DE3838480A1 - LIGHT STABILIZED FLAME RESISTANT METHYL METHACRYLATE POLYMERS AND COPOLYMERS - Google Patents
LIGHT STABILIZED FLAME RESISTANT METHYL METHACRYLATE POLYMERS AND COPOLYMERSInfo
- Publication number
- DE3838480A1 DE3838480A1 DE3838480A DE3838480A DE3838480A1 DE 3838480 A1 DE3838480 A1 DE 3838480A1 DE 3838480 A DE3838480 A DE 3838480A DE 3838480 A DE3838480 A DE 3838480A DE 3838480 A1 DE3838480 A1 DE 3838480A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- hydrogen
- formula
- alkoxy
- methyl
- 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.)
- Withdrawn
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 229920001577 copolymer Polymers 0.000 title claims abstract description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 8
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- -1 2,2,6,6-tetramethylpiperidine compound Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 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
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 230000008832 photodamage Effects 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000006704 (C5-C6) cycloalkyl group Chemical group 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
- 125000002947 alkylene 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
- 125000005037 alkyl phenyl group Chemical group 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 239000004611 light stabiliser Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 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
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000003118 aryl 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
- 238000004519 manufacturing process Methods 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
- 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
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-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
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio 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
- 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
- 238000001746 injection moulding Methods 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 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
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 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
Abstract
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 PolymerenIt has been found that methyl methacrylate polymers and copolymers protect very well against the destructive effects of sunlight and can reduce the flammability at the same time if you Polymers
- a) eine Oxalsäureanilid- oder 2,2,6,6-Tetramethylpiperidinverbindung (Komponente a) als Stabilisator gegen die Lichtschädigung unda) an oxalic acid anilide or 2,2,6,6-tetramethylpiperidine compound (Component a) as a stabilizer against light damage and
- b) eine flammhemmende organische Phosphor-Verbindung (Komponente b)b) a flame retardant organic phosphorus compound (component b)
zusetzt.adds.
Wohl sind z. B. aus Europ. OS 16 870 Polymethylmethacrylate bekannt, denen zur Verhinderung der Lichtschädigung Tetraalkylpiperidyl-Verbindungen zugesetzt wurden. Andererseits sind z. B. aus DE-OS 35 10 417 Methyl methacrylat-Polymer- und -Copolymermassen bekannt, die ausgewählte, organische Phosphorverbindungen als Flammschutzmittel enthalten.Well z. B. from Europ. OS 16 870 polymethyl methacrylates known to whom to prevent light damage tetraalkylpiperidyl compounds were added. On the other hand, e.g. B. from DE-OS 35 10 417 methyl known methacrylate polymer and copolymer compositions, the selected, contain organic phosphorus compounds as flame retardants.
Die Kombination von Phosphorverbindungen, insbesondere Halogen enthaltenden Phosphorverbindungen als Flammschutzmittel und Tetraalkyl piperidinverbindungen als Lichtstabilisatoren ergibt in Polyalkylenen, 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.The combination of phosphorus compounds, especially halogen-containing ones Phosphorus compounds as flame retardants and tetraalkyl piperidine compounds as light stabilizers in polyalkylenes, especially polypropylene, and very unsatisfactory results in ABS: The phosphorus compounds have a neutralizing effect on the light stabilizers, this means that the light-protecting effect is reduced or is completely canceled out, in some cases it even turns yellow of plastics.
Es war daher überraschend zu finden, daß die bekannten negativen Effekte einer Kombination von Flammschutz- und Lichtschutzmitteln in Methylmethacrylat-Polymeren und -Copolymeren nicht auftreten.It was therefore surprising to find that the known ones negative effects of a combination of flame retardants and light stabilizers not in methyl methacrylate polymers and copolymers occur.
Bevorzugte Stabilisatoren gegen die Lichtschädigung (Komponente a) sind die Verbindungen der Formeln I und IIPreferred 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
R₁ unabhängig voneinander Wasserstoff, C1-18-Alkyl,
C1-18-Alkoxy, Halogen, Hydroxy, Phenyl oder Phenoxy und
die beiden R₂ unabhängig voneinander Wasserstoff, Halogen,
Hydroxy, C1-18-Alkyl oder C1-18-Alkoxy,
R₁₀ Wasserstoff, Sauerstoff, C1-8-Alkyl oder eine Gruppe der
Formel -CO-R₁₅,
R₁₁ Wasserstoff, C1-22-Alkyl, C1-22-Alkoxy oder eine Gruppe der
Formel -N(R)-CO-CO-R₂₀, -NH-C(R)=N-R₂₁ oderwhere the two
R independently of one another hydrogen or methyl, the two
R₁ independently of one another hydrogen, C 1-18 alkyl, C 1-18 alkoxy, halogen, hydroxy, phenyl or phenoxy and the two R₂ independently of one another hydrogen, halogen, hydroxy, C 1-18 alkyl or C 1-18 - Alkoxy,
R₁₀ is hydrogen, oxygen, C 1-8 alkyl or a group of the formula -CO-R₁₅,
R₁₁ is hydrogen, C 1-22 alkyl, C 1-22 alkoxy or a group of the formula -N (R) -CO-CO-R₂₀, -NH-C (R) = N-R₂₁ or
R₁₂ Wasserstoff oder C1-8-Alkyl oder R₁₁ und R₁₂ gemeinsam, mit dem an sie gebundenen Kohlenstoffatom eine Gruppe der Formel aR₁₂ is hydrogen or C 1-8 alkyl or R₁₁ and R₁₂ together, with the carbon atom attached to them a group of formula a
R₁₅ C1-6-Alkyl, Phenyl, Benzyl, Benzoyl, Carboxy oder eine Gruppe
der Formel -C(R)=CH₂, -CO-O-C1-12-Alkyl oder -NR₁₇R₁₈,
R₁₇ Wasserstoff, C1-12-Alkyl, C5-6-Cycloalkyl, (vorzugsweise
Cyclohexyl), Phenyl, Phenyl-C1-4-alkyl oder
C1-12-Alkyl-phenyl,
R₁₈ Wasserstoff oder C1-12-Alkyl,
R₂₀ eine Amid-bildende Gruppe und
R₂₁ C1-18-Alkyl, unsubstituiertes oder bis zu 3 Substituenten
aus der Gruppe Halogen, C1-18-Alkyl
und C1-4-Alkoxy tragendes Phenyl und
R Wasserstoff oder Methyl
bedeuten.R₁₅ C 1-6 alkyl, phenyl, benzyl, benzoyl, carboxy or a group of the formula -C (R) = CH₂, -CO-OC 1-12 alkyl or -NR₁₇R₁₈,
R₁₇ is hydrogen, C 1-12 -alkyl, C 5-6 -cycloalkyl, (preferably cyclohexyl), phenyl, phenyl-C 1-4 -alkyl or C 1-12 -alkyl-phenyl,
R₁₈ is hydrogen or C 1-12 alkyl,
R₂₀ is an amide-forming group and
R₂₁ C 1-18 alkyl, unsubstituted or up to 3 substituents from the group halogen, C 1-18 alkyl and C 1-4 alkoxy-bearing phenyl and
R is hydrogen or methyl
mean.
In Formel I bedeuten die beiden R vorzugsweise Wasserstoff, die beiden R₁ Wasserstoff, Hydroxy, C1-4-Alkyl oder C1-4-Alkoxy und die beiden R₂, unabhängig voneinander Wasserstoff, Hydroxy, C1-4-Alkyl oder C1-4-Alkoxy, vorzugsweise ein R₂ an jedem Benzolring Wasserstoff, das andere R₂ an einem Benzolring C1-4-Alkyl und am anderen Benzolring C1-4-Alkoxy. In formula I, the two R are preferably hydrogen, the two R₁ are hydrogen, hydroxy, C 1-4 alkyl or C 1-4 alkoxy and the two R₂, independently of one another, are hydrogen, hydroxy, C 1-4 alkyl or C 1 -4 alkoxy, preferably one R₂ on each benzene ring hydrogen, the other R₂ on a benzene ring C 1-4 alkyl and on the other benzene ring C 1-4 alkoxy.
Als Amid-bildende Gruppen sind diejenigen der Formel -NR₁₃R₁₄ bevorzugt, wobei R₁₃ Wasserstoff oder C1-4-Alkyl und R₁₄ ein aliphatischer, cyclo aliphatischer aromatischer oder heterocyclischer (nicht aromatischen oder aromatischen Charakters) organischer Rest ist, der bis zu drei Substituenten aus der Reihe C1-4-Alkoxy, C1-4-Alkoxy-C1-12-alkyl, C1-4- Alkoxy-C1-4-alkoxy, Hydroxy, C1-12-Alkylamino, C1-12-Alkylamino-C1-12- alkylamino, Phenoxy, C1-12-Alkylmercapto, Phenylmercapto oder Phenylamino tragen kann.Preferred amide-forming groups are those of the formula -NR₁₃R₁₄, where R₁₃ is hydrogen or C 1-4 -alkyl and R₁₄ is an aliphatic, cyclo aliphatic aromatic or heterocyclic (non-aromatic or aromatic character) organic radical which consists of up to three substituents the series C 1-4 alkoxy, C 1-4 alkoxy-C 1-12 alkyl, C 1-4 alkoxy-C 1-4 alkoxy, hydroxy, C 1-12 alkylamino, C 1-12 -Alkylamino-C 1-12 - alkylamino, phenoxy, C 1-12 alkylmercapto, phenylmercapto or phenylamino can wear.
Die aliphatischen Reste können ferner gegebenenfalls weiter substituiertes Phenyl, die aromatischen Reste können auch Halogen oder C1-4-Alkyl 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 also optionally further substituted phenyl, the aromatic radicals can also carry halogen or C 1-4 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 IIa bzw. IIbParticularly preferred light stabilizers correspond to formula II formulas IIa and IIb
undand
worin alle
R′₁₀ Wasserstoff, C1-4-Alkyl oder -CO-R′₁₅,
die beiden
R′₁₂ Wasserstoff oder Methyl, vor allem Wasserstoff und
R′₁₅ C1-4-Alkyl oder eine Gruppe der Formel
-CO-O-C1-4-Alkyl bedeuten.in which all
R'₁₀ hydrogen, C 1-4 alkyl or -CO-R'₁₅, the two
R'₁₂ is hydrogen or methyl, especially hydrogen and
R'₁₅ C 1-4 alkyl or a group of the formula -CO-OC 1-4 alkyl.
Bevorzugte flammhemmende organische Phosphorverbindungen (Komponente b) entsprechen den Formeln III bzw. IVPreferred flame retardant organic phosphorus compounds (component b) correspond to formulas III and IV
undand
worin die beiden
R unabhängig voneinander Wasserstoff oder Methyl,
alle
R₃ unabhängig voneinander Wasserstoff, C1-6-Alkyl, das ein oder
zwei Halogenatome als Substituenten tragen kann oder unsubstituiertes
oder ein Halogenatom oder eine C1-4-Alkoxygruppe tragendes C2-6-Alkenyl
oder Phenyl,
R₄ C1-17-Alkyl, vorzugsweise Methyl oder Äthyl, insbesondere
Methyl,
R₅ Wasserstoff oder Halogen, vorzugsweise Wasserstoff, Chlor
oder Brom, insbesondere Chlor,
R₆ C1-4-Alkylen,
die beiden
R₇ unabhängig voneinander eine der Bedeutungen von R₃,
n eine ganze Zahl von 1 bis 10 und
X Sauerstoff oder Schwefel bedeuten.where the two
R independently of one another hydrogen or methyl, all
R₃ independently of one another are hydrogen, C 1-6 -alkyl which can carry one or two halogen atoms as substituents or unsubstituted or C 2-6 -alkenyl or phenyl carrying a halogen atom or a C 1-4 alkoxy group,
R₄ C 1-17 alkyl, preferably methyl or ethyl, especially methyl,
R₅ is hydrogen or halogen, preferably hydrogen, chlorine or bromine, especially chlorine,
R₆ C 1-4 alkylene, the two
R₇ independently of one another have one of the meanings of R₃,
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 preferably chlorine or bromine, in particular To understand chlorine. In particular come as aliphatic radicals Alkyl residues into consideration.
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 C1-6-Alkylreste 1 bis 4 Kohlenstoffatome, vor allem sind dabei Methyl und Äthyl bevorzugt.All alkyl radicals (including the alkoxy and alkylamino radicals), even if C 1-21 , C 1-18 or C 1-17 is indicated, preferably contain 1 to 12 carbon atoms, in particular these and also the other C 1-12 -, -C 1-8 - and C 1-6 alkyl radicals 1 to 4 carbon atoms, especially methyl and ethyl are preferred.
Alle R₃ in Formel III sind vorzugsweise Monochlor- oder Monobrom-C1-4-alkyl, insbesondere eine Gruppe der Formel -CH₂CH₂Cl. 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-C 1-4 alkyl, in particular a group of the formula -CH₂CH₂Cl. All R₄ are preferably methyl or ethyl, especially methyl. In this formula III, n is preferably 2 on average.
R₆ in Formel IV ist vorzugsweise Methylen oder Äthylen, insbesondere Methylen.R₆ in formula IV is preferably methylene or ethylene, in particular Methylene.
Unter den Verbindungen der Formel III sind diejenigen der Formel III′ bevorzugt,Among the compounds of the formula III are those of the formula III ′ prefers,
worin jedes R₁₉ ein Halogenatom, vorzugsweise ein Brom- oder Chloratom, insbesondere ein Chloratom ist.wherein each R₁₉ represents a halogen atom, preferably a bromine or chlorine atom, in particular is a chlorine atom.
Unter den Verbindungen der Formel IV sind diejenigen der Formel IV′ bevorzugt,Among the compounds of the formula IV are those of the formula IV ′ prefers,
worin alle
R₇ unabhängig voneinander Wasserstoff, Methyl oder Äthyl,
vorzugsweise Methyl und
X ein Sauerstoffatom oder Schwefel, vorzugsweise Sauerstoff bedeuten.in which all
R₇ independently of one another hydrogen, methyl or ethyl, preferably methyl and
X represents an oxygen atom or sulfur, preferably oxygen.
Die Verbindungen der Formeln I bis IV sind bekannt, bzw. lassen sich in Analogie zu bekannten Methoden zur Herstellung ähnlicher Verbindungen leicht herstellen.The compounds of formulas I to IV are known, or can be in Analogy to known methods for producing similar compounds easy to manufacture.
Die erfindungsgemäß auszurüstenden Methylmethacrylat-Polymeren und -Copolymeren, üblicherweise unter dem Namen "Plexiglas" bekannt, werden ebenfalls nach allgemein bekannten Herstellungsverfahren erhalten.The methyl methacrylate polymers and Copolymers, commonly known as "plexiglass" also obtained by generally known manufacturing processes.
Für die Copolymerisation werden z. B. die folgenden α,β-ungesättigten Comonomere verwendet. Methacrylsäure-C2-8-alkylester, Acrylsäure-C1-8- alkylester, α-Cyanacrylsäure-C1-8-alkylester (die Äthyl-, Butyl- oder Cyclohexylester sind bevorzugt), Styrol, Methylstyrol, Acrylnitril, Methacrylnitril oder α-Chloracrylnitril.For the copolymerization z. B. uses the following α , β- unsaturated comonomers. Methacrylic acid C 2-8 alkyl esters, acrylic acid-C 1-8 - alkyl esters, α-cyanoacrylic acid C 1-8 alkyl ester (the ethyl, butyl or cyclohexyl are preferred), styrene, methyl styrene, acrylonitrile, methacrylonitrile or α -Chloracrylonitrile.
Bevorzugt verwendete Copolymere werden durch Polymerisation von Methylmethacrylaten in Gegenwart von Glycidylacrylat und/oder Glycidylmethacrylat, vorzugsweise in Gegenwart von Glycidylmethacrylat hergestellt. Vorzugsweise enthalten solche Copolymere 0,1 bis 10 Gewichtsprozent, insbesondere 0,5 bis 6 Gewichtsprozent (bezogen auf die gesamte Polymermasse) der entsprechenden Glycidylverbindungen. 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, Dibenzolperoxid, 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 are preferably used by polymerizing methyl methacrylates in the presence of glycidyl acrylate and / or glycidyl methacrylate, preferably produced 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 will components a and b (light stabilizers and flame retardants) the monomers or prepolymers, at temperatures between about 20 and 150 ° C admixed, whereupon the polymerization in the presence of a polymerization catalyst, e.g. B. azo to isobutyronitrile, dibenzene peroxide, Dilauryl peroxide or tert-butoxy perpivalate is carried out. The Components a and b can also be melted by known methods Polymers and copolymers are incorporated, e.g. B. in 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 preferable to work between 3 and 30%, in particular 8 to 25% of components a and b, based on the weight of the monomers or Polymer masses. If a glycidyl acrylate or glycidyl methacrylate containing polymer stabilized, smaller amounts of stabilizers are used, e.g. B. only 3 to 25%, preferably 8 to 15% (again based on the weight of the mono- or polymer masses). It is to choose the ratio of components a: b so that in the polymer mass finally 0.01 to 0.5, preferably 0.02 to 0.2 percent by weight Light stabilizers are present, that is, the weight ratio a: b is about 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.
47,5 Teile frisch destilliertes Methylmethacrylat werden mit 0,04 Teilen Dilaurylperoxid, 0,03 Teilen Azoisobuttersäuredinitril, 2,5 Teilen der Verbindung der Formel 1a47.5 parts of freshly distilled methyl methacrylate are mixed with 0.04 parts Dilauryl peroxide, 0.03 part of azoisobutyronitrile, 2.5 parts of the Compound of formula 1a
und 0,1 Teil der Verbindung der Formel 1band 0.1 part of the compound of formula 1b
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 between two glass plates (with a rubber spacer on one Distance of 3 mm set) poured, the glass plates with transparent Adhesive tape secured, stored at 50 ° for 16 hours and then 4 Heated to 115 ° for hours.
Die erhaltene, tadellos transparente Platte zeigt sowohl sehr geringe Entflammbarkeit als auch ausgezeichnete Resistenz gegen Lichtschädigung.The perfectly transparent plate obtained shows both very small Flammability as well as excellent resistance to light damage.
In einem Arbury 200 Spritzguß-Extruder werden 90 Teile handelsübliches PMMA (Polymethylmethacrylat) mit 0,2 Teilen der Verbindung der Formel 1b (Beispiel 1) und 10 Teilen der Verbindung der Formel 2aIn an Arbury 200 injection molding extruder, 90 parts are commercially available PMMA (polymethyl methacrylate) with 0.2 parts of the compound of formula 1b (Example 1) and 10 parts of the compound of formula 2a
worin n im Mittel 2 ist, 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.wherein n is 2 on average, mixed at 200 ° to 220 ° and extruded into 3 mm thick plates. The work pieces thus obtained are characterized by good light stability and low flammability.
Gemäß der Arbeitsvorschrift des Beispiels 2 werden PMMA-Platten hergestellt, die jedoch an Stelle des dort verwendeten UV-Absorbers (Verbindung 1b) die gleiche Menge der Verbindung 3a, bzw. 4a enthalten.According to the working procedure of Example 2, PMMA boards are produced but instead of the UV absorber used there (connection 1b) contain the same amount of compound 3a or 4a.
Claims (7)
- 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) enthalten.
- a) an oxalic acid anilide or 2,2,6,6-tetramethylpiperidine compound (component a) as a stabilizer against light damage and
- b) contain a flame retardant organic phosphorus compound (component b).
R unabhängig voneinander Wasserstoff oder Methyl, die beiden
R₁ unabhängig voneinander Wasserstoff, C1-18-Alkyl, C1-18-Alkoxy, Halogen, Hydroxy, Phenyl oder Phenoxy und die beiden
R₂ unabhängig voneinander Wasserstoff, Halogen, Hydroxy, C1-18-Alkyl oder C1-18-Alkoxy bedeuten. 2. Methyl methacrylate polymers and copolymers according to claim 1, wherein component a is a compound of formula I. where the two
R independently of one another hydrogen or methyl, the two
R₁ is independently hydrogen, C 1-18 alkyl, C 1-18 alkoxy, halogen, hydroxy, phenyl or phenoxy and the two
R₂ are independently hydrogen, halogen, hydroxy, C 1-18 alkyl or C 1-18 alkoxy.
R Wasserstoff, die beiden
R₁ Wasserstoff, Hydroxy, C1-4-Alkyl oder C1-4-Alkoxy, vorzugsweise Wasserstoff, und die beiden
R₂ unabhängig voneinander Wasserstoff, Hydroxy, C1-4-Alkyl oder C1-4-Alkoxy, vorzugsweise ein R₂ an jedem Benzolring Wasserstoff, das andere R₂ an einem Benzolring C1-4-Alkyl, und am anderen Benzolring C1-4-Alkoxy
bedeuten.3. methyl methacrylate polymers and copolymers of formula I, according to claim 2, wherein the two
R hydrogen, the two
R₁ is hydrogen, hydroxy, C 1-4 alkyl or C 1-4 alkoxy, preferably hydrogen, and the two
R₂ independently of one another hydrogen, hydroxyl, C 1-4 alkyl or C 1-4 alkoxy, preferably one R₂ on each benzene ring hydrogen, the other R₂ on a benzene ring C 1-4 alkyl, and on the other benzene ring C 1-4 -Alkoxy
mean.
R₁₀ Wasserstoff, Sauerstoff, C1-8-Alkyl oder eine Gruppe der Formel -CO-R₁₅,
R₁₁ Wasserstoff, C1-22-Alkyl, C1-22-Alkoxy oder eine Gruppe der Formel -N(R)-CO-CO-R₂₀, -NH-C(R)=N-R₂₁, oder R₁₂ Wasserstoff oder C1-8-Alkyl oder R₁₁ und R₁₂ gemeinsam, mit dem an sie gebundenen Kohlenstoffatom eine Gruppe der Formel a, R₁₅ Wasserstoff, C1-6-Alkyl, Phenyl, Benzyl, Benzoyl, Carboxy oder eine Gruppe der Formel -C(R)=CH₂, -CO-O-C1-12-Alkyl oder -NR₁₇R₁₈,
R₁₇ Wasserstoff, C1-12-Alkyl, C5-6-Cycloalkyl, Phenyl, Phenyl-C1-4-alkyl oder C1-12-Alkyl-phenyl,
R₁₈ Wasserstoff oder C1-12-Alkyl,
R₂₀ eine Amid-bildende Gruppe und
R₂₁ C1-18-Alkyl, unsubstituiertes oder bis zu 3 Substituenten aus der Gruppe Halogen, C1-18-Alkyl und C1-4-Alkoxy tragendes Phenyl und
R Wasserstoff oder Methyl
bedeuten.4. Methyl methacrylate polymers and copolymers according to claim 1, wherein component a is a compound of formula II wherein
R₁₀ is hydrogen, oxygen, C 1-8 alkyl or a group of the formula -CO-R₁₅,
R₁₁ is hydrogen, C 1-22 alkyl, C 1-22 alkoxy or a group of the formula -N (R) -CO-CO-R₂₀, -NH-C (R) = N-R₂₁, or R₁₂ is hydrogen or C 1-8 alkyl or R₁₁ and R₁₂ together, with the carbon atom attached to them a group of the formula a, R₁₅ is hydrogen, C 1-6 -alkyl, phenyl, benzyl, benzoyl, carboxy or a group of the formula -C (R) = CH₂, -CO-OC 1-12 -alkyl or -NR₁₈R₁₈,
R₁₇ is hydrogen, C 1-12 alkyl, C 5-6 cycloalkyl, phenyl, phenyl-C 1-4 alkyl or C 1-12 alkylphenyl,
R₁₈ is hydrogen or C 1-12 alkyl,
R₂₀ is an amide-forming group and
R₂₁ C 1-18 alkyl, unsubstituted or up to 3 substituents from the group halogen, C 1-18 alkyl and C 1-4 alkoxy-bearing phenyl and
R is hydrogen or methyl
mean.
R unabhängig voneinander Wasserstoff oder Methyl, alle
R₃ unabhängig voneinander Wasserstoff, C1-6-Alkyl, das ein oder zwei Halogenatome als Substituenten tragen kann oder unsubstituiertes oder ein Halogenatom oder eine C1-4-Alkoxygruppe tragendes C2-6-Alkenyl oder Phenyl, vorzugsweise Chlor- oder Brom-C1-4-Alkyl, insbesondere β-Chloräthyl,
R₄ C1-17-Alkyl, vorzugsweise Methyl oder Äthyl, insbesondere Methyl, oder
R₅ Wasserstoff oder Halogen, vorzugsweise Wasserstoff, Chlor oder Brom, insbesondere Chlor,
R₆ C1-4-Alkylen, die beiden
R₇ unabhängig voneinander eine der Bedeutungen von R₃,
n eine ganze Zahl von 1 bis 10 vorzugsweise im Mittel 2 und
X Sauerstoff oder Schwefel bedeuten.5. methyl methacrylate polymers and copolymers according to any one of the preceding claims, wherein component b is a compound of formula III or IV, where the two
R independently of one another hydrogen or methyl, all
R₃ independently of one another are hydrogen, C 1-6 -alkyl, which can carry one or two halogen atoms as substituents or unsubstituted or C 2-6 alkenyl or phenyl, preferably chlorine or bromine, or a C 1-4 alkoxy group C 1-4 alkyl, especially β- chloroethyl,
R₄ C 1-17 alkyl, preferably methyl or ethyl, especially methyl, or
R₅ is hydrogen or halogen, preferably hydrogen, chlorine or bromine, especially chlorine,
R₆ C 1-4 alkylene, the two
R₇ independently of one another have one of the meanings of R₃,
n is an integer from 1 to 10, preferably on average 2 and
X is oxygen or sulfur.
R′₇ unabhängig voneinander Wasserstoff, Methyl oder Äthyl und
X Sauerstoff oder Schwefel bedeuten.7. methyl methacrylate polymers and copolymers according to claim 5, wherein the compound of formula IV corresponds to formula IV ' where the two
R'₇ independently of one another hydrogen, methyl or ethyl and
X is oxygen or sulfur.
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 |
|---|---|
| DE3838480A1 true DE3838480A1 (en) | 1989-06-08 |
Family
ID=10627436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE3838480A Withdrawn DE3838480A1 (en) | 1987-11-24 | 1988-11-12 | LIGHT STABILIZED FLAME RESISTANT METHYL METHACRYLATE POLYMERS AND COPOLYMERS |
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) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1148090A1 (en) * | 2000-04-17 | 2001-10-24 | Clariant Finance (BVI) Limited | Flame retardant polymers |
| US6716950B2 (en) * | 2000-08-11 | 2004-04-06 | Roehm Gmbh & Co. Kg | Material for solar benches |
| 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 |
| EP1777257A2 (en) * | 2005-10-20 | 2007-04-25 | Arkema France | Fireproof methacrylic composition |
| FR2892422A1 (en) * | 2005-10-20 | 2007-04-27 | Arkema Sa | Fire-proof methacrylic composition, useful to manufacture cover e.g. for television set, comprises a methacrylic polymer and a fire-proofing phosphorus compound |
| WO2010054906A1 (en) * | 2008-11-13 | 2010-05-20 | Evonik Röhm Gmbh | Molding compounds for the production of solar cell modules |
| DE102008043713A1 (en) | 2008-11-13 | 2010-05-20 | Evonik Röhm Gmbh | Production of solar cell modules |
| DE102010030508A1 (en) | 2010-06-25 | 2011-12-29 | Evonik Röhm Gmbh | Production of solar cell modules |
Families Citing this family (4)
| 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 |
| 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 |
| WO2016088767A1 (en) * | 2014-12-05 | 2016-06-09 | 大日精化工業株式会社 | Manufacturing method for granular resin additive, granular resin additive obtained by said manufacturing method, thermoplastic resin composition, and molded article |
| WO2018033502A1 (en) * | 2016-08-15 | 2018-02-22 | 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 GB GB8827132A patent/GB2212807B/en not_active Expired - Lifetime
- 1988-11-21 CH CH4307/88A patent/CH676242A5/de not_active IP Right Cessation
- 1988-11-22 JP JP63293733A patent/JPH01167357A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1148090A1 (en) * | 2000-04-17 | 2001-10-24 | Clariant Finance (BVI) Limited | Flame retardant polymers |
| US6716950B2 (en) * | 2000-08-11 | 2004-04-06 | Roehm Gmbh & Co. Kg | Material for solar benches |
| 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 |
| EP1777257A2 (en) * | 2005-10-20 | 2007-04-25 | Arkema France | Fireproof methacrylic composition |
| FR2892422A1 (en) * | 2005-10-20 | 2007-04-27 | Arkema Sa | Fire-proof methacrylic composition, useful to manufacture cover e.g. for television set, comprises a methacrylic polymer and a fire-proofing phosphorus compound |
| EP1777257A3 (en) * | 2005-10-20 | 2011-03-23 | Arkema France | Fireproof methacrylic composition |
| WO2010054906A1 (en) * | 2008-11-13 | 2010-05-20 | Evonik Röhm Gmbh | Molding compounds for the 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 |
| DE102008043713A1 (en) | 2008-11-13 | 2010-05-20 | Evonik Röhm Gmbh | Production of solar cell modules |
| DE102010030508A1 (en) | 2010-06-25 | 2011-12-29 | Evonik Röhm Gmbh | Production of solar cell modules |
| WO2011160925A1 (en) | 2010-06-25 | 2011-12-29 | Evonik Röhm Gmbh | Production of solar cell modules |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01167357A (en) | 1989-07-03 |
| GB2212807B (en) | 1991-08-14 |
| GB2212807A (en) | 1989-08-02 |
| GB8827132D0 (en) | 1988-12-29 |
| GB8727452D0 (en) | 1987-12-23 |
| IT8848573A0 (en) | 1988-11-21 |
| IT1224575B (en) | 1990-10-04 |
| CH676242A5 (en) | 1990-12-28 |
| FR2623515A1 (en) | 1989-05-26 |
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