CH676242A5 - - Google Patents
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- CH676242A5 CH676242A5 CH4307/88A CH430788A CH676242A5 CH 676242 A5 CH676242 A5 CH 676242A5 CH 4307/88 A CH4307/88 A CH 4307/88A CH 430788 A CH430788 A CH 430788A CH 676242 A5 CH676242 A5 CH 676242A5
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- hydrogen
- alkyl
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- methyl
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 42
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- -1 2,2,6,6-tetramethylpiperidine compound Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 230000008832 photodamage Effects 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229910052717 sulfur Chemical group 0.000 claims description 4
- 239000011593 sulfur Chemical group 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 2
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical compound OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 description 11
- 239000004611 light stabiliser Substances 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- VIMMECPCYZXUCI-MIMFYIINSA-N (4s,6r)-6-[(1e)-4,4-bis(4-fluorophenyl)-3-(1-methyltetrazol-5-yl)buta-1,3-dienyl]-4-hydroxyoxan-2-one Chemical compound CN1N=NN=C1C(\C=C\[C@@H]1OC(=O)C[C@@H](O)C1)=C(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VIMMECPCYZXUCI-MIMFYIINSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
Classifications
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
-
- 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
- C08K5/20—Carboxylic acid amides
-
- 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
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/5398—Phosphorus bound to sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Hydrogenated Pyridines (AREA)
Description
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CH 676 242 A5 CH 676 242 A5
Beschreibung description
Es wurde gefunden, dass man Methylmethacrylat-Polymere und -Copolymere sehr gut gegen die zerstörende Wirkung von Sonnenlicht schützen und gleichzeitig die Entflammbarkeit herabsetzen kann, wenn man diesen Polymeren a) eine Oxalsäureanilid- oder 2,2,6,6-Tetramethylpiperidinverbindung (Komponente a) als Stabilisator gegen die Lichtschädigung und b) eine flammhemmende organische Phosphor-Verbindung (Komponente b) It has been found that methyl methacrylate polymers and copolymers can be protected very well against the destructive effects of sunlight and at the same time reduce the flammability if these polymers a) are treated with an oxalic acid anilide or 2,2,6,6-tetramethylpiperidine compound (component a ) as a stabilizer against light damage and b) a flame-retardant organic phosphorus compound (component b)
Wohl sind z.B. aus Europ.OS 16 870 Poiymethylmethacrylate bekannt, denen zur Verhinderung der Lichtschädigung Tetraalkylpiperidyi-Verbindungen zugesetzt wurden. Andererseits sind z.B. aus DE-OS 3 510 417 Methylmethacrylat-Polymer- und -Copolymermassen bekannt, die ausgewählte, organische Phosphorverbindungen als Flammschutzmittel enthalten. For example, from Europ.OS 16 870 Poiymethylmethacrylate known to which tetraalkylpiperidyi compounds were added to prevent light damage. On the other hand, e.g. known from DE-OS 3 510 417 methyl methacrylate polymer and copolymer compositions which contain selected organic phosphorus compounds as flame retardants.
Die Kombination von Phosphorverbindungen, insbesondere Halogen enthaltenden Phosphorverbindungen als Flammschutzmittel und Tetraalkylpiperidinverbindungen als Lichtstabilisatoren ergibt in Poly-alkylenen, insbesondere Polypropylen, und in ABS sehr unbefriedigende Resultate: Die Phosphorverbindungen wirken auf die Lichtschutzmittel neutralisierend, das heisst die lichtschützende Wirkung vermindert sich, bzw. wird gänzlich aufgehoben, in einigen Fällen tritt sogar eine Gelbfärbung der Kunststoffe auf. Es war daher überraschend zu finden, dass die bekannten negativen Effekte einer Kombination von Flammschutz- und Lichtschutzmitteln in Methylmethacrylat-Polymeren und -Copolyme-ren nicht auftreten. The combination of phosphorus compounds, in particular halogen-containing phosphorus compounds as flame retardants and tetraalkylpiperidine compounds as light stabilizers gives very unsatisfactory results in polyalkylenes, in particular polypropylene, and in ABS: The phosphorus compounds have a neutralizing effect on the light stabilizers, that is to say the light-protecting effect is reduced or is reduced completely canceled, in some cases the plastics even turn yellow. It was therefore surprising to find that the known negative effects of a combination of flame retardants and light stabilizers do not occur in methyl methacrylate polymers and copolymers.
Bevorzugte Stabilisatoren gegen die Lichtschädigung (Komponente a) sind die Verbindungen der Formeln I und II Preferred stabilizers against light damage (component a) are the compounds of the formulas I and II
worin die beiden R unabhängig voneinander Wasserstoff oder Methyl, die beiden Ri unabhängig voneinander Wasserstoff, Ci-18-Alkyl, Ci-i8-Alkoxy, Halogen, Hydroxy, Phenyl oder Phenoxy und die beiden R2 unabhängig voneinander Wasserstoff, Halogen, Hydroxy, Ci_i8-Alkyl oder Ci-is-Alkoxy, R10 Wasserstoff, Sauerstoff, Ci-e-Alkyl oder eine Gruppe der Formel -CO-R15, wherein the two R independently of one another are hydrogen or methyl, the two Ri independently of one another hydrogen, Ci-18-alkyl, Ci-i8-alkoxy, halogen, hydroxy, phenyl or phenoxy and the two R2 independently of one another hydrogen, halogen, hydroxy, Ci_i8- Alkyl or Ci-is-alkoxy, R10 hydrogen, oxygen, Ci-e-alkyl or a group of the formula -CO-R15,
R11 Wasserstoff, Ci-22-Alkyl, Ci-22-Aikoxy oder eine Gruppe der Formel -N(R)-CO-CO-R20, -NH-C(R)=N-R2i oder zusetzt. R11 is hydrogen, Ci-22-alkyl, Ci-22-aikoxy or a group of the formula -N (R) -CO-CO-R20, -NH-C (R) = N-R2i or adds.
(I) (I)
B B
CH3 CH3 CH3 CH3
R R
-0-C0 -(CH2)6-12 - CO-O -0-C0 - (CH2) 6-12 - CO-O
CH3 CH3 CH3 CH3
2 2nd
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CH 676 242 A5 CH 676 242 A5
Ri2 Wasserstoff oder Ci_8-Alkyl oder Ru und R12 gemeinsam, mit dem an sie gebundenen Kohlenstoffatom eine Gruppe der Formel a Ri2 is hydrogen or Ci_8-alkyl or Ru and R12 together, with the carbon atom bonded to them a group of the formula a
Ris C-i-6-Alkyl, Phenyl, Benzyl, Benzoyl, Carboxy oder eine Gruppe der Formel -C(R)=CH2, -CCMD-Ci-12-Alkyl oder-NRi7Ris, Ris C-i-6-alkyl, phenyl, benzyl, benzoyl, carboxy or a group of the formula -C (R) = CH2, -CCMD-Ci-12-alkyl or-NRi7Ris,
R17 Wasserstoff, Ci-12-Alkyl, Cs-e-Cycloalkyl, (vorzugsweise Cyclohexyl), Phenyl, Phenyl-Ci-4-alkyl oder Ci-12-Alkyl-phenyl, R17 is hydrogen, Ci-12-alkyl, Cs-e-cycloalkyl, (preferably cyclohexyl), phenyl, phenyl-Ci-4-alkyl or Ci-12-alkylphenyl,
R18 Wasserstoff oder Ci-12-Alkyl, R18 is hydrogen or Ci-12-alkyl,
R20 eine Amid-bildende Gruppe und R20 is an amide-forming group and
R21 Ci-18-Alkyl, unsubstituiertes oder bis zu 3 Substituenten aus der Gruppe Halogen, Ci-ts-Alkyl und Ci_4-Alkoxy tragendes Phenyl und R Wasserstoff oder Methyl bedeuten. R21 Ci-18-alkyl, unsubstituted or up to 3 substituents from the group halogen, Ci-ts-alkyl and Ci_4-alkoxy-bearing phenyl and R is hydrogen or methyl.
In Formel i bedeuten die beiden R vorzugsweise Wasserstoff, die beiden Ri Wasserstoff, Hydroxy, Ci-4-Alkyl oder Ci_4-Alkoxy und die beiden R2, unabhängig voneinander Wasserstoff, Hydroxy, Ci_4-Alkyl oder Ci-4-Alkoxy, vorzugsweise ein R2 an jedem Benzolring Wasserstoff, das andere R2 an einem Benzolring Ci-^-Alkyl und am anderen Benzolring Ci-4-Alkoxy. In formula i, the two R are preferably hydrogen, the two R i are hydrogen, hydroxy, Ci-4-alkyl or Ci_4-alkoxy and the two R2, independently of one another hydrogen, hydroxy, Ci_4-alkyl or Ci-4-alkoxy, preferably an R2 hydrogen on each benzene ring, the other R2 on a benzene ring Ci - ^ - alkyl and on the other benzene ring Ci-4-alkoxy.
Als Amid-bildende Gruppen sind diejenigen der Formel -NR13R14 bevorzugt, wobei R13 Wasserstoff oder Ci^-Alkyl und R14 ein aliphatischer, cycioaliphatischer aromatischer oder heterocyclischer (nicht aromatischen oder aromatischen Charakters) organischer Rest ist, der bis zu drei Substituenten aus der Reihe Ci-4-Alkoxy, Ci-4-Alkoxy-Ci-i2-alkyl, Ci_4-Alkoxy-Ci-4-alkoxy, Hydroxy, Ci-12-Alkylami-no, Ci-i2-Alkylamino-Gi_i2-alkylamino, Phenoxy, Ci-12-Alkylmercapto, Phenylmercapto oder Phenyl-amino tragen kann. Preferred amide-forming groups are those of the formula -NR13R14, where R13 is hydrogen or Ci ^ alkyl and R14 is an aliphatic, cycioaliphatic aromatic or heterocyclic (non-aromatic or aromatic character) organic radical which has up to three substituents from the Ci series -4-alkoxy, Ci-4-alkoxy-Ci-i2-alkyl, Ci_4-alkoxy-Ci-4-alkoxy, hydroxy, Ci-12-alkylamino-no, Ci-i2-alkylamino-Gi_i2-alkylamino, phenoxy, Ci -12-Alkylmercapto, phenylmercapto or phenylamino can wear.
Die aliphatischen Reste können ferner gegebenenfalls weiter substituiertes Phenyl, die aromatischen Reste können auch Halogen oder Ci-4-AIkyl als Substituenten tragen. Die aliphatischen Reste können linear (bevorzugt) oder verzweigt sein, sie enthalten im allgemeinen 1 bis 22, vorzugsweise 1 bis 12 Kohlenstoffatome. Als cycloaliphatische Reste sind Cyclohexyl und Methyl-substituiertes Cyclohexyl bevorzugt. Unter aromatischen Resten ist vorzugsweise Phenyl zu verstehen. The aliphatic radicals can furthermore optionally further substituted phenyl, the aromatic radicals can also carry halogen or Ci-4-alkyl as substituents. The aliphatic radicals can be linear (preferred) or branched, they generally contain 1 to 22, preferably 1 to 12, carbon atoms. Cyclohexyl and methyl-substituted cyclohexyl are preferred as cycloaliphatic radicals. Aromatic radicals are preferably to be understood as phenyl.
Insbesondere bevorzugte Lichtstabilisatoren der Formel II entsprechen den Formeln II a, bzw. II b und Particularly preferred light stabilizers of the formula II correspond to the formulas II a and II b and
•coocg.^kyi (Ii b), • coocg. ^ Kyi (Ii b),
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ch 676 242 a5 ch 676 242 a5
worin alle Rio,' Wasserstoff, Ci-4-Alkyl oder -CO-R15', where all Rio, 'hydrogen, Ci-4-alkyl or -CO-R15',
die beiden R12' Wasserstoff oder Methyl, vor allem Wasserstoff und the two R12 'are hydrogen or methyl, especially hydrogen and
Rir Ou'Myl oder eine Gruppo der formel -îW-y-îi-ifilhy! Reuten. Rir Ou'Myl or a group of the formula -îW-y-îi-ifilhy! Reuten.
Bevorzugte flammhemmende organische Phosphorverbindungen (Komponente b) entsprechen den Formeln III, bzw. IV Preferred flame-retardant organic phosphorus compounds (component b) correspond to the formulas III and IV
ILO—P- ILO — P-
3 I 3 I
r30 r30
r. 0 r. 0
«* m «* M
-CHO-P- -CHO-P-
R30j r4 0 R30j r4 0
-cho-p—orj R, -cho-p — orj R,
(III) (III)
und and
P—0—R; P-0-R;
-c-(ch2r5)2 (iv) -c- (ch2r5) 2 (iv)
worin die beiden R unabhängig voneinander Wasserstoff oder Methyl, wherein the two R are independently hydrogen or methyl,
alle R3 unabhängig voneinander Wasserstoff, Ci-e-Alkyl, das ein oder zwei Halogenatome als Substituenten tragen kann oder unsubstituiertes oder ein Halogenatom oder eine Ci-^-Alkoxygruppe tragendes C2-6-Alkenyl oder Phenyl, all R3 independently of one another are hydrogen, Ci-e-alkyl, which can carry one or two halogen atoms as substituents or unsubstituted or C2-6-alkenyl or phenyl carrying a halogen atom or a Ci - ^ - alkoxy group,
R4 Ci-17-Alkyl, vorzugsweise Methyl oder Äthyl, insbesondere Methyl, R4 Ci-17-alkyl, preferably methyl or ethyl, especially methyl,
R5 Wasserstoff oder Halogen, vorzugsweise Wasserstoff, Chlor oder Brom, insbesondere Chlor, R6 Ci-4-Alkylen, R5 is hydrogen or halogen, preferably hydrogen, chlorine or bromine, in particular chlorine, R6 Ci-4-alkylene,
die beiden R7 unabhängig voneinander eine der Bedeutungen von R3, the two R7 independently of one another have one of the meanings of R3,
n eine ganze Zahl von 1 bis 10 und X Sauerstoff oder Schwefel bedeuten. n is an integer from 1 to 10 and X is oxygen or sulfur.
Unter Halogen ist hier allgemein vorzugsweise Chlor oder Brom, insbesondere Chlor zu verstehen. Als aliphatische Reste kommen insbesondere Alkylreste in Betracht. Halogen here is generally to be understood as preferably chlorine or bromine, in particular chlorine. Alkyl residues are particularly suitable as aliphatic residues.
Alle Alkylreste (auch die Alkoxy- und Alkylaminoreste) enthalten, auch wenn C1-21, C1-18 oder C1-17 angegeben ist, vorzugsweise 1 bis 12 Kohlenstoffatome, insbesondere enthalten diese und auch die übrigen C1-12, -C1-8 und Ci-e-Alkylreste 1 bis 4 Kohlenstoffatome, vor allem sind dabei Methyl und Äthyl bevorzugt. All alkyl radicals (including the alkoxy and alkylamino radicals), even if C1-21, C1-18 or C1-17 are indicated, preferably contain 1 to 12 carbon atoms, in particular these and also the other C1-12, C1-8 and Ci-e-alkyl radicals 1 to 4 carbon atoms, especially methyl and ethyl are preferred.
Alle R3 in Formel III sind vorzugsweise Monochlor- oder Monobrom-Ci-4-alkyl, insbesondere eine Gruppe der Formel -CH2CH2CI. Alle R4 sind vorzugsweise Methyl oder Äthyl, insbesondere Methyl. In dieser Formel III bedeutet n im Mittel vorzugsweise 2. All R3 in formula III are preferably monochloro- or monobromo-Ci-4-alkyl, in particular a group of the formula -CH2CH2CI. All R4 are preferably methyl or ethyl, especially methyl. In this formula III, n is preferably 2 on average.
Rß in Formel IV ist vorzugsweise Methylen oder Äthylen, insbesondere Methylen. Rß in formula IV is preferably methylene or ethylene, especially methylene.
Unter den Verbindungen der Formel III sind diejenigen der Formel III' bevorzugt, Preferred compounds of the formula III are those of the formula III '
(R,/H2CH20*2—1>- (R, / H2CH20 * 2—1> -
CH, CH,
I «3 -CH- I «3 -CH-
0 « 0 «
-0—P- -0 — P-
/ J / J
0ch2ch2rls ch— 0— p-ch2ch2rig 2 och2ch2R^ 0ch2ch2rls ch— 0— p-ch2ch2rig 2 och2ch2R ^
(III'), (III '),
worin jedes R19 ein Halogenatom, vorzugsweise ein Brom- oder Chloratom, insbesondere ein Chloratom ist. wherein each R19 is a halogen atom, preferably a bromine or chlorine atom, especially a chlorine atom.
Unter den Verbindungen der Formel IV sind diejenigen der Formel IV' bevorzugt, Preferred compounds of the formula IV are those of the formula IV '
4 4th
5 5
10 10th
15 15
20 20th
25 25th
30 30th
35 35
40 40
45 45
50 50
55 55
60 60
65 65
CH 676 242 A5 CH 676 242 A5
\/2 \; \ / 2 \;
- p - p
-y -y
*7 * 7
A A
P—0—CHÔ P — 0 — CHÔ
■c(ch2c1)2 ■ c (ch2c1) 2
(IV'), (IV '),
worin alle R7 unabhängig voneinander Wasserstoff, Methyl oder Äthyl, vorzugsweise Methyl und X ein Sauerstoffatom oder Schwefel, vorzugsweise Sauerstoff bedeuten. wherein all R7 independently of one another are hydrogen, methyl or ethyl, preferably methyl and X is an oxygen atom or sulfur, preferably oxygen.
Die Verbindungen der Formein I bis IV sind bekannt, bzw. lassen sich in Analogie zu bekannten Methoden zur Herstellung ähnlicher Verbindungen leicht herstellen. The compounds of forms I to IV are known or can be easily prepared analogously to known methods for the preparation of similar compounds.
Die erfindungsgemäss auszurüstenden Methylmethacrylat-Polymeren und -Copolymeren, üblicherweise unter dem Namen «Plexiglas» bekannt, werden ebenfalls nach allgemein bekannten Hersteilungsverfahren erhalten. The methyl methacrylate polymers and copolymers to be finished according to the invention, usually known under the name “Plexiglas”, are also obtained by generally known production processes.
Für die Copolymerisation werden z.B. die folgenden a, ß-ungesättigten Comonomere verwendet. Methacrylsäure-C2-8-aikylester, Acrylsäure-Ci-s-alkylester, a-Cyanacryisäure-Ci-s-alkylester (die Äthyl-, Butyl- oder Cyclohexylester sind bevorzugt), Styrol, Methylstyrol, Acrylnitril, Methacryinitrii oder a-Chloracrylnitril. For the copolymerization e.g. the following a, β-unsaturated comonomers used. C2-8 methacrylate, Ci-s-alkyl acrylate, Ci-s-alkyl a-cyanoacrylic acid (the ethyl, butyl or cyclohexyl esters are preferred), styrene, methyl styrene, acrylonitrile, methacrylonitrile or a-chloroacrylonitrile.
Bevorzugt verwendete Copolymere werden durch Polymerisation von Methylmethacrylaten in Gegenwart von Glycidylacrylat und/oder Glycidylmethacrylat, vorzugsweise in Gegenwart von Glycidylmeth-acrylat hergestellt. Vorzugsweise enthalten solche Copolymere 0,1 bis 10 Gewichtsprozent, insbesondere 0,5 bis 6 Gewichtsprozent (bezogen auf die gesamte Polymermasse) der entsprechenden Glycidylver-bindungen. im allgemeinen werden die Komponenten a und b (Lichtschutz- und Flammschutzmittel) den Monomeren oder Präpolymeren, bei Temperaturen zwischen etwa 20 und 150°C beigemischt, worauf die Polymerisation in Gegenwart eines Polymerisationskatalysators, z.B. Azo- bis -iso-butyronitril, Diben-zoylperoxid, Dilaurylperoxid oder tert-Butoxyperpivalat durchgeführt wird. Die Komponenten a und b können auch nach bekannten Methoden in die geschmolzenen Polymerisate und Copolymerisate eingearbeitet werden, z.B. im Extruder. Copolymers used with preference are prepared by polymerizing methyl methacrylates in the presence of glycidyl acrylate and / or glycidyl methacrylate, preferably in the presence of glycidyl methacrylate. Such copolymers preferably contain 0.1 to 10 percent by weight, in particular 0.5 to 6 percent by weight (based on the total polymer mass) of the corresponding glycidyl compounds. generally components a and b (light stabilizers and flame retardants) are added to the monomers or prepolymers at temperatures between about 20 and 150 ° C, whereupon the polymerization in the presence of a polymerization catalyst, e.g. Azo to isobutyronitrile, dibenzoyl peroxide, dilauryl peroxide or tert-butoxyperpivalate is carried out. Components a and b can also be incorporated into the molten polymers and copolymers by known methods, e.g. in the extruder.
Vorzugsweise arbeitet man zwischen 3 und 30%, insbesondere 8 bis 25% der Komponenten a und b, bezogen auf das Gewicht der Monomeren oder der Polymermassen ein. Wird ein Glycidylacrylat- oder Glycidylmethacrylat-enthaltendes Polymer stabilisiert, können geringere Mengen der Stabilisatoren verwendet werden, z.B. nur 3 bis 25%, vorzugsweise 8 bis 15% (bezogen wieder auf das Gewicht der Mono- oder Polymermassen). Dabei ist das Verhältnis der Komponenten a:b so zu wählen, dass in der Polymermasse schliesslich 0,01 bis 0,5, vorzugsweise 0,02 bis 0,2 Gewichtsprozente Lichtschutzmittel vorhanden sind, das heisst also, das Gewichtsverhältnis a:b ist etwa 3:97 bis 15:85. It is preferred to work in between 3 and 30%, in particular 8 to 25%, of components a and b, based on the weight of the monomers or of the polymer compositions. If a polymer containing glycidyl acrylate or glycidyl methacrylate is stabilized, smaller amounts of the stabilizers can be used, e.g. only 3 to 25%, preferably 8 to 15% (again based on the weight of the mono- or polymer masses). The ratio of components a: b is to be selected such that finally 0.01 to 0.5, preferably 0.02 to 0.2 percent by weight of light stabilizers is present in the polymer mass, that is to say that the weight ratio a: b is approximately 3:97 to 15:85.
In den folgenden Beispielen bedeuten die Teile Gewichtsteile, die Temperaturen sind in Celsiusgraden angegeben. In the following examples, the parts mean parts by weight, the temperatures are given in degrees Celsius.
Beispiel 1 example 1
47,5 Teile frisch destilliertes Methylmethacrylat werden mit 0,04 Teilen Dilaurylperoxid, 0,03 Teilen Azoisobuttersäuredinitril, 2,5 Teilen der Verbindung der Formel 1 a 47.5 parts of freshly distilled methyl methacrylate are mixed with 0.04 part of dilauryl peroxide, 0.03 part of azoisobutyronitrile, 2.5 parts of the compound of formula 1a
(ClCHgCHgO)^—P (ClCHgCHgO) ^ - P
5 5
und 0,1 Teil der Verbindung der Formel 1 b and 0.1 part of the compound of formula 1 b
ÇH3 OCHgCHgCI CH3 CHgCHjCI ÇH3 OCHgCHgCI CH3 CHgCHjCI
(1 a) (1 a)
0-C0-NH ~^0) C2HS 0c2«5 0-C0-NH ~ ^ 0) C2HS 0c2 «5
(1 b) (1 b)
gemischt, auf 115°C erhitzt, 7 Minuten bei dieser Temperatur belassen, dann zwischen zwei Glasplatten (mit einem Gummi-Distanzhalter auf einen Abstand von 3 mm eingestellt) gegossen, die Glasplatten mit transparentem Klebeband gesichert, 16 Stunden bei 50° gelagert und danach 4 Stunden auf 115° erhitzt. mixed, heated to 115 ° C, left at this temperature for 7 minutes, then poured between two glass plates (adjusted to a distance of 3 mm with a rubber spacer), the glass plates secured with transparent adhesive tape, stored at 50 ° for 16 hours and then Heated to 115 ° for 4 hours.
5 5
5 5
10 10th
15 15
20 20th
25 25th
30 30th
35 35
40 40
45 45
50 50
55 55
60 60
65 65
CH 676 242 A5 CH 676 242 A5
Die erhaltene, tadellos transparente Platte zeigt sowohl sehr geringe Entflammbarkeit als auch ausgezeichnete Resistenz gegen Lichtschädigung. The perfectly transparent plate obtained shows both very low flammability and excellent resistance to light damage.
Beispiel 2 Example 2
In einem ArLury 000 SpritzgulI-BMll1 Wltìifl 90 Tflllfl flQIldQl£ÜDIICHQE FMMA In an ArLury 000 SpritzgulI-BMll1 Wltìifl 90 Tflllfl flQIldQl £ ÜDIICHQE FMMA
(Polymethylmethacryiat) mit 0,2 Teilen der Verbindung der Formel 1 b (Beispiel 1) und 10 Teilen der Verbindung der Formel 2 a (Polymethyl methacrylate) with 0.2 part of the compound of formula 1 b (Example 1) and 10 parts of the compound of formula 2 a
/ V-o/ / V-o /
worin n im Mittel 2 ist, where n is 2 on average,
bei 200° bis 220° gemischt und zu 3 mm dicken Platten extrudiert. Die so erhaltenen Werkstücke zeichnen sich durch gute Lichtstabilität und geringe Entflammbarkeit aus. mixed at 200 ° to 220 ° and extruded into 3 mm thick sheets. The work pieces thus obtained are characterized by good light stability and low flammability.
Beispiele 3 und 4 Examples 3 and 4
Gemäss der Arbeitsvorschrift des Beispiels 2 werden PMMA-Platten hergestellt, die jedoch an Stelle des dort verwendeten UV-Absorbers (Verbindung 1 b) die gleiche Menge der Verbindung 3a, bzw. 4a enthalten. According to the working procedure of Example 2, PMMA plates are produced which, however, contain the same amount of compound 3a or 4a instead of the UV absorber used there (compound 1b).
^»2)11 ^ »2) 11
0—LcH2CH2-C00C12H25(n) 0 — LcH2CH2-C00C12H25 (n)
(3 a) (3 a)
«afa «Afa
Ç—(CH2)8 Ç. 3 0 0 Ç— (CH2) 8 Ç. 3 0 0
(4 a) (4 a)
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878727452A GB8727452D0 (en) | 1987-11-24 | 1987-11-24 | Organic compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH676242A5 true CH676242A5 (en) | 1990-12-28 |
Family
ID=10627436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH4307/88A CH676242A5 (en) | 1987-11-24 | 1988-11-21 |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH01167357A (en) |
| CH (1) | CH676242A5 (en) |
| DE (1) | DE3838480A1 (en) |
| FR (1) | FR2623515A1 (en) |
| GB (2) | GB8727452D0 (en) |
| IT (1) | IT1224575B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9121575D0 (en) * | 1991-10-11 | 1991-11-27 | Sandoz Ltd | Improvements in or relating to organic compounds |
| EP1148090A1 (en) * | 2000-04-17 | 2001-10-24 | Clariant Finance (BVI) Limited | Flame retardant polymers |
| DE10040060A1 (en) * | 2000-08-11 | 2002-02-28 | Roehm Gmbh | Improved tanning bed material |
| DE10311641A1 (en) * | 2003-03-14 | 2004-09-23 | Röhm GmbH & Co. KG | Polymethyl methacrylate shaped body or molding useful as a tanning aid contains UV-stabilizers and UV-absorbers with specified transmission values |
| EP1777257B1 (en) * | 2005-10-20 | 2018-08-22 | Arkema France | Fireproof methacrylic composition |
| FR2892422B1 (en) * | 2005-10-20 | 2011-08-05 | Arkema | FLAME RETARDANT METHACRYLIC COMPOSITION |
| US8466096B2 (en) | 2007-04-26 | 2013-06-18 | Afton Chemical Corporation | 1,3,2-dioxaphosphorinane, 2-sulfide derivatives for use as anti-wear additives in lubricant compositions |
| DE102008043713A1 (en) | 2008-11-13 | 2010-05-20 | Evonik Röhm Gmbh | Production of solar cell modules |
| DE102008043719A1 (en) * | 2008-11-13 | 2010-05-20 | Evonik Röhm Gmbh | Molding compounds for the production of solar cell modules |
| DE102010030508A1 (en) | 2010-06-25 | 2011-12-29 | Evonik Röhm Gmbh | Production of solar cell modules |
| JP6346305B2 (en) * | 2014-12-05 | 2018-06-20 | 大日精化工業株式会社 | Manufacturing method of additive for granular resin, additive for granular resin, thermoplastic resin composition, and molded product obtained by the manufacturing method |
| EP3497159A1 (en) * | 2016-08-15 | 2019-06-19 | Evonik Röhm GmbH | Acrylic materials for use in an ultraviolet light engine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH501699A (en) * | 1965-12-08 | 1971-02-26 | Ciba Geigy Ag | Use of symmetrical oxalic acid diarylamides as ultraviolet protection agents for organic materials outside the textile industry |
| DE2913853A1 (en) * | 1979-04-06 | 1980-10-23 | Roehm Gmbh | METHOD FOR POLYMERIZING METHYL METHACRYLATE |
| CH667275A5 (en) * | 1985-03-22 | 1988-09-30 | Sandoz Ag | FLAME RETARDED METHYL METHACRYLATE POLYMER AND COPOLYMER. |
-
1987
- 1987-11-24 GB GB878727452A patent/GB8727452D0/en active Pending
-
1988
- 1988-11-12 DE DE3838480A patent/DE3838480A1/en not_active Withdrawn
- 1988-11-17 FR FR8815082A patent/FR2623515A1/en not_active Withdrawn
- 1988-11-21 IT IT8848573A patent/IT1224575B/en active
- 1988-11-21 CH CH4307/88A patent/CH676242A5/de not_active IP Right Cessation
- 1988-11-21 GB GB8827132A patent/GB2212807B/en not_active Expired - Lifetime
- 1988-11-22 JP JP63293733A patent/JPH01167357A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB8827132D0 (en) | 1988-12-29 |
| GB2212807B (en) | 1991-08-14 |
| IT1224575B (en) | 1990-10-04 |
| GB8727452D0 (en) | 1987-12-23 |
| FR2623515A1 (en) | 1989-05-26 |
| DE3838480A1 (en) | 1989-06-08 |
| JPH01167357A (en) | 1989-07-03 |
| IT8848573A0 (en) | 1988-11-21 |
| GB2212807A (en) | 1989-08-02 |
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