CH667275A5 - FLAME RETARDED METHYL METHACRYLATE POLYMER AND COPOLYMER. - Google Patents
FLAME RETARDED METHYL METHACRYLATE POLYMER AND COPOLYMER. Download PDFInfo
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- CH667275A5 CH667275A5 CH967/86A CH96786A CH667275A5 CH 667275 A5 CH667275 A5 CH 667275A5 CH 967/86 A CH967/86 A CH 967/86A CH 96786 A CH96786 A CH 96786A CH 667275 A5 CH667275 A5 CH 667275A5
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- Prior art keywords
- alkyl
- methyl methacrylate
- hydrogen
- parts
- flame
- Prior art date
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims description 21
- 229920000642 polymer Polymers 0.000 title claims description 17
- 229920001577 copolymer Polymers 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 239000003063 flame retardant Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 229910052717 sulfur Chemical group 0.000 claims description 3
- 239000011593 sulfur Chemical group 0.000 claims description 3
- 239000012757 flame retardant agent Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004849 alkoxymethyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000011521 glass Substances 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 241000251730 Chondrichthyes Species 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001746 injection moulding Methods 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
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-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
- 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 239000003963 antioxidant agent Substances 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- -1 glycidyl compound Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 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
- C08K5/52—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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
BESCHREIBUNG Die vorliegende Erfindung betrifft Methylmethacrylatpo-30 lymere und Copolymere, welche ausgewählte Phosphorverbindungen als flammhemmende Mittel enthalten. DESCRIPTION The present invention relates to methyl methacrylate polymers and copolymers which contain selected phosphorus compounds as flame retardants.
So betrifft die Erfindung flammgehemmte Methylmethacrylatpolymere und -copolymere, welche als flammhem-mende Mittel mindestens eine Verbindung der Formel I The invention thus relates to flame-retardant methyl methacrylate polymers and copolymers which, as flame-retardant agents, comprise at least one compound of the formula I.
35 35
R. R_ R, X CL 0 R. R_ R, X CL 0
1\ / \« 1\ / \"
CA 1 CA 1
enthalten, worin included in what
Ri unabhängig voneinander Wasserstoff, Alkyl(Ci^), Phe-nyl, -CO-O-Alkyl(C^), -CH2-0-Alkyl(C,_2), Ri independently of one another hydrogen, alkyl (Ci ^), phenyl, -CO-O-alkyl (C ^), -CH2-0-alkyl (C, _2),
R2a und R2b unabhängig voneinander Wasserstoff, Alkyl(Ci^t), -CO-O-Alkyl(C^), R2a and R2b independently of one another hydrogen, alkyl (Ci ^ t), -CO-O-alkyl (C ^),
R3 und R» unabhängig voneinander Wasserstoff oder Alkyl(C^), R3 and R »independently of one another are hydrogen or alkyl (C ^),
R5 unabhängig voneinander Wasserstoff oder Methyl und X Sauerstoff oder Schwefel bedeuten. R5 are independently hydrogen or methyl and X is oxygen or sulfur.
In der obigen Formel I bedeutet R[ jeweils vorzugsweise R'i, d.h. Wasserstoff, Alkyl(Ci^), (Ci,2)-Alkoxymethyl oder (C ! ,2)-Al ko xy carbo nyl, vorzugsweise R"i, d.h. Alkyl(Ci_3), In formula I above, R [preferably each represents R'i, i.e. Hydrogen, alkyl (Ci ^), (Ci, 2) -alkoxymethyl or (C!, 2) -Al ko xy carbo nyl, preferably R "i, i.e. alkyl (Ci_3),
vorzugsweise Alkyl(C12) und dieses insbesondere Methyl. preferably alkyl (C12) and this in particular methyl.
R2a bedeutet jeweils vorzugsweise R'2a, d.h. Wasserstoff, Alkyl(Ci^t) oder (Ci>2)-Alkoxycarbonyl, vorzugsweise R"2a, d.h. Alkyl(C2^), vorzugsweise Alkyl(C2(3), insbesondere 50 Äthyl. R2b bedeutet vorzugsweise R'2b, d.h. Wasserstoff, Alkyl(C|^) oder (C[ 2)-Alkoxycarbonyl, vorzugsweise R"2b, d.h. Alkyl(Ci_3), vorzugsweise Methyl. R3 bedeutet vorzugsweise R'3, d.h. Wasserstoff oder Alky^Cu), vorzugsweise Wasserstoff. R4 und R5 bedeuten vorzugsweise Wasserstoff. X 55 bedeutet vorzugsweise Sauerstoff. R2a each preferably denotes R'2a, i.e. Hydrogen, alkyl (Ci ^ t) or (Ci> 2) alkoxycarbonyl, preferably R "2a, ie alkyl (C2 ^), preferably alkyl (C2 (3), in particular 50 ethyl. R2b preferably means R'2b, ie hydrogen , Alkyl (C | ^) or (C [2) -alkoxycarbonyl, preferably R "2b, ie alkyl (Ci_3), preferably methyl. R3 preferably denotes R'3, ie hydrogen or alky ^ Cu), preferably hydrogen. R4 and R5 are preferably hydrogen. X 55 preferably means oxygen.
Bevorzugt sind Verbindungen der Formel Compounds of the formula are preferred
0 /°—CH2 0 / ° —CH2
X' X '
0 CH R 0 CH R
2b 2 B
Ia, Yes,
und insbesondere and particularly
3 3rd
667 275 667 275
CH, .CHÄ-R2"a CH?- CH, .CHÄ-R2 "a CH? -
î/ î /
-0 P -0 p
-CH, .CH, -CH, .CH,
S./ S. /
Ib. Ib.
./ \ ./ \
R" 2 b R "2 b
Die Verbindungen der Formel I stellt man in an sich bekannter Weise her, zum Beispiel durch Umsetzung eines Mol einer Verbindung der Formel II The compounds of the formula I are prepared in a manner known per se, for example by reacting one mole of a compound of the formula II
R. ,Re ' R., Re '
"Hai "Shark
\ / \ /
», )c—u, )/ »,) C — u,) /
«2a XÇ«—»' R* «2a XÇ« - »'R *
worin Hai Chlor oder Brom bedeutet, mit einem Mol einer Verbindung der Formel III wherein shark is chlorine or bromine, with one mole of a compound of formula III
R4 /R5 R4 / R5
Ve- Ve
Nc Nc
\» Np- \ »Np-
,<v y , <v y
CH CH
I I.
R R
worin Hai Chlor oder Brom und X Sauerstoff oder Schwefel bedeuten, und 1 Mol Wasser, in Gegenwart eines Halogenwasserstoffakzeptors, z.B. Pyridin. wherein shark is chlorine or bromine and X is oxygen or sulfur, and 1 mole of water in the presence of a hydrogen halide acceptor, e.g. Pyridine.
Die Verbindungen der Formel I werden erfindungsgemäss zum flammhemmenden Ausrüsten von Methylmethacrylatpo-lymeren und Copolymeren verwendet. Überraschenderweise zeigen Verbindungen der Formel I gemäss der obigen Definition, worin R3 eine von Wasserstoff verschiedene Bedeutung hat oder R] oder R2a und R2b eine von Aethyl verschiedene Bedeutung haben, eine bessere Löslichkeit in monomerem Methylmethacrylat und können darum schon vor der Polymerisation derselben eingesetzt werden. Die Verbindung 8 der Tabelle und ähnliche Verbindungen mit schlechterer Löslichkeit in Methylmethacrylat können jedoch (gemäss Beispiel 6) in einer geeigneten Apparatur (z. B. in einem Extruder) ohne weiteres bei Schmelztemperatur in Polymethylmethacrylat eingearbeitet werden und entfalten dann die gleiche Wirkung wie die übrigen Verbindungen. According to the invention, the compounds of the formula I are used for the flame-retardant finishing of methyl methacrylate polymers and copolymers. Surprisingly, compounds of the formula I according to the above definition, in which R3 has a meaning different from hydrogen or R] or R2a and R2b have a meaning other than ethyl, show better solubility in monomeric methyl methacrylate and can therefore be used even before the polymerization thereof. However, compound 8 in the table and similar compounds with poorer solubility in methyl methacrylate (according to example 6) can be easily incorporated into polymethyl methacrylate at a melting temperature in a suitable apparatus (e.g. in an extruder) and then develop the same effect as the others Links.
Die Methylmethacrylatpolymere werden in an sich bekannter Weise durch Polymerisation von Methylmethacrylat mit gegebenenfalls weiteren Comonomeren erhalten. Für die Herstellung von Copolymerisaten kommen als Comono-mere a, ß-einfach ungesättigte Verbindungen, z.B. Alkyl-(C2_ 8)ester der Methacrylsäure oder Alkyl-(Ci_8)ester der Acryl-säure, Alkyl-(Ci_8)ester der a-Cyanacrylsäure wie die entsprechenden Äthyl-, Butyl- oder Cyclohexylester, im weiteren auch Styrol, Methylstyrol, Acrylnitril, Methacrylnitril, a-Chloracrylnitril und verwandte Verbindungen in Frage, vorzugsweise Alkyl-(C2-8)-methacrylate oder Alkyl-(Ci_8)-acry-late. The methyl methacrylate polymers are obtained in a manner known per se by polymerizing methyl methacrylate with optionally further comonomers. Comonomers for the preparation of copolymers are a, β-monounsaturated compounds, e.g. Alkyl (C2_8) esters of methacrylic acid or alkyl (Ci_8) esters of acrylic acid, alkyl (Ci_8) esters of a-cyanoacrylic acid such as the corresponding ethyl, butyl or cyclohexyl ester, and also styrene, methylstyrene, acrylonitrile , Methacrylonitrile, a-chloroacrylonitrile and related compounds in question, preferably alkyl (C2-8) methacrylates or alkyl (Ci_8) acrylic latex.
Eine bevorzugte Form eines Copolymerisates wird erhalten, wenn die Polymerisation des Methylmethacrylates in Gegenwart von Glycidylacrylat und/oder Glycidylmethacry-lat, vorzugsweise Glycidylmethacrylat, durchgeführt wird. Vorzugsweise enthalten die Methylmethacrylatpolymeren A preferred form of a copolymer is obtained when the polymerization of the methyl methacrylate is carried out in the presence of glycidyl acrylate and / or glycidyl methacrylate, preferably glycidyl methacrylate. The methyl methacrylate polymers preferably contain
0,1-10 Gew.% und bevorzugt 0,5-6 Gew.% der Glycidylver-bindung, bezogen auf die Summe von Methylmethacrylat, io und gegebenenfalls weitere Comonomere. 0.1-10% by weight and preferably 0.5-6% by weight of the glycidyl compound, based on the sum of methyl methacrylate, 10% and optionally further comonomers.
Zur Einarbeitung der flammhemmenden Mittel in die Methylmethacrylatpolymeren können die verschiedenen bekannten Verfahren angewendet werden. Verbindungen der (II), Formel I oder deren Gemische können den Monomeren bzw. i5 den Präpolymeren beigemischt werden, wobei sich die Verbindungen bei einer Temperatur von 20-60 ° C lösen sollen. Darauf werden die erfindungsgemässen flammgehemmten Polymere in an sich bekannter Weise, vorzugsweise mittels Blockpolymerisation in Gegenwart von Polymerisationskata-20 lysatoren, z. B. Azo- bis -isobutyronitril, Dibenzoylperoxid, Dilaurylperoxid oder Tertiärbutoxyperpivalat, hergestellt. Die flammhemmenden Mittel können auch in das geschmolzene Polymere eingearbeitet werden, worauf man das geschmolzene Material nach an sich bekannten Methoden, 25 z. B. Spritzguss oder Extrusion, in geformte Teile überführt. Bevorzugt verwendet man 3-30 Gew.%, vorzugsweise 8-25 Gew.% der Verbindungen der Formel I oder deren Gemische Hai (III), bezogen auf die eingesetzten Monomeren bzw. auf das einge setzte Polymer. The various known methods can be used to incorporate the flame retardants into the methyl methacrylate polymers. Compounds of (II), formula I or mixtures thereof can be added to the monomers or i5 to the prepolymers, the compounds being said to dissolve at a temperature of 20-60 ° C. The flame-retardant polymers according to the invention are then analyzed in a manner known per se, preferably by means of block polymerization in the presence of polymerization catalysts, e.g. B. azo bis isobutyronitrile, dibenzoyl peroxide, dilauryl peroxide or tertiary butoxyperpivalate. The flame retardants can also be incorporated into the molten polymer, whereupon the molten material can be prepared by methods known per se, e.g. B. injection molding or extrusion, converted into molded parts. It is preferred to use 3-30% by weight, preferably 8-25% by weight, of the compounds of the formula I or their mixtures of shark (III), based on the monomers used or on the polymer used.
30 Die Herstellung erfindungsgemäss flammgehemmter Copolymeren des Methylmethacrylats und gegebenenfalls weiterer Comonomerer mit Glycidylacrylat und/oder Glycidylmethacrylat erfolgt ausschliesslich mittels Blockpolymerisation. In diesem Falle verwendet man bevorzugt 3-25 35 Gew.%, vorzugsweise 8-15 Gew.% der Verbindungen der Formel I oder deren Gemische bezogen auf die eingesetzten Monomeren. 30 The flame-retardant copolymers of methyl methacrylate and, if appropriate, further comonomers with glycidyl acrylate and / or glycidyl methacrylate are produced exclusively by means of block polymerization. In this case, 3-25 35% by weight, preferably 8-15% by weight, of the compounds of the formula I or their mixtures, based on the monomers used, are preferably used.
Weitere Additive können zugegeben werden, z.B. Polymerisationsregler, Weichmacher, UV-Stabilisatoren, Antioxyd-40 antien, Pigmente usw. Die flammgehemmten Methylmethacrylatpolymeren können in an sich bekannter Weise weiter zu Formkörpern, z.B. Platten, Rohren oder Folien verarbeitet werden. Other additives can be added, e.g. Polymerization regulators, plasticizers, UV stabilizers, antioxidants, antigens, pigments, etc. The flame-retardant methyl methacrylate polymers can be further formed into shaped articles, e.g. Sheets, pipes or foils can be processed.
In den folgenden Beispielen bedeuten die Teile Gewichts-45 teile; die Prozente Gewichtsprozente. Die Temperaturen sind in Celsiusgraden angegeben. In the following examples the parts mean 45 parts by weight; the percentages by weight. The temperatures are given in degrees Celsius.
Beispiel 1 example 1
In einem Rührgefäss werden 23,6 Teile 2-Äthyl-2-methyl-5o 1,3-propandiol bei 50° geschmolzen. Es werden 30,7 Teile Phosphoroxytrichlorid zugetropft und die Mischung 15 Stunden bei Raumtemperatur gerührt. Anschliesend wird im Vakuum 1 Stunde auf 50° erwärmt. Zum erhaltenen Kristallbrei werden bei Raumtemperatur 21 Teile Pyridin und 1,8 55 Teile Wasser gegeben und die Mischung 1 Stunde bei Raumtemperatur, anschliessend 4 Stunden bei 40° gerührt. Nach beendeter Reaktion kühlt man auf Raumtemperatur und filtriert vom Niederschlag ab. Nach dem Einengen der organischen Phase wird der Rückstand in Toluol aufgenommen, 6o mehrmals mit verdünnter wässriger Salzsäure gewaschen und über Natriumsulfat getrocknet. Danach wird das organische Lösungsmittel abdestilliert. 23.6 parts of 2-ethyl-2-methyl-5o-1,3-propanediol are melted at 50 ° in a stirred vessel. 30.7 parts of phosphorus oxytrichloride are added dropwise and the mixture is stirred at room temperature for 15 hours. The mixture is then heated to 50 ° in a vacuum for 1 hour. 21 parts of pyridine and 1.8 55 parts of water are added to the crystal slurry obtained at room temperature and the mixture is stirred at room temperature for 1 hour and then at 40 ° for 4 hours. When the reaction is complete, the mixture is cooled to room temperature and the precipitate is filtered off. After concentrating the organic phase, the residue is taken up in toluene, washed several times with dilute aqueous hydrochloric acid and dried over sodium sulfate. The organic solvent is then distilled off.
Man erhält die Verbindung Nr. 1 der Tabelle 1. In analoger Weise erhält man die anderen Verbindungen 65 der Tabelle 1. Compound No. 1 in Table 1 is obtained. The other compounds 65 in Table 1 are obtained in an analogous manner.
Beispiel 2 Example 2
a) Man verfährt gemäss Beispiel 1, verwendet jedoch ein a) The procedure is as in Example 1, but one is used
667 275 667 275
4 4th
Gemisch von 10,4 Teilen 2,2-Dimethyl-l,3-propandiol und 11,8 Teilen 2-Äthyl-2-methyl-l,3-propandiol, welches man mit 30,7 Teilen Phosphoroxychlorid umsetzt. Man erhält so ein Gemisch gemäss Nr. 12 der Tabelle 1 der Formel Mixture of 10.4 parts of 2,2-dimethyl-l, 3-propanediol and 11.8 parts of 2-ethyl-2-methyl-l, 3-propanediol, which is reacted with 30.7 parts of phosphorus oxychloride. A mixture according to No. 12 of Table 1 of the formula is thus obtained
Beispiel 4 Example 4
Man verfährt wie im Beispiel 3, verwendet jedoch 25 Teile einer Mischung gemäss Beispiel 2a. Man erhält selbstverlöschendes Verhalten. The procedure is as in Example 3, but 25 parts of a mixture according to Example 2a are used. You get self-extinguishing behavior.
worin die Anteile mittels HPLC wie folgt ermittelt wurden: Ra = Rb = CHJ: 5,2 Teile where the proportions were determined by HPLC as follows: Ra = Rb = CHJ: 5.2 parts
Ra = Rb = C2H5 : 6,2 Teile Ra = Rb = C2H5: 6.2 parts
Ra = CH3, Rb = C2H5 : 12,0 Teile b) Verwendet man als Ausgangsmaterial 13,2 Teile 2-Methyl-2-n-propyl-l,3-propandiol mit 10,4 Teilen 2,2-Dimethyl-l,3-propandiol, so erhält man die folgenden Anteile im Gemisch (Bsp. 13 der Tabelle): Ra = CH3, Rb = C2H5: 12.0 parts b) If 13.2 parts of 2-methyl-2-n-propyl-l, 3-propanediol with 10.4 parts of 2,2-dimethyl-l are used as the starting material, 3-propanediol, the following proportions are obtained in the mixture (Ex. 13 of the table):
Ra=Rb = CH3: 3,9 Teile Ra = Rb = CH3: 3.9 parts
Ra = Rb = CîHt : 5,9 Teile Ra = Rb = CîHt: 5.9 parts
Ra = CHb, Rb = C3H7(n): 11,4 Teile c) In analoger Weise stellt man die Verbindung Nr. 14 her, die im Gemisch zu 46,4 Gew.% und die symmetrische Verbindung mit zwei n-Propylresten zu 36,3 Gew.% vorhanden ist. Die symmetrische Verbindung, worin Ra = Rb = CH3, ist zu 17,3% vorhanden. Ra = CHb, Rb = C3H7 (n): 11.4 parts c) In an analogous manner, compound No. 14 is prepared, the mixture of 46.4% by weight and the symmetrical compound with two n-propyl residues of 36 , 3% by weight is present. The symmetrical compound, in which Ra = Rb = CH3, is 17.3% present.
Beispiel 3 Example 3
100 Teile frisch destilliertes Methylmethacrylat werden mit 0,08 Teilen Dilaurylperoxid, 0,06 Teilen Azoisobuttersäu-redinitril und 20 Teilen der Verbindung Nr. 1 der Tabelle gut vermischt. Die Mischung wird kurz zum Sieden erwärmt und zwischen Glasplatten gegossen, die mit Gummiplatten und Klebstreifen seitlich abgedichtet sind. Die Glasplatten werden 16 Stunden bei 50° im Wasserbad und danach 3 Stunden bei 100° im Trockenschrank erhitzt. Nach Ablösen der Glasplatten erhält man 3 mm dicke Platten. 100 parts of freshly distilled methyl methacrylate are mixed well with 0.08 part of dilauryl peroxide, 0.06 part of azoisobutyric acid redinitrile and 20 parts of compound no. 1 in the table. The mixture is briefly heated to boiling and poured between glass plates that are sealed on the side with rubber plates and adhesive strips. The glass plates are heated in a water bath at 50 ° for 16 hours and then in a drying cabinet at 100 ° for 3 hours. After the glass plates have been removed, 3 mm thick plates are obtained.
Die Platten zeigen nach ASTM D 635 selbstverlöschendes Verhalten. The plates show self-extinguishing behavior in accordance with ASTM D 635.
Beispiel 5 Example 5
100 Teile frisch destilliertes Methylmethacrylat werden 10 mit 2,2 Teilen Glycidylmethacrylat, 0,1 Teilen Dilaurylperoxid, 0,08 Teilen Azoisobuttersäuredinitril und 8,3 Teilen der Verbindung 1 der Tabelle gut vermischt. Die Mischung wird kurz zum Sieden erwärmt und zwischen Glasplatten gegossen, die mit Gummiplatten und Klebstreifen seitlich abge-15 dichtet sind. Die Glasplatten werden 16 Stunden bei 50° im Wasserbad und danach 3 Stunden bei 100° im Trockenschrank erhitzt. Nach Ablösen der Glasplatten erhält man 3 mm dicke Platten. 100 parts of freshly distilled methyl methacrylate are mixed 10 well with 2.2 parts of glycidyl methacrylate, 0.1 part of dilauryl peroxide, 0.08 part of azoisobutyronitrile and 8.3 parts of compound 1 in the table. The mixture is briefly heated to boiling and poured between glass plates, which are sealed on the sides with rubber plates and adhesive strips. The glass plates are heated in a water bath at 50 ° for 16 hours and then in a drying cabinet at 100 ° for 3 hours. After the glass plates have been removed, 3 mm thick plates are obtained.
Die Platten zeigen nach ASTM D 635 selbstverlöschendes 20 Verhalten. Entsprechend hergestellte Platten ohne Verwendung von Glycidylmethacrylat brennen bei diesem Test durch. The plates show self-extinguishing behavior in accordance with ASTM D 635. Correspondingly produced plates without the use of glycidyl methacrylate burn out in this test.
Beispiel 6 Example 6
300 Teile eines handelsüblichen Polymethylmethacrylat-Granulats vom mittleren Molekulargewicht 120 000 werden 4 Stunden bei 80° und einem Vakuum von 20 mm Hg getrock-30 net und mit 53 Teilen einer Verbindung der Nr. 8 in einer Schüttelmaschine trocken vermischt. Die Mischung wird bei 230° zu einem Strang extrudiert, welcher anschliessend granuliert wird. Das so erhaltene Granulat wird 6 Stunden bei 80° und einem Vakuum von 20 mm Hg getrocknet und 35 danach in einer Spritzgussmaschine zu 3 mm dicken Platten verformt. Die Platten werden nach der Methode des Sauerstoffindex (ASTM D 2863-77) geprüft und erreichen gute Werte. Sie zeigen nach ASTM D 635 selbstverlöschendes Verhalten. 300 parts of a commercially available polymethyl methacrylate granulate with an average molecular weight of 120,000 are dried for 4 hours at 80 ° and a vacuum of 20 mm Hg and mixed dry with 53 parts of a compound of No. 8 in a shaker. The mixture is extruded at 230 ° to a strand, which is then granulated. The granules obtained in this way are dried for 6 hours at 80 ° and a vacuum of 20 mm Hg and then 35 molded into 3 mm thick plates in an injection molding machine. The plates are tested according to the oxygen index method (ASTM D 2863-77) and achieve good values. They show self-extinguishing behavior according to ASTM D 635.
40 Die übrigen Verbindungen der Tabelle 1 verwendet man in analoger Weise zu den Beispielen 3-6. 40 The other compounds in Table 1 are used in an analogous manner to Examples 3-6.
Tabelle table
Nr. No.
Struktur structure
ït>. (°C) ït>. (° C)
CH3n>c/CH2( CH3n> c / CH2 (
C2U5^ C2U5 ^
154 - 155 154-155
ch3 /CH20 ch3 / CH20
CK3 ^ÇHO l c3H7(n)_ CK3 ^ ÇHO l c3H7 (n) _
134 - 138 134-138
CH, CH,
\ \
(n)C3H? (n) C3H?
ch2o ch2o
C' —0 C '-0
62 - 65 62-65
5 5
667 275 667 275
Nr. No.
10 10th
11 11
12 12
Struktur structure
13 13
CHk CHk
^CH2O ^ CH2O
/ C88c)C4Hg / C88c) C4Hg
^CH20 ^ CH20
CH, !> CH,!>
^CH2o ^ CH2o
ch3 ch3
CHO ' CHO '
/f h2c / f h2c
^CHr ^ CHr
:h- :H-
ch, ch,
T— 0 _ T— 0 _
CjHJO-Ö^ .Ch'20. CjHJO-Ö ^ .Ch'20.
C P- C P-
W-^ CSjO-^J W- ^ CSjO- ^ J
2!I5\ /"ÎV 2! I5 \ / "ÎV
- r N> - r N>
c2h5 c2h5
C2H50CH2 C2H50CH2
•CH20' 0 • CH20 '0
ch2o ch2o
CH CH
C.H20' 0 C.H20 '0
,CHoO. , CHoO.
ch3och2 ^v„2v ch3och2 ^ v „2v
CH. CH.
OHjO^J OHjO ^ J
-OCH -Oh
2 2nd
•2\< • 2 \ <
ch2o ch2o
—o—y . ch20 [J J^XJCHjf —O — y. ch20 [J J ^ XJCHjf
CH. CH.
CH. CH.
CH3. .CH20 /<>CH~ CH3 CH3. .CH20 / <> CH ~ CH3
c^ —o—^cr c ^ —o— ^ cr
C3H7/ ^^CHgO jj 0 0CH2 C3H7 / ^^ CHgO jj 0 0CH2
CH. CH.
rp.(°c) rp. (° c)
78-80 78-80
115 - 116 115-116
m - ii4 m - ii4
103 - 104 103-104
134 - 136 134-136
flüssig liquid
97 - 99 97-99
115-122 115-122
*) *)
* enthält auch syrrrrstrischs Anteile ira Gemisch. * also contains syrrrrstrisch's ira mixture.
667 275 667 275
6 6
Hr. Mr.
Struktur structure
Fp. (°C) Mp (° C)
14 14
ö3\ ö3 \
/C\ /?" / C \ /? "
Oij CHO 0 Oij CHO 0
0 " "\ xc\ 0 "" \ xc \
o och£ oî3 o och £ oî3
*x) * x)
15 15
CH, CH-0 CH, CH-0
\ / 2 \ \ / 2 \
\c P-0-/ \ \ c P-0- / \
CH3 CH2O o CH3 CH2O or
.OCH-/ \ .OCH- / \
S ^0CH£ S ^ 0CH £
/CH3 / CH3
C\ C \
3 3rd
o un in o un in
* Enthält auch symmetrische Anteile im Gemisch. * Also contains symmetrical components in the mixture.
G G
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3510417 | 1985-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH667275A5 true CH667275A5 (en) | 1988-09-30 |
Family
ID=6266038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH967/86A CH667275A5 (en) | 1985-03-22 | 1986-03-10 | FLAME RETARDED METHYL METHACRYLATE POLYMER AND COPOLYMER. |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS61221256A (en) |
| AT (1) | AT389706B (en) |
| CH (1) | CH667275A5 (en) |
| FR (1) | FR2579212B1 (en) |
| GB (1) | GB2172600B (en) |
| IT (1) | IT1203753B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8727452D0 (en) * | 1987-11-24 | 1987-12-23 | Sandoz Ltd | 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH581163A5 (en) * | 1974-07-30 | 1976-10-29 | Sandoz Ag | |
| WO1980002844A1 (en) * | 1979-06-19 | 1980-12-24 | Sandoz Ag | Fire-proof acrylic polymers |
| FR2549074B1 (en) * | 1983-06-25 | 1987-04-30 | Sandoz Sa | NOVEL FLAME RETARDANT AND STABILIZING COMPOSITIONS OF POLYETHYLENE |
| DE3323761A1 (en) * | 1983-07-01 | 1985-01-03 | Robert Bosch Gmbh, 7000 Stuttgart | FUEL INJECTION PUMP FOR INTERNAL COMBUSTION ENGINES |
-
1986
- 1986-03-10 CH CH967/86A patent/CH667275A5/en not_active IP Right Cessation
- 1986-03-18 FR FR8603969A patent/FR2579212B1/en not_active Expired
- 1986-03-19 GB GB08606811A patent/GB2172600B/en not_active Expired
- 1986-03-20 IT IT47794/86A patent/IT1203753B/en active
- 1986-03-20 JP JP61060997A patent/JPS61221256A/en active Pending
- 1986-03-21 AT AT0075686A patent/AT389706B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2579212B1 (en) | 1988-11-10 |
| IT8647794A0 (en) | 1986-03-20 |
| AT389706B (en) | 1990-01-25 |
| IT1203753B (en) | 1989-02-23 |
| GB8606811D0 (en) | 1986-04-23 |
| GB2172600B (en) | 1988-07-20 |
| FR2579212A1 (en) | 1986-09-26 |
| ATA75686A (en) | 1989-06-15 |
| GB2172600A (en) | 1986-09-24 |
| JPS61221256A (en) | 1986-10-01 |
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| PL | Patent ceased |