GB2172600A - Flame retardant methyl methacrylate polymers - Google Patents
Flame retardant methyl methacrylate polymers Download PDFInfo
- Publication number
- GB2172600A GB2172600A GB08606811A GB8606811A GB2172600A GB 2172600 A GB2172600 A GB 2172600A GB 08606811 A GB08606811 A GB 08606811A GB 8606811 A GB8606811 A GB 8606811A GB 2172600 A GB2172600 A GB 2172600A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polymer
- alkyl
- formula
- compound
- hydrogen
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 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 title 1
- 239000003063 flame retardant Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005864 Sulphur Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 13
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 claims 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000011888 foil Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 7
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- VNAWKNVDKFZFSU-UHFFFAOYSA-N 2-ethyl-2-methylpropane-1,3-diol Chemical compound CCC(C)(CO)CO VNAWKNVDKFZFSU-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 acryionitrile Chemical compound 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101100073357 Streptomyces halstedii sch2 gene Proteins 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 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
- 150000002009 diols Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 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
- 239000007788 liquid Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 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 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)
Abstract
A methylmethacrylate polymer or co-polymer containing a flameproofing amount of a compound of formula I <IMAGE> in which each R1, independently, is hydrogen, C1-4alkyl, phenyl, -CO-O-C1-6 alkyl or -CH2-O-C1-2alkyl; R2 is hydrogen, C1-4alkyl or -CO-O-C1-6alkyl; R3 has a significance of R2 independent of R2; each R4 independently, is hydrogen or C1-4alkyl; each R5 independently, is hydrogen or methyl and X is oxygen or sulphur. These polymers may be used for forming tubes, sheets or foils.
Description
SPECIFICATION
Improvements in or relating to organic compounds
The invention relates to methylmethacrylate polymers and copolymers containing phosphoric flameproofing compounds.
According to the invention there is provided a methylmethacrylate polymer or copolymer containing a flameproofing amount of a compound of formula I
in which R1, independently, is hydrogen, C14alkyl, phenyl, -CO-O-C1-6alkyl or -CH2-O-C1-2alkyl;
R2 is hydrogen, C1 4alkyl or -CO-O-C1 6alkyl; each R4 independently, is hydrogen or C1 4alkyl; each Rg independently, is hydrogen or methyl and Xis oxygen or sulphur.
In this specification where a symbol appears more than once in a formula its significances are independent of one another. Unless stated to the contrary, C1 6alkyl is preferably C1-4alkyl which in turn is preferably methyl or ethyl.
Preferably R1 is R1 where R1 is hydrogen, C14alkyl, -CH2-O-C12akIyl or -CO-O-C1-2alkyl, R1 is more preferably R1'where R; is C1-3alkyf, preferably C1-2alkylm more preferably methyl.
Preferably R2 is R2 where R2 is hydrogen, C1-4alkyl or -CO-O-C1-2alkyl; more preferably R2 is R2'where R2 is C1-alkyl, preferably C1~2alkyl, more preferably ethyl.
Preferably R4 is R4' where R4 is hydrogen or C1~3alkyl, more preferably hydrogen.
Preferably Rs is hydrogen.
Preferably X is oxygen
Preferred compounds of formula 1 are of formula la
where the symbols are as defined above.
More preferred compounds of formula I are of formula Ib
where R2 is as defined above.
Compounds of formula I can be prepared from appropriate reactants by known methods for example by reacting 1 mole of a compound of formula II
in which R7 is chlorine or bromine with 1 mole of a compound of formula III
where the symbols are as defined above and 1 mole of water in the presence of hydrogen halide acceptor such as pyridine.
Polymers according to the invention can be prepared according to known methods from appropriate reactants, optionally with comonomers. For copolymerisation the following a, p-unsaturated comonomers may be used: C28alkyI ester of methacrylic acid, C1~8alkyl ester of acrylic acid, C1 -8 alkyl ester of a-cyanoacrylic acid, (as the ethyl, butyl or cyclohexyl ester), styrene, methylstyrene, acryionitrile, methacrylonitrile or o-chloroacrylonitrile.
A preferred copolymer according the invention is formed by the polymerisation of methylmethacrylate in the presence of glycidylacrylate and/or glycidyl methacrylate, preferably in the presence of glycidyl methacrylate. Preferably in such copolymer 0.1 to 10 %, more preferably 0.5 to 6 % by weight (based on the weight of methacrylate and other comonomers if present) of the glycidyl compound is present in the copolymer of the invention.
The working of the compound of formula I into a polymer or copolymer according to the invention, can be carried out according to known methods. For example, the compound of formula I can be added to the monomer or prepolymer at room or elevated temperatures since the compounds of formula I tend to dissolve therein at 20 to 60"C. The polymers and copolymers according to the invention can be prepared by known methods from appropriate reactants, preferably by block polymerisation in the presence of a polymerisation catalyst, for example azo-bis-iso-butyronitrile, dibenzoylperoxide, dilauryl peroxide or tertiary butoxyperpivalate. Compounds of formula I can also be worked into the melted polymer or copolymer by known methods such as extrusion and the polymers can be converted into shaped articles.
Preferably 3 to 30%, more preferably 8 to 25% by weight of a compound of formula I in the polymer based on the weight of polymer or monomers is used.
One preferred method for preparing a copolymer according to the invention is copolymerisation with glycidyl acrylate or glycidylmethacrylate. By using the glycidyl acrylate or glycidyl methacrylate a lesser amount of a compound of formula I may be used to achieve flameproofing. In such a case the preferred amount of a compound of formula I present is from 3 to 25 % move preferably 8 to 15 % by weight of the polymer or of the comonomers used.
Further additives can be added to a polymer or copolymer according ot the invention such as polymerisation regulators, softeners, U.V. light stabilisers, antioxidants and pigments.
The polymers and copolymers of the invention can be made into various shaped articles such as sheets, tubing or foils by known methods.
For the avoidance of doubt, reference to a compound of formula I includes mixtures of compounds of formula I or a mixture of one of more compounds of formula I with one or more other flameproofing agents.
Further, in this specification where a range is given, the figures defining the range are included therein.
The invention will now be illustrated by the following Examples in which all parts and percentages are by weight and all temperatures are in "C.
EXAMPLE 1
23.6 Parts of 2-ethyl-2-methyl-1 ,3-propanediol are melted at 50 in a vessel. 30.7 Parts of phosphorusoxychloride are added dropwise and the reaction mixture is stirred at room temeperature for 15 minutes. The mixture is then warmed at 500 under vacuum for 1 hour. To the so produced crystalline mass, 21 parts of pyridine and 1.8 parts of water are added and the reaction mixture is stirred for 1 hour at room temperature followed by stirring for 4 hours at 400. Then the mixture is brought to room temperature and is filtered from the precipitate. After concentrating the organic phase, the residue is taken up in toluene, washed with dilute hydrochloric acid and dried over sodium sulphate. The organic medium is then distilled off.
The compound of formula la
is formed, having a melting point of 154-155 .
EXAMPLE 2
Instead of the reactants in Example 1, a mixture of 10.4 parts of 2,2-dimethyl-1,3-propanediol and 11.8 parts of 2-ethyl-2-methyl-1 ,3-propanediol are reacted with 30.7 parts of phosphorusoxychloride according to the method of Example 1.
A mixture of 5.2 parts of the compound offormula 2a
6.2 parts of the compound of formula 2b
and 12.0 parts of the compound of formula 2c
(determined by HPLC) results.
EXAMPLE 3
Instead of the diol reactants of Example 1, 13.2 parts of 2-methyl-2-n-propyl-1 ,3-propanediol and 10.4 parts of 2,2-di-methyl-1 3-propanediol are reacted according to the method of Example 1.
A mixture of 3.9 parts of the compound of formula 2a defined in Example 2,5.9 parts of the compound of formula 3a
and 11.4 parts of the compound of formula 3b
results.
EXAMPLE 4
Starting from appropriate reactants, a mixture of 46.4% of the compound of formula 4a
36.3 % of the compound of formula 4b
and 17.3 % of the compound of formula 2a (defined in Example 2) can be prepared according to the method of
Example 1.
EXAMPLES 5 to 15
Compounds having the structures given in the Table below can be prepared according to Example 1 from appropriate reactants.
EX. melting Doint No. 5 t r u c t u r e ( C) 5 c cCH2ONWo CH3 C3N7 (D)t 2 134-138 I C 6 (n) C3117 \i0 62-65 OH, 0 7 Eec)C zC/C 2 0 fo32 78-80 :eec) CqEI4 012 c2o cit cE2ON 8 C P CH3CHO ,, II 115-116 I f2 -i-C3H,7 9 //cH 0 l 0 111-114 A CH3 2
Table continued
s EX. 5 t r u c t u Melting point No. 5 t r u c t u r e ("c) ioeHs o /CH20\ I 10 p;2R5 6\ wCH2 \ per :03-104 C2HSO-f/ t 2H50-2 CB20 oJ 2 11 c2it -1 194-196 11 02 5 wCH2O I 2 C2ll50CR2 wca2 \ 0 liquid c.it2oollj7 0 J2 13 CH3Z/o\CX20/PI 2 g7-gg 14 \ CH,2o o 115-122 14 2 2 15 /CH,O\pO-P::OCH2-"3 C P CH3 "r" SCH2 CH3 CH2O 0 EXAMPLE A
100 Parts of freshly distilled methylmethacrylate are well mixed with 2.2 parts of glycidyl methacrylate, 0.1 parts of dilaurylperoxide, 0.08 parts of dilaurylperoxide, 0.06 parts of azoisobutanoic acid dinitrile and 20 parts of the compound of formula 1a defined in Example 1.
The mixture is warmed to boiling and poured between glass plates which are sealed by a rubber seal and adhesive tape. The glass plates are immersed for 16 hours in a water bath at 500 and then heated at 1000 in a dry chamber for 3 hours. After removal of the glass plates, 3 mm thick methacrylate polymer sheets are obtained.
The sheets are self-extinguishing according to ASTM 635.
EXAMPLE B
100 Parts of freshly distilled methylmethacrylate are well mixed with 2.2 parts of glycidyl methacrylate, 0.1 parts of dilaurylperoxide, 0.08 parts of azoisobutanoic acid dinitrile and 8.3 parts of the compound of formula 1 a defined in Example 1. The mixture is then treated according to Application Example A. The products are self-extinguishing according to ASTM D 635.
EXAMPLE C
300 Parts of a commercially available polymethylmethacrylate granules of mid range molecular weight (120 000) are dried at 80"C for 4 hours under a vacuum of 20 mm Hg and then are dry mixed with 53 parts of the compound of Example 11 in a shaker. The mixture is extruded to a thread at 230 and then granulated.
The resultant granulate is dried for 6 hours at 80" and under 20 mm of Hg and then formed from an extruder into 3 mm thick sheets. The sheets are tested according to the oxygen index test (ASTM D 2863-77) and give good results. They are self-extinguishing according to ASTM D 635.
Application Example D
Instead of using the compound of formula 1 a in Application Example 1A, 25 parts of the mixture of
Example 2 is used. The product is self extinguishing according to ASTM D 635.
Instead of the compound of formula 1 a in any one of Application Examples A to C, an appropriate amount of the compound of any one of Examples 2 to 15 can be used.
Claims (16)
1. A methylmethacrylate polymer or co-polymer containing a flameproofing amount of a compound of formula I
in which each R1, independently, is hydrogen, C14 alkyl, phenyl, -CO-O-C1-6 alkyl or -CH2-O-C12 alkyl;
R2 is hydrogen, C14 alkyl or -CO-O-C18 alkyl;
each R4 independently, is hydrogen or C14 alkyl;
each R8 independently, is hydrogen or methyl and Xis oxygen or sulphur.
2. A polymer or co-polymer according to Claim 1, in which in the compound of formula I, R1 is R; where each R; independently is hydrogen, C14 alkyl, -CH2-O-C1-2 alkyl or -CO-O-C12 alkyl.
3. A polymer or co-polymer according to Claim 2, in which in the compound of formula I, R1 is R"1 where each R"1 independently, is C13 alkyl.
4. A polymer or co-polymer according to any one of Claims 1 to 3, in which, in the compound of formula
I, R2 is R2, where F2, is hydrogen, C14 alkyl or -CO-O-C,~2 alkyl.
5. A polymer or co-polymer according to Claim 4, in which in the compound of formula I, F2 is F2" where R2 is C1~4 alkyl.
6. A polymer or co-polymer according to any one of the preceding claims, in which in the compound of formula I, R4 is F4 where each R4 is hydrogen or C1 3 alkyl.
7. A polymer or co-polymer according to Claim 6, in which in the compound of formula I, R4 is hydrogen.
8. A polymer or co-polymer according to any one of the preceding claims, in which, in the compound of formula I, Xis oxygen.
9. A polymer or co-polymer according to Claim 1, in which the compound offormula I is offormula la
in which each R; independently, is hydrogen, C1-4 alkyl, -CH2-O-C1.2 alkyl or -CO-O-C1.2 alkyl; F2 is hydrogen, C1-4 alkyl or -CO-O-C1-2 alkyl: and each R4independently, is hydrogen or C1 3 alkyl.
10. A polymer or co-polymer according to Claim 1, in which the compound of formula I is of formula Ib
in which R'2 is C1-4 alkyl.
11. A polymer according to Claim 1 substantially as herein described with reference to any one of
Examples 1 to 15.
12. A polymer or co-polymer according to any one of the preceding claims in which 3 to 30 % by weight of a compound of formula I defined in Claim 1 is present.
13. A polymer or co-polymer according to Claim 12, in which 8 to 25% by weight of a compound of formula I defined in Claim 1 is present.
14. A co-polymer according to any one of the preceding claims in which the polymer has been co-polymerised with one or more comonomers selected from C2.8 alkyl ester of methacrylic acid, Ci.8 alkyl ester of acrylic acid, C1.8 alkyl ester of a-cyanoacrylic acid, styrene, methylstyrene, acrylonitrile, methacrylonitrile or a-chloroacrylonitrile.
15. A co-polymer according to any one of the preceding claims in which the polymer has been co-polymerised with glycidyl acrylate or glycidyl methacrylate.
16. A polymer or co-oolymer according to any one of the preceding claims containing one or more additive selected from the group consisting of polymerisation regulators, softeners, U.V. light stabilisers, antioxidant and pigments.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3510417 | 1985-03-22 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8606811D0 GB8606811D0 (en) | 1986-04-23 |
| GB2172600A true GB2172600A (en) | 1986-09-24 |
| GB2172600B GB2172600B (en) | 1988-07-20 |
Family
ID=6266038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08606811A Expired GB2172600B (en) | 1985-03-22 | 1986-03-19 | Flame retardant methacrylate polymers |
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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2623515A1 (en) * | 1987-11-24 | 1989-05-26 | Sandoz Sa | POLYMERIC COMPOSITION BASED ON METHYL METHACRYLATE |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1510381A (en) * | 1974-07-30 | 1978-05-10 | Sandoz Ltd | Dioxaphosphorinane derivatives as flameproofing agents |
| GB2053235A (en) * | 1979-06-19 | 1981-02-04 | Sandoz Ltd | Flame retardant polyacrylonitrile |
| GB2142338A (en) * | 1983-06-25 | 1985-01-16 | Sandoz Ltd | Stabiliser mixture for polyethylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1510381A (en) * | 1974-07-30 | 1978-05-10 | Sandoz Ltd | Dioxaphosphorinane derivatives as flameproofing agents |
| GB2053235A (en) * | 1979-06-19 | 1981-02-04 | Sandoz Ltd | Flame retardant polyacrylonitrile |
| GB2142338A (en) * | 1983-06-25 | 1985-01-16 | Sandoz Ltd | Stabiliser mixture for polyethylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2623515A1 (en) * | 1987-11-24 | 1989-05-26 | Sandoz Sa | POLYMERIC COMPOSITION BASED ON METHYL METHACRYLATE |
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 |
| CH667275A5 (en) | 1988-09-30 |
| GB8606811D0 (en) | 1986-04-23 |
| GB2172600B (en) | 1988-07-20 |
| FR2579212A1 (en) | 1986-09-26 |
| ATA75686A (en) | 1989-06-15 |
| JPS61221256A (en) | 1986-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1133485A (en) | Copolymeric light stabilisers and uv-absorbers | |
| US4260768A (en) | Copolymerizable, ultraviolet light absorber 2-(2H-benzotriazol-2-yl)-4-alkylphenol acrylic acid esters | |
| ATE159536T1 (en) | POLYMETHACRYLATE MOLDING COMPOUND WITH HIGH HEAT RESISTANCE AND HIGH STABILITY AGAINST THERMAL DEGRADATION | |
| US2472811A (en) | Polymers of alpha-fluoromethyl acrylic acid esters | |
| US3426104A (en) | Dye receptive acrylonitrile polymers comprising copolymerized alkyl allyloxy benzene sulfonates | |
| US3752802A (en) | Mono azo compounds containing an acylating function | |
| US4965321A (en) | Thermoplastic copolymer | |
| BR8401839A (en) | RETICULATED COPOLIMERO, PROCESS FOR ITS PREPARATION AND ITS APPLICATIONS | |
| US3449303A (en) | Polymers of phosphate esters | |
| JPH01167357A (en) | Polymer composition containing fire retardant agent and light stabilizer | |
| GB2172600A (en) | Flame retardant methyl methacrylate polymers | |
| EP0291297B1 (en) | Fluorine-containing ab-type block copolymer | |
| US3225014A (en) | Ethylene dicarboxylic esters of 1,2 alkane ketals | |
| US3225008A (en) | Itaconic esters of 1,2 alkane carbonates, polymers, and copolymers thereof | |
| US5200545A (en) | Thiuram disulphides containing phosphate or phosphonate functional groups, their preparation and their use in the manufacture of fireproofing vinyl polymers | |
| US3821336A (en) | 2,3-dibromopropyl methyl acid phosphate | |
| US4075286A (en) | Preparation of block polymers using polyazo sequential free radical initiators | |
| US3220988A (en) | Polyhalogen containing bicyclic compounds and polymers thereof | |
| US4095019A (en) | Free radical polymerization process utilizing novel initiators | |
| US3424730A (en) | Vinylidenearylenealkylene carbamates and polymers thereof | |
| US5420209A (en) | Preparation of (meth) acrylic/glutarimide copolymers | |
| US4041012A (en) | Acrylate esters of dihaloneopentyl glycol phosphates (phosphorinanes) and their use as flame retardants | |
| US3219640A (en) | Flame-resistant polymer compositions | |
| US4072810A (en) | Coupled peroxides | |
| US3875123A (en) | Polymers and copolymers based on alkenoyl-oxybenzylidene-malonic esters as uv-absorbers and plastics stabilized therewith |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930319 |