosane and 80 ml of acetic anhydride are stirred for 24 hours at 90-95C. Excess anhydride and the acetic acid formed are distilled off in vacuo as completely as possible. The crystalline residue is recrystallised from acetonitrile affording 3-acetyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro~5.1.11.2]-heneicosane with a melting point of 113-114C (stabiliser 8).
Analysis C27 46 2 3 C 72.6 H 10.38 N 6.27%
(446.8~ found: 72.5 10.2 6.4 1~9~3~37 The following compounds are obtained in similar manner from the corresponding starting materials:
3-acetyl-2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diaza-21-oxo-dispiro~5.1.11.2]heneicosane with a melting point of 128-129C (stabiliser 9), 3-acetyl-2,2,4,4-tetramethyl-20-butylcarbamoyl-7-oxa-3,20-diaæa-21-oxo-dispiro[5.1.11.2~heneicosane with a melting point of 176-178C (stabiliser 10), 3-acetyl-2,2,4,4-tetramethyl-20-hexyl-7-oxa-3,20-diaza-21-oxo-dispirol5.1.11.2]heneicosane with a melting point of 89-91C (stabiliser 11), 1,4-bis(3-acetyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2~heneicosyl-20)-but-2-ene with a melting point of 156-158C (stabiliser 12).
Example 6: A solution of 2.48 g of phosgene is stirred dropwise at 0C over 1 hour into a solution of 20.2 g of 2,2,4,4-tetramethyl-20-allYl-7-oxa-3,20-diaza-21-oxo-dispiro-[5.1.11.2~heneicosane in 120 ml of ethyl acetate. Stirring is continued for 16 hours at room temperature and then a solution of 1.5 g of ethanol and 2.5 g of triethylamine in 10 ml of ethyl acetate is added dropwise. After stirring for 8 hours the reaction mixture is filtered and the filtrate is washed twice with water, three times with ice-cold n-HCl and again with water, dried over Na2S04 and concentrated in vacuo.
The residual crude product is purified by chromatography over a silica gel column with a 3:2 mixture of diethyl ether/
hexane as eluant, and recrystallised from pentane. The pure 3-ethoxycarbonyl-2,2,4,4-tetramethyl-20-allyl-7~oxa-3,20-diaza-21-oxo-dispiro~5.1.11.2]heneicosane has a melting point of 81-82C (stabiliser 13).
~ 3 - 23 ~
~nalysis C28H48N204 calc.: C 70.55 H 10.15 N 5.88%
(476.7) found: 70.8 10.0 6.0 %.
The 1H-NMR spectrum is in accord with the indicated structure.
Exam~le 7: Stabilisation of polypropylene against 1 gh-t 100 parts of polypropylene powder (Moplen, ~ibre grade, manufactured by Montedison), 0.2 part of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid octadecyl ester, 0.1 part of calcium stearate and 0.25 part of a stabiliser of Table 1 are homogenised in a Brabender plastograph for 10 minutes at 200C. The resultant plastic mass is removed from the kneader as quickly as possible and pressed to a 2-3 mm sheet in a toggle press. A portion of the sheet is cut out and pressed between two ultra-gloss rigid aluminium sheets with a hand-operated hydraulic laboratory press for 6 minutes at 260 to a 0.1 mm sheet, which is immediately chilled in cold water. Segments are then punched out of this sheet and exposed in the xeno~est 1200. These samples are taken out of the exposureapparatus at regular intervals and examined for their carbonyl content in a IR spectrophotometer. The increase in the carbonyl extinction at 5.85 ~ during exposure is a reference value for the degradation of the polymer by photooxidation [see L. Balaban et al., J. Polymer Sci., Part Ci 22, 1059-1071 (1969)] and, as experience shows, is associated with a decrease in the mechanical properties of the polymer. The time taken till a carbonyl extinction of about 0.3 is reached, at which value the comparison sheet is brittle, serves as an indication of the protective action.
Table I
,Stabiliser exp..u.. ti n~ in: ~rs 2 > 2100 3 > 2200 4 > 2200 > 1600 6 >2200 7 > 1700 8 > 2200 9 ~ 2200 > 1700 without 880 -xample 8: Stabilisation of a two-coat metallic stoving lacquer Recipe for the priming lacquer 27 parts of polyester resin (L 1850, available from Dynamit Nobel AG), 3 parts of melamine resin (Maprenal RT, available from Hoechst AG), 2 parts of cellulose acetobutyrate (CAB 531, available from Eastman Chem. Corp.), 3 parts of aluminium bronze (ALCOA 726, available Erom the Aluminium Corp. of America), 10 parts of toluene, 7 parts o xylene, 3 parts of butanol, 25 parts of butyl acetate and 15 parts of a mixture of aromatic solvents (Solvesso ~ 150, available f-com ESSO AG).
~:~98~37 - 2s -Recipe for the finishin~ lacquer 58.3 parts of acrylic resin (Viacryl ~J VC 373~ available from Vianova AG), 27.3 parts of melamin~ resin (M~prenal ~ MF 590, available from Hoechst AG), 1.0 part of a 1% solution of a silicone oil in xylene 4.0 parts of a mixture of aromatic solvents (Solvesso ~ , available from ESS0 AG),
Examples of compounds of t~e formula Ib, wherein n is 2, are:
. . ~ 3 CH3 CH3 1 ~ 3 3 2 \.=.~ CH2 Il \-/-~ ~O - ~ 2)11 ( ~ ~3~ 3 0 CH2=CH-c - ~. ./ ~ ! ! \._.~ 2 CH3 CH3 \ ~0 ~ ~ 3 3 CH2 - CH = C~l C~2 - 10 ~
~ NH-~- < ~ 2)11 l CH2~CH2-CH
The compounds of the formula Ia can be prepared from the corresponding compounds of the formula IIa ~n R5 lla by substitution at the piperidine-nitrogen. Suitable methods are those generally employed for the N-acylation of secondary amines. Alkanoyl, alkenoyl, aroyl, aryl-alkanoyl and alkylaroyl radicals can be introduced by reaction with the corresponding carboxylic acid chlorides R Cl, in the presence of a proton acceptor, or with the carboxylic acid anhydrides (Rl)20. A carbamoyl radical -Co-N(R6)(R7) can be introduced by the stepwise reaction of IIa with a) phosgene and b) an amine R6-NH-R7, or by reaction with a carbamoyl chloride (R6)(R )N-CO-Cl.
Carbamoyl radicals, in which R6 is hydrogen, are obtained from IIa by reaction with an isocyanate R -NCO.
34~7 If a start is made from a compound IIa in which R
is hydrogen, then both nitrogen atoms can also be subs~i-tuted simultaneously in these acylation reactions to give compounds of the formula Ia, wherein R5 has the same meaning as Rl.
The introduction of a cyanomethyl radical as R can be effected by reaction of IIa with formaldehyde and hydrogen cyanide or formaldehyde and an alkali cyanideO
The compounds of the formula Ib can be prepared in analogous manner from he compounds of the formula IIb ~ R5 IIb by substitution at the piperidine-nitrogen.
Compounds of the formulaeIIa and IIb are known compounds. Their preparation is described e.g. in German Offenlegungsschrift specifications 26 06 026, 28 34 962 and 29 33 732, or can be erfected in analogous manner.
The compounds of formulae Ia and Ib are suitable as stabilisers for organic polymers against the action of light, heat and oxygen and have, in particular, an outstanding light stabilising action.
~ 3 Examples of such polymers are:
1. Polymers of mono- and diole~ins, for example polyethylene (which can be crosslinked), polypropylene, polyisobutylene, polybut~l-ene, polymethylpent-l-ene, polyisoprene or polybutadiene, and polymers of cycloolefins, e.g. of cyclopentene or norbornene.
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyethylene or with polyisobutylene.
3. Copolymers of mono- and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, propylene/but-l-ene copolymers, propylene/iso-butylene copolymers, ethylene/but-l-ene copolymers, propylene/
butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkylacrylate copolymers, ethylene/alkylmethacrylate copolymers, ethylene/v-nyl acetate copolymers, or ~thylene/
acrylic acid copolymers and salts thereof (ionomers), and also terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene.
4. Polystyrene.
S. Copolymers of styrene or ~-methylstyrene with dienes or acrylic derivatives, fGr example styrene/buta-diene, styrene/acrylonitrile, styrene/alkylmethacrylate, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength obtained from styrene copolymers and another polymer, ~or example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and also bl~c~ copolymers of styrene, for example styrene/
butadiene/styrene, styrene/isoprene/styrene, styrene/
ethylene-butylene/styrene, or styrene-ethyl~ne/propylene-styrene, 6. Graft copolymers of styrene, e~g. styrene with polybutadiene, styrene and acrylonitrile with polybutadiene, styrene and maleic anhydride with polybutadiene, styrene and alkyl acrylates or alkyl methacrylates with polybutadiene, styrene and acrylonitrile with ethylene-propylene-diene terpolymers, styrene and acrylonitrile with polyalkyl-acrylates or polyalkylmethacrylates, styrene and acrylo-nitrile with acrylate-butadiene copolymers, and mixtures thereof with the copolymers listed under 5), known e.g. as ABS, MBS, ASA or AES polymers.
7. Halogen-containing polymers, e.g. polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated poly-ethylene, especially polymers of halogenated vinyl compounds, e.~. polyvinyl chloride, polyvinylidene chLoride, polyvinyl fluoride, polyvinylidene fluoride, and their copolymers such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate.
8. Polymers which are derived from ~,~-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles.
9. Copolymers of the ~onomers listed in 8) with one another or with other unsaturated monomers, e.g. acrylo-nitrile/butadiene copolymers, acrylonit ile/alkyl acrylate copolymers, acrylonitrile/vinyl chloride copolymers, or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
10. Polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, 8~
such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleat~, polyvinyl-butyral, polyallyl phthalate, polyallylmelamine.
11. Homopolymers and copolymers of cyclic ethers such as polyethylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bis-glycidyl ethers.
12. Polyac~tals such as polyoxymethylene, and also those polyoxymethylenes w~ich contain a comonomer, e,g. ethylene oxide.
13. Polyphenylene oxides and sulfides.
14. Polyurethanes which are derived on the one hand from polyethers, polyesters and polybutadienes containing hydroxyl end groups, and from aliphatic or aromatic polyisocyanates on the other, as well as their precursors (polyisocyanates, polyols, prepolymers).
15. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, poly-2,4,4-trimethylhexamethyleneterephthal-amide, poly~m-pheny~ene-isophthalamide, and their copolymers with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
16. Polyureas, polyamides and polyamide imides.
17. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene tere-~L~9~437 phthalate, polybutylene terephthalate and poly-1,4-dimethylolcyclohexane terephthalate, poly-[2,2 bis(4-hydroxy-phenyl)propane~-terephthalate, polyhydroxybenzoates, and also block polyether esters which are derived from polyethers having hydroxyl end groups, dialcohols and dicarboxylic acids.
18. Polycarbonates.
19. Polysulfones and polyether sulfones.
20. Crosslinked polymers which are derived from alde-hydes on the one hand and from phenols, ureas and melamines on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.
Zl. Drying and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from copolyesters of saturated and un~aturated dicarboxy-lic acids with polyhydric aclcohols and vinyl compounds as crosslinking agents, and also their halogen-containing flame-resistant modifications.
23. Crosslinkable acrylic resins which are derived from substituted acrylic esters, e.g, from epoxy acrylates, urethane acrylates or polyester acrylates.
24. Alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins~
polyisocyanates or epoxy resins.
25. Crosslinked epoxy resins which are derived from polyepoxides, e.g. bis-glycidyl ethers, or from cyclo-aliphatic diepoxides.
Z6. Naturally occurring polymers, such as ce~ulose,na~ral rubber and gelatin, and also the chemically modified homo-logous derivatives thereof, such as cellulose acetates~
cellulose propionates and cellulose butyrates, and cellulose ethers such as methylcellulose.
Of particular importance is the stabilising of lacquers such as alkyd, acrylic and polyester lacquers .?
in particular the stabilising of acid catalysed stoving lacquers.
The stabilisers of this invention are incorporated in the polymers in a concentration o~ 0.01 to 5% by weight, based on the material to be stabilised. Preferably 0.1 to 2% by weight of the compounds, based on the material to be stabilised, is incorporated thereinto.
Incorporation can be effected after polymerisation, for e~ample by blending the compounds and, if desired, further additives, into the melt by methods conventionally employed in the art, before or during the manufacture of shaped articles therefrom, or also by applying the dissolved or dispersed compounds to the polymer, with or without subsequent evaporation of the solvent.
The stabilisers can also be added in the form of a master batch which contains these compounds, for example in a concentration of 2.5 to 25% by weight, to the polymers to be stabilised.
In addition to the compounds of the formulae Ia and Ib, still further known stabilisers can also be incorporated in the polymers. These stabilisers can be e.g.
antioxidants, light stabilisers or metal deactivators, or also costabilisers, for example thos of the phosphite type. Furthermore, other additives customary in plastics technology, for example flame retardants, antistatic agents, plasticisers, lubricants, blowing agents, pigments, reinforcinv materials or fillers, can also be added.
When known stabilisers are used concurr~ntly, synergistic effects can be obtained. This frequently happens especially when other light stabilisers or organic phosphites are used concurrently. The concurrent use of antioxidants when stabilising polyolefins is of particular importance.
The invention therefore also relates to the plas-tics stabilised by the addition of 0.1 to 5% by weight of a compound of the formula I, which plastics, if desired, can also contain other known and customary additives. The stabilised plastics can be used in very diverse forms, for example as films, fibres, ribbons or profiles, but especially as binders for lacquers.
The manufacture and use of the compounds of the invention is described in more detail in the following Examples. Parts and percentages are by weight.
Example 1: 51 g (0.14 mole) of 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2~heneicosane in 400 ml of acetic anhydride and 4 ml of dimethyl formamide are heated for 22 hours to 110-115C. With stirring, the reaction mixture is then cooled to room temperature and filtered.
The filtrate is worked up as described hereinbelow. The crystalline precipitate is recrystallised from dimethyl formamide, washed with water and then with acetone and vacuum dried, affording 3-acetyl-2,2,4,4-tetramethyl-7-oxa-3720-diaza-21-oxo-dispiro~5.1.11.2]heneicosane of the formula C\3/C~3 (/~ 72) 11 /4 5\ /~
\ .2 _ ./ \ 21 1H
which melts at 234-236C (stabiliser 1).
Analysis C24H42N203 calc.: c 70.89 H 10.41 N 6.~9%
(406 . 61 ) found: c 70 . 6 H 10 .5 N 7 .0 %
The acetic anhydride fîltrate obtained above is evaporated to dryness in vacuo. The residue, which crystallises after a short time, is recrystallised twice from acetonitrile, affording pure 3,20-diacetyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane of the formula -( ()2) CH CO 1~
which melts at 183-185C.
Y 26 44 2 4 calc,: C 69.60 H 9.88N 6.24%
(448.65) found: 69.6 9.8 6~4 %
The mono- and diacetyl compounds can be readily identified by thin-layer chromatography and show the expected signals in the lH-NMR spectrum.
Example 2. 27.3 g of 2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diaza-21-oxa-dispiro[5.1.11.2]heneicosane are dissolved in 130 ml of toluene. After addition of 5.4 g of paraform-aldehyde the contents of the flask are heated to 85C.
Hydrocyanic acid is then introduced at this temperature over about l~ hours into the reaction mixture (a total of 8.2 g), which is subsequently stirred for 12 hours at 85C. Then, still at the same temperature, nitrogen is passed through the yellow solution over 6 hours. The solvent is stripped off in vacuo and the residue is recrystallised from methyl ethyl ketone with the addition of activated carbon, yielding 3-cyanomethyl~2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diazo 21-oxo-dispirol5.1.11.2]heneicosane which melts at 191~192C(stabiliser 2~.
9~437 Analysis C31H47N302 calc-: C 75~41 H 9.60 N 8.51%
(493.7) found: 75.1 9.3 8.4 %
Example 3: 25 g (55mmoles) of 2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diazo-21-oxo-dispiro[5.1.11.2~heneicosane, 9.5 ml of triethylamine and 100 mg of 2,6-di-tert-butyl-4-methyl-phenol are dissolved in 70 ml of chloroform ~nd the solution is cooled to -20C. A solution of 5.23 g (58~,moles) of acryloyl chloride in 10 ml of chloroform is added dropwise at -10 to -12C over about 1 hour to the above solution.
The reaction mixture is then stirred for 4 hours at -10C
and the contents of the flask are diluted with 250 ml of hexane, clarified, and extracted with four 25 ml portions of water. The organic phase is dried over Na2S04 and then concentrated i~ vacuo. Crystallisation of the residue from acetonitrile/methyl ethyl ketone yields 3-acryloyl-2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20~diaza-21-oxo-dispiro[5.1.11.2]-heneicosane with a melting point of 174-176C (stabiliser 3).
Analysis C32H48~203 calc-: C 75.55 H 9.51 N 5.51%
(508.7) found: 75.4 9.3 5.5 %.
In corresponding manner, reaction cf 2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2~heneicosane and diethylcarbamoyl chloride gives 3-diethylcarbamoyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]-heneicosane with a melting point of 99-101C (stabiliser 4).
Analysis C30H53N303 calc.: C 71.53 H 10.60 N 8.34%
(503.8) found: 71.7 10.4 8.1 %.
Example 4- 13.6 g (30 mmoles) of 2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane and 0.03 g of 1,4-diazabicyclo[2.2.2]octane (DABC0) are dissolved in 70 ml of benzene. A solution of 2.97 g (30 mmoles) of butyl isocyanate in 10 ml of benzene is added dropwise at room temperature over about 45 minutes to the above solution and the reaction is allowed to go completion for 24 hours at room temperature. The reaction mixture is concentrated to half of its volume and diluted with diethyl ether. The colourless precipitate is filtered with suction, washed with ethyl ether and dried, affording 3-butyl-carbamoyl-2,2,4,4-tetrame~hyl-20-benzyl-7-oxa-3,20-diaza-21-oxo-dispiro~5.1.11.2~-heneicosane with a melting point of 148-150C (stabiliser 5).
Analysis C34H55N303 calc.: C 73.74 H 10.~1 N 7.59%
(553.8) found: 73.3 10.0 7.9%
The following compounds are obtained in the same manner from the corresponding starting materials:
3-cyclohexylcarbamoyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane with a melting point of 140-142C (s~abiliser 6), 3-phenylcarbamoyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane with a melting point of 124-127C (stabiliser 7).
Example 5: 19,6 g of 2,2,4,4-tetramethyl-20-allyl-7-oxa-3920-diaza-21-oxo-dispiro[5.1.11.2]heneicosane and 80 ml of acetic anhydride are stirred for 24 hours at 90-95C. Excess anhydride and the acetic acid formed are distilled off in vacuo as completely as possible. The crystalline residue is recrystallised from acetonitrile affording 3-acetyl-2,2,4,4-tetramethyl-20-allyl-7-oxa-3,20-diaza-21-oxo-dispiro~5.1.11.2]-heneicosane with a melting point of 113-114C (stabiliser 8).
Analysis C27 46 2 3 C 72.6 H 10.38 N 6.27%
(446.8~ found: 72.5 10.2 6.4 1~9~3~37 The following compounds are obtained in similar manner from the corresponding starting materials:
3-acetyl-2,2,4,4-tetramethyl-20-benzyl-7-oxa-3,20-diaza-21-oxo-dispiro~5.1.11.2]heneicosane with a melting point of 128-129C (stabiliser 9), 3-acetyl-2,2,4,4-tetramethyl-20-butylcarbamoyl-7-oxa-3,20-diaæa-21-oxo-dispiro[5.1.11.2~heneicosane with a melting point of 176-178C (stabiliser 10), 3-acetyl-2,2,4,4-tetramethyl-20-hexyl-7-oxa-3,20-diaza-21-oxo-dispirol5.1.11.2]heneicosane with a melting point of 89-91C (stabiliser 11), 1,4-bis(3-acetyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2~heneicosyl-20)-but-2-ene with a melting point of 156-158C (stabiliser 12).
Example 6: A solution of 2.48 g of phosgene is stirred dropwise at 0C over 1 hour into a solution of 20.2 g of 2,2,4,4-tetramethyl-20-allYl-7-oxa-3,20-diaza-21-oxo-dispiro-[5.1.11.2~heneicosane in 120 ml of ethyl acetate. Stirring is continued for 16 hours at room temperature and then a solution of 1.5 g of ethanol and 2.5 g of triethylamine in 10 ml of ethyl acetate is added dropwise. After stirring for 8 hours the reaction mixture is filtered and the filtrate is washed twice with water, three times with ice-cold n-HCl and again with water, dried over Na2S04 and concentrated in vacuo.
The residual crude product is purified by chromatography over a silica gel column with a 3:2 mixture of diethyl ether/
hexane as eluant, and recrystallised from pentane. The pure 3-ethoxycarbonyl-2,2,4,4-tetramethyl-20-allyl-7~oxa-3,20-diaza-21-oxo-dispiro~5.1.11.2]heneicosane has a melting point of 81-82C (stabiliser 13).
~ 3 - 23 ~
~nalysis C28H48N204 calc.: C 70.55 H 10.15 N 5.88%
(476.7) found: 70.8 10.0 6.0 %.
The 1H-NMR spectrum is in accord with the indicated structure.
Exam~le 7: Stabilisation of polypropylene against 1 gh-t 100 parts of polypropylene powder (Moplen, ~ibre grade, manufactured by Montedison), 0.2 part of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid octadecyl ester, 0.1 part of calcium stearate and 0.25 part of a stabiliser of Table 1 are homogenised in a Brabender plastograph for 10 minutes at 200C. The resultant plastic mass is removed from the kneader as quickly as possible and pressed to a 2-3 mm sheet in a toggle press. A portion of the sheet is cut out and pressed between two ultra-gloss rigid aluminium sheets with a hand-operated hydraulic laboratory press for 6 minutes at 260 to a 0.1 mm sheet, which is immediately chilled in cold water. Segments are then punched out of this sheet and exposed in the xeno~est 1200. These samples are taken out of the exposureapparatus at regular intervals and examined for their carbonyl content in a IR spectrophotometer. The increase in the carbonyl extinction at 5.85 ~ during exposure is a reference value for the degradation of the polymer by photooxidation [see L. Balaban et al., J. Polymer Sci., Part Ci 22, 1059-1071 (1969)] and, as experience shows, is associated with a decrease in the mechanical properties of the polymer. The time taken till a carbonyl extinction of about 0.3 is reached, at which value the comparison sheet is brittle, serves as an indication of the protective action.
Table I
,Stabiliser exp..u.. ti n~ in: ~rs 2 > 2100 3 > 2200 4 > 2200 > 1600 6 >2200 7 > 1700 8 > 2200 9 ~ 2200 > 1700 without 880 -xample 8: Stabilisation of a two-coat metallic stoving lacquer Recipe for the priming lacquer 27 parts of polyester resin (L 1850, available from Dynamit Nobel AG), 3 parts of melamine resin (Maprenal RT, available from Hoechst AG), 2 parts of cellulose acetobutyrate (CAB 531, available from Eastman Chem. Corp.), 3 parts of aluminium bronze (ALCOA 726, available Erom the Aluminium Corp. of America), 10 parts of toluene, 7 parts o xylene, 3 parts of butanol, 25 parts of butyl acetate and 15 parts of a mixture of aromatic solvents (Solvesso ~ 150, available f-com ESSO AG).
~:~98~37 - 2s -Recipe for the finishin~ lacquer 58.3 parts of acrylic resin (Viacryl ~J VC 373~ available from Vianova AG), 27.3 parts of melamin~ resin (M~prenal ~ MF 590, available from Hoechst AG), 1.0 part of a 1% solution of a silicone oil in xylene 4.0 parts of a mixture of aromatic solvents (Solvesso ~ , available from ESS0 AG),
5.4 parts of xylene !
4.0 parts of ethyl glycol acetate.
The finishing lacquer is stabilised by adding to it 0.6 part of a stabiliser of the invention, corresponding to a concentration of 1% by weight, based on the solids content of the clear lacquer. The pigmented primer lacquer is sprayed to give a coating of 15 ~m onto aluminium sheets to which an undercoat of a polyester/epoxy resin lacquer has been applied.
After 10 minutes the finishing lacquer is sprayed to give a coating of 30 ,um on top of the priming lacquer coating. The samples ar~ exposed to the air for 15 minutes and then stoved for 30 minutes at 120C.
The coated aluminium sheets are stored for a week under normal climatic conditions (23C/5% relative humidity) and then exposed to weathering in a QUV device in accordance with ASTM
G 53-77. In this text, the samples are moistened for 4 hours at 50C and irradiated by UV light for 4 hours in a humid atmosphere at 60C.
The samples are examined at regular intervals and their appearance is assessed by the TNS crack initiation scale.
'rhis scale has 10 degrees of intensity (1-10) and classifies different types of crack formations (A-P) and crack depth (a-f). The weathering time in the exposure device up to a crack formation of 6-8b according to the TN0 scale is indicated in Table 2 as crack stability.
Table 2 Stabiliser ¦Crack stability in hours _ _.
la > 1500 2 > 1500 7 ~ 15()0 9 > 1500 without llOo
4.0 parts of ethyl glycol acetate.
The finishing lacquer is stabilised by adding to it 0.6 part of a stabiliser of the invention, corresponding to a concentration of 1% by weight, based on the solids content of the clear lacquer. The pigmented primer lacquer is sprayed to give a coating of 15 ~m onto aluminium sheets to which an undercoat of a polyester/epoxy resin lacquer has been applied.
After 10 minutes the finishing lacquer is sprayed to give a coating of 30 ,um on top of the priming lacquer coating. The samples ar~ exposed to the air for 15 minutes and then stoved for 30 minutes at 120C.
The coated aluminium sheets are stored for a week under normal climatic conditions (23C/5% relative humidity) and then exposed to weathering in a QUV device in accordance with ASTM
G 53-77. In this text, the samples are moistened for 4 hours at 50C and irradiated by UV light for 4 hours in a humid atmosphere at 60C.
The samples are examined at regular intervals and their appearance is assessed by the TNS crack initiation scale.
'rhis scale has 10 degrees of intensity (1-10) and classifies different types of crack formations (A-P) and crack depth (a-f). The weathering time in the exposure device up to a crack formation of 6-8b according to the TN0 scale is indicated in Table 2 as crack stability.
Table 2 Stabiliser ¦Crack stability in hours _ _.
la > 1500 2 > 1500 7 ~ 15()0 9 > 1500 without llOo
Claims (4)
1. A compound of the formula Ia or Ib (Ia) (Ib) wherein n is 1 or 2, R1 is C2-C30alkanoyl, C3-C20alkenoyl, -CH2CN, -CO-N(R6)(R7), C7-C11aroyl, C8-C14arylalkanoyl or C8-C20alkylaroyl;
R2 is hydrogen or C1-C4alkyl, each of R3 and R4 independently of the other is hydrogen, C1-C30alkyl, unsubstituted or chlorine- or alkyl-substituted C6-C10aryl, unsubstituted or alkyl-substituted C7-C11aralkyl, or R3 and R4, together with the carbon atom to which they are attached, form a cycloalkane or alkylcycloalkane ring containing 5 to 18 carbon atoms,or a group of the formula R5, when n is 1, is C1-C30alkyl, C3-C20alkenyl, unsubsti-tuted or alkyl-substituted C7-C11aralkyl, or is C5-C12cycloalkyl, C2-C18alkanoyl, C3-C18alkenoyl, C7-C11aroyl, C8-C14arylalkanoyl or C8-C20alkylaroyl, or R5, when n is 2, is C2-C30alkylene, C2-C30alkenylene or C8-C18arylenedialkylene;
R6 is hydrogen, C1-C18alkyl, C5-C8cycloalkyl, C7-C15aralkyl or C6-C10aryl;
R7 is C1-C18alkyl, C5-C8cycloalkyl, C7-C15aralkyl or C6-C10aryl; or R6 and R7, together with the nitrogen atom, form a 5- to 7-membered ring which can be interrupted by further hetero-atoms; and R8 is hydrogen, C1-C12alkyl, C3-C5alkenyl, C3-C5alkynyl, unsubstituted or alkyl-substituted C7-C11aralkyl, C2-C18alkanoyl, C3-C18alkenoyl, -CH2CN or -CO-N(R6)(R7).
R2 is hydrogen or C1-C4alkyl, each of R3 and R4 independently of the other is hydrogen, C1-C30alkyl, unsubstituted or chlorine- or alkyl-substituted C6-C10aryl, unsubstituted or alkyl-substituted C7-C11aralkyl, or R3 and R4, together with the carbon atom to which they are attached, form a cycloalkane or alkylcycloalkane ring containing 5 to 18 carbon atoms,or a group of the formula R5, when n is 1, is C1-C30alkyl, C3-C20alkenyl, unsubsti-tuted or alkyl-substituted C7-C11aralkyl, or is C5-C12cycloalkyl, C2-C18alkanoyl, C3-C18alkenoyl, C7-C11aroyl, C8-C14arylalkanoyl or C8-C20alkylaroyl, or R5, when n is 2, is C2-C30alkylene, C2-C30alkenylene or C8-C18arylenedialkylene;
R6 is hydrogen, C1-C18alkyl, C5-C8cycloalkyl, C7-C15aralkyl or C6-C10aryl;
R7 is C1-C18alkyl, C5-C8cycloalkyl, C7-C15aralkyl or C6-C10aryl; or R6 and R7, together with the nitrogen atom, form a 5- to 7-membered ring which can be interrupted by further hetero-atoms; and R8 is hydrogen, C1-C12alkyl, C3-C5alkenyl, C3-C5alkynyl, unsubstituted or alkyl-substituted C7-C11aralkyl, C2-C18alkanoyl, C3-C18alkenoyl, -CH2CN or -CO-N(R6)(R7).
2, A compound according to claim 1 of the formula Ia or Ib, wherein R1 is C2-C12alkanoyl, C3-C5alkenoyl, phenylacetyl, -CH2CN
or -CO-N(R6)(R7);
R2 is hydrogen;
each of R3 and R4 independently of the other is hydrogen, C1-C12-alkyl, C7-C12aralkyl or phenyl substituted by C1-C4-alkyl, or R3 and R4, together with the carbon atom to which they are attached, form a cycloalkane or alkylcycloalkane ring containing 5 to 12 carbon atoms or a group of the formula R5, when n is 1, is C1-C18alkyl, C3-C6alkenyl, C5-C6cyclo-alkyl, C7-C12aralkyl, C2-C12alkanoyl or C3-C12-alkenoyl, and when n is 2, is C2-C18alkylene, C4-C12alkenylene or xylylene;
R6 is hydrogen, C1-C12alkyl, C5-C6cycloalkyl, C7-C12aralkyl or phenyl;
R7 is C1-C12alkyl, C5-C6cycloalkyl, C7-12aralkyl or C6-C10aryl, or R6 and R7, together with the nitrogen atom to which they are attached, form a 5- to 7-membered ring, and R8 is hydrogen, C1-C6alkyl, C3-C5alkenyl, benzyl, C2-C12-alkanoyl, C3-C12alkenoyl, propargyl or cyanomethyl.
or -CO-N(R6)(R7);
R2 is hydrogen;
each of R3 and R4 independently of the other is hydrogen, C1-C12-alkyl, C7-C12aralkyl or phenyl substituted by C1-C4-alkyl, or R3 and R4, together with the carbon atom to which they are attached, form a cycloalkane or alkylcycloalkane ring containing 5 to 12 carbon atoms or a group of the formula R5, when n is 1, is C1-C18alkyl, C3-C6alkenyl, C5-C6cyclo-alkyl, C7-C12aralkyl, C2-C12alkanoyl or C3-C12-alkenoyl, and when n is 2, is C2-C18alkylene, C4-C12alkenylene or xylylene;
R6 is hydrogen, C1-C12alkyl, C5-C6cycloalkyl, C7-C12aralkyl or phenyl;
R7 is C1-C12alkyl, C5-C6cycloalkyl, C7-12aralkyl or C6-C10aryl, or R6 and R7, together with the nitrogen atom to which they are attached, form a 5- to 7-membered ring, and R8 is hydrogen, C1-C6alkyl, C3-C5alkenyl, benzyl, C2-C12-alkanoyl, C3-C12alkenoyl, propargyl or cyanomethyl.
3. A compound according to claim 1 of the formula Ia, wherein n is 1; R1 is C2-C12alkanoyl, C3-C5alkenoyl, -CO-N(R6)(R7) or -CH2CN; R2 is hydrogen; each of R3 and R4 independently of the other is hydrogen, C1-C4alkyl, benzyl or phenyl, or R3 and R4, together with the carbon atom to which they are attached, form a C5-C12cycloalkane ring;
R5 is C1-C6alkyl, C3-C5alkenyl, benzyl, C2-C12alkanoyl or C3-C5alkenoyl; R6 is hydrogen, C1-C6alkyl, cyclohexyl, benzyl or phenyl; and R7 is C1-C6alkyl, cyclohexyl, benzyl or phenyl; or R6 and R7, together with the nitrogen atom to which they are attached, form a 5- to 7-membered ring.
R5 is C1-C6alkyl, C3-C5alkenyl, benzyl, C2-C12alkanoyl or C3-C5alkenoyl; R6 is hydrogen, C1-C6alkyl, cyclohexyl, benzyl or phenyl; and R7 is C1-C6alkyl, cyclohexyl, benzyl or phenyl; or R6 and R7, together with the nitrogen atom to which they are attached, form a 5- to 7-membered ring.
4. An organic polymer which is stabilised against the action of light, heat and oxygen, and which contains, as stabiliser, 0.01 to 5% by weight, based on the polymer to be stabilised, of a compound of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH660081 | 1981-10-15 | ||
| CH6600/81-0 | 1981-10-15 |
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| CA1198437A true CA1198437A (en) | 1985-12-24 |
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|---|---|
| US (1) | US4419512A (en) |
| EP (1) | EP0079850A1 (en) |
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| 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 |
| 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 |
| DE3643890A1 (en) * | 1986-12-22 | 1988-06-30 | Basf Ag | NEW POLYALKYLPIPERIDE INDEXIVES WITH ALKYLENE BRIDGES, THEIR USE AS A STABILIZER AND INTERMEDIATE PRODUCTS |
| US4859759A (en) * | 1988-04-14 | 1989-08-22 | Kimberly-Clark Corporation | Siloxane containing benzotriazolyl/tetraalkylpiperidyl substituent |
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|---|---|---|---|---|
| DE2063573A1 (en) * | 1970-12-23 | 1972-07-13 | Yoshitomi Pharmaceutical Industries Ltd., Osaka (Japan) | Oxadiazaspiro decanes and undecanes - useful as reserpine antagonists and hypoglycaemics |
| 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 |
| 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 |
| DE2933732A1 (en) * | 1979-08-21 | 1981-03-26 | Hoechst Ag, 65929 Frankfurt | ALKYLATED DIAZASPIRODECANE, THEIR PRODUCTION AND USE AS A LIGHT PROTECTION AGENT |
-
1982
- 1982-09-30 US US06/430,647 patent/US4419512A/en not_active Expired - Fee Related
- 1982-10-11 EP EP82810419A patent/EP0079850A1/en not_active Withdrawn
- 1982-10-13 JP JP57179705A patent/JPS5877884A/en active Pending
- 1982-10-13 CA CA000413272A patent/CA1198437A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5877884A (en) | 1983-05-11 |
| US4419512A (en) | 1983-12-06 |
| EP0079850A1 (en) | 1983-05-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |