EP4168459A1 - Acrylate résistant à la flamme - Google Patents
Acrylate résistant à la flammeInfo
- Publication number
- EP4168459A1 EP4168459A1 EP21733425.9A EP21733425A EP4168459A1 EP 4168459 A1 EP4168459 A1 EP 4168459A1 EP 21733425 A EP21733425 A EP 21733425A EP 4168459 A1 EP4168459 A1 EP 4168459A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acrylate
- meth
- diacrylate
- methacrylate
- monomers
- 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.)
- Pending
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 64
- 239000000178 monomer Substances 0.000 claims abstract description 88
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 30
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 37
- 239000003063 flame retardant Substances 0.000 claims description 29
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 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 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 238000005292 vacuum distillation Methods 0.000 claims description 18
- 238000007334 copolymerization reaction Methods 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 11
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims 1
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 63
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 4
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 abstract 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000000243 solution Substances 0.000 description 42
- 238000012360 testing method Methods 0.000 description 34
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 31
- 239000003921 oil Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 20
- 235000019400 benzoyl peroxide Nutrition 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 239000004342 Benzoyl peroxide Substances 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 13
- 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 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 11
- 238000007792 addition Methods 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- -1 methyl-ethylcarboxy-phosphinic acid Chemical compound 0.000 description 9
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 7
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 6
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 5
- 230000008034 disappearance Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- XXHSFOMKJAVUID-KRWDZBQOSA-N (2s)-5-amino-2-[[4-[(2-amino-4-oxo-1h-quinazolin-6-yl)methylamino]benzoyl]amino]pentanoic acid Chemical group C1=CC(C(=O)N[C@@H](CCCN)C(O)=O)=CC=C1NCC1=CC=C(NC(N)=NC2=O)C2=C1 XXHSFOMKJAVUID-KRWDZBQOSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 2
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical group CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000007706 flame test Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OOHZIRUJZFRULE-UHFFFAOYSA-N 2,2-dimethylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)C OOHZIRUJZFRULE-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-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
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- BZNXCLGEDPFXKD-UHFFFAOYSA-N 2-methoxybenzene-1,4-diol;4-methoxyphenol Chemical compound COC1=CC=C(O)C=C1.COC1=CC(O)=CC=C1O BZNXCLGEDPFXKD-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Definitions
- the present invention relates to a process for the production of oxaphosphaphenantrenoxide acrylate monomers, the monomers obtainable therewith and their use for the production of flame-retardant thermoplastic (meth) acrylate polymers and a process for the production of flame-retardant thermoplastic (meth) acrylate polymers with the monomers thus obtainable Polymers and their use for the production of films and sheets.
- Thermoplastic acrylate and methacrylate polymers are versatile plastics because of their transparency and UV resistance. For example, they can be used as a protective layer in decorative films for coating windows, doors and other components.
- (meth) acrylate polymers are comparatively easily inflammable and combustible.
- flame retardants are added.
- Inorganic flame retardants such as metal hydroxides, are poorly suited, since the high loads required for adequate effectiveness suffer from transparency.
- Halogen-containing flame retardants are widespread, but have come under fire because of toxicological and ecological concerns.
- a wide variety of phosphorus-containing flame retardants have been proposed as halogen-free alternatives. If these are mixed in as low molecular weight compounds, the desired flame retardant effect is obtained, but the transparency can suffer and, in addition, migration of the flame retardants is frequent. This reduces their effect and the surface is changed or, in the case of multilayer films, the adhesion to adjacent layers is impaired.
- a particularly effective group of phosphorus flame retardants are phosphinic acid derivatives such as 9,10-dihydro-9-oxa-10-phosphaphenantren-10-oxide (DOPO for short).
- DOPO 9,10-dihydro-9-oxa-10-phosphaphenantren-10-oxide
- DOPO and other phosphorus-containing flame retardants are known per se.
- US 2014/0346418 A1, WO 2015/096127 A1 and US 2017/0029704 A1 describe flame retardancy by copolymerization with phosphorus-containing monomers.
- DOPO other organic phosphates are described.
- additives based on DOPO which carry a carboxylic acid group or its ester on phosphorus.
- additives with several DOPO groups result.
- a copolymerization is not provided, however, the additives should be mixed with the polymer and only polyamide and polyester are mentioned as polymers.
- WO 2014/124933 A2 describes duromers made from DOPO and polyvalent acrylates with at least 3 acrylic groups, which are further reacted with (meth) acrylate. These thermosets should be suitable as flame retardant additives.
- DOPO is converted into a monomer via a reaction with formaldehyde and then with acrylic acid chloride and then copolymerized with methyl methacrylate.
- the procedure is analogous in EP 1 544227 A1, first of all the DOPO is coupled to an alcohol group, which is then reacted with acrylic acid chloride to form the DOPO acrylate monomer.
- Acrylic acid chlorides are very reactive substances whose use on an industrial scale is problematic.
- Wang et al. "Flexible, transparent flame retardant membrane Fire and Materials 2018, Vol. 42, pp. 99-108, describes a reaction of methyl-ethylcarboxy-phosphinic acid with acrylic acid-hydroxyethyl ester.
- DE 102013223915 A1, DE 102013 101 487 A1 and WO 2019/141572 A1 disclose phosphorus-containing (meth) acrylate monomers for producing flame-retardant, thermoplastic resin compositions.
- DOPO-oxymethylene methacrylate monomer is described as a phosphorus-containing (meth) acrylate monomer.
- the monomer is reacted with one or more at least trivalent (meth) acrylate monomers to form a copolymer, which then forms part of the resin composition as a flame retardant.
- the polymers of the first two documents mentioned are supposed to be thermosets and are.
- slightly crosslinked or uncrosslinked copolymers are to be obtained by direct copolymerization with (meth) acrylate monomers by preparing phosphorus-containing triacrylate monomers from approximately equimolar amounts of phosphorus compound and acrylate groups in the triacrylate.
- DOPO acrylate monomers are to be obtained by Michael addition with a DOPO deficit.
- the document contains long lists of possible (meth) acrylates, including 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate.
- the aim is to achieve crosslinkable coatings in which the refractive index is set with DOPO. Copoly merization with acrylates is described.
- the person skilled in the art can neither infer from this document that non-crosslinking monomers can be prepared, nor how this could be achieved.
- the above object is therefore achieved by a process for the preparation of oxaphosphaphenantrene oxide acrylate monomers by phospha-Michael addition to ⁇ , w-alkyldiol diacrylates having 2 to 6 carbon atoms in the alkyl chain in the presence of a sterically hindered, non-nucleophilic base and a polymerization inhibitor , the oxaphosphaphenanthrene oxide being reacted with the ⁇ , w-alkyl diol diacrylate in a molar ratio of 1: 1.5 to 1:10 at temperatures of 70 to 120 ° C.
- w-alkyl diol diacrylate - is separated off - preferably by vacuum distillation.
- the object is also achieved by the oxaphosphaphenantrene oxide acrylate monomers obtainable in this way, their use for the production of (meth) acrylate polymers and a process for the production of transparent, thermoplastic (meth) acrylate polymers by copolymerization of the oxaphosphaphenantrene oxide acrylate monomers with (meth) acrylate monomers.
- the term (meth) acrylate polymer includes methacrylate polymers and acrylate polymers, as well as copolymers of one or more acrylic acid ester monomer (s) and / or one or more methacrylic acid ester monomer (s). Both homopolymers and copolymers, terpolymers, etc. are thus included, the monomers being acrylic acid ester monomers, methacrylic acid ester monomers, or both acrylic acid ester and methacrylic acid ester monomers.
- the (meth) acrylate polymers contain, in addition to the oxaphosphaphenantrene oxide acrylate monomer (s) according to the invention, only (meth) acrylate monomer (s).
- Typical acrylic acid ester monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, and benzyl acrylate.
- Usual methacrylic acid ester monomers are methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutymethacrylate, tert-butyl methacrylate, neopentyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate.
- Monomers that are less prone to chain transfer, such as ethyl acrylate, are particularly beneficial.
- Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutymethacrylate and tert-butymethacrylate, in particular methyl methacrylate, are preferred.
- the monomers are also collectively referred to herein as (meth) acrylate monomers.
- acrylic acid and methacrylic acid can also be used as monomers, but these are not readily miscible with oxaphosphaphenantrene oxides such as DOPO and are therefore preferably not used.
- Preferred (meth) acrylate polymers are polymethyl methacrylate (PMMA) and copolymers of methyl methacrylate (MMA) with methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA) and n-butyl methacrylate (BMA).
- additional comonomers such as acrylonitrile, can be polymerized in order to further improve the desired properties, including the fire behavior.
- Oxaphosphaphenantrene oxides are known per se, including the preferred 9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide (DOPO), and are commercially available. According to the invention, these are reacted with a, w-alkyldiol diacrylate to give oxaphosphaphenantrene oxide acrylate monomers, which are then used as Comonomers can be polymerized into (meth) acrylate polymers.
- Suitable a, w-alkyldiol diacrylates are those with 2 to 6 carbon atoms in the alkyl chain.
- the reaction takes place at a molar ratio of oxaphosphaphenantrene oxide to ⁇ , w-alkyldiol diacrylate of 1: 1.5 to 1:10, preferably 1: 3 to 1: 7 and in particular of about 1: 5.
- the choice of the ratio represents a compromise between the effort involved in removing the excess ⁇ , w-alkyl diol diacrylate and the selectivity of the reaction.
- the temperature is generally from 70 to 120.degree. C., preferably from 80 to 100.degree.
- Either an aprotic solvent with good dissolving power for the phosphaphenantrene oxide or an excess of ⁇ , w-alkyl diol diacrylate is used as the reaction medium.
- the reaction is carried out without a solvent. This makes it easier to isolate the oxaphosphaphenanthene oxide acrylate monomer, which lowers costs.
- a solvent has the advantage that the risk of premature polymerization is reduced, and solvents can also be more easily distilled off.
- Preferred solvents are toluene, xylenes, ethyl acetate, acetonitrile and tetrahydrofuran, in particular toluene and xylenes (o-xylene, p-xylene, m-xylene and Mixtures thereof), most preferably toluene.
- Suitable amounts are, for example, volumes of solvent to the sum of the volumes of starting materials and base from 1: 5 to 5: 1, preferably from 1: 2 to 2: 1.
- the base used is sterically hindered and non-nucleophilic compounds, for example tertiary alkylamines, typically in amounts of 0.15 to 2.0 mol per mole of oxaphosphaphenantrenoxide, preferably from 0.5 to 1.2 mol per mol, particularly preferably from 0, 9 to 1.1 moles per mole.
- the molar ratio of amine to DOPO can be reduced to about 0.15: 1; if the amount of amine is reduced still further, the addition becomes much slower and less selective. An excess of base is economically disadvantageous, but has little influence on the reaction.
- Tertiary alkylamines are particularly suitable as bases, triethylamine being the most suitable in terms of price, boiling point and low toxicity.
- N-ethyldiisopropylamine and tripropylamine as well as tributylamine can also be used, while trimethylamine is less suitable because of its very low boiling point.
- Tertiary aromatic amines such as pyridine are also possible, but less preferred. It can be advantageous to add further base after the reaction has taken place for some time.
- a polymerization inhibitor is added to prevent premature polymerization of the oxaphosphaphenantrene oxide acrylate and the ⁇ , w-alkyl diol diacrylate.
- hydroquinone, phenothiazine, 1-dodecanethiol, hydroquinone monobenzyl ether, methoxyhydroquinone and other known substances are suitable.
- Hydroquinone and methoxyhydroquinone are preferred.
- the necessary quantities are known per se. For example, the amount of stabilizer contained in commercial ⁇ , w-alkyl diol diacrylate can be sufficient.
- oxaphosphaphenantrene oxides can react with water and base with ring opening, the reaction takes place with exclusion of water.
- Water leads to ring opening and thus to side reactions, i.e. to the formation of the triethylammonium salt of the ring-opened oxaphosphaphenantrene oxide.
- the absence of water means a maximum content of less than 1% by weight of water, preferably less than 0.1% by weight of water and particularly preferably less than 0.05% by weight of water in the liquid phase.
- the reaction is preferably carried out under a dry protective gas such as nitrogen.
- a dry protective gas such as nitrogen.
- a reaction in air is not recommended for reasons of explosion protection.
- triethylamine for example, is somewhat sensitive to oxidation and the reaction mixture could turn dark in the presence of air.
- small amounts of oxygen are not a problem and can even be advantageous if the most frequently used inhibitor methoxyhydroquinone is used, since this is only active in the presence of traces of oxygen. In this respect, removal of oxygen from the starting materials and other components of the reaction solution is not necessary and is preferably not carried out.
- the reaction is carried out until the oxa-phosphaphenantrene oxide has essentially completely reacted, which typically takes from 1 to 10 hours, often from 2 to 5 hours.
- the oxaphosphaphenanthrene oxide is added either in portions or continuously, e.g. with a solids feeder, for example in the course of 2.5-3 hours.
- the reaction temperature is maintained for a further 45-60 minutes after the addition has ended.
- the addition in portions or continuously is advisable, since the addition reaction is moderately exothermic. If, in larger batches, all of the oxaphosphaphenanthrene oxide is added at the beginning, too much heat of reaction is released in a short time, so that the temperature could rise too high.
- the reaction product used is primarily oxaphosphaphenantrene oxide acrylate, in addition to small amounts of di-oxaphosphaphenantrene oxide acrylate and the excess a, w-alkyldiol diacrylate obtained.
- Substantially complete conversion means that a maximum of 5 mol%, preferably a maximum of 2 mol% of the oxaphosphaphenantrene oxide have not been converted.
- the time to essentially complete conversion can be determined, for example, by means of 31 P-NMR. After the time for specific conditions has been determined, no further controls are necessary.
- the reaction should be essentially complete, since residues of unconverted oxaphosphaphenantrene oxide are undesirable, but too long a reaction time does not bring any advantages.
- the excess ⁇ , w-alkyldiol diacrylate and, if appropriate, the solvent are removed, preferably by means of vacuum distillation.
- the excess ⁇ , w-alkyl diol diacrylate and, if necessary, the solvent can also be removed by liquid-liquid extraction.
- the necessary temperature depends on the available vacuum and the necessary residence time at the high temperature. A thin-film evaporator is best suited because it only warms up for a very short time, which minimizes the risk of spontaneous polymerization. Here 75 - 140 ° C are useful. If the vacuum distillation is to be used for a longer period of time, 120 ° C should not be exceeded.
- a pressure of 0.01 to 0.2 mbar, preferably 0.02 to 0.2 mbar, is used.
- a liquid-liquid extraction with a hydrocarbon solvent such as cyclohexane is carried out to separate the reaction product from the excess ⁇ , w-alkyldiol diacrylate.
- a hydrocarbon solvent such as cyclohexane
- alkanes such as n-hexane, heptane, etc. can also be used, as can mixtures of alkanes, but cyclohexane was the most efficient of all the solvents tested.
- the solution of the reaction product is mixed intensively with the hydrocarbon solvent, if appropriate before or after the distillation, if appropriate after the addition of solvent, and the hydrocarbon solvent phase which is separated off is drawn off. This can be repeated a few times, e.g. 2, 3, 4 or 5 times.
- the vacuum distillation can be done before and / or take place after the separation of the ⁇ , w-alkyldiol diacrylate by extraction.
- oxaphosphaphenantrene oxide acrylate monomer is obtained with a maximum of 3 mol% of diacrylate, in particular with a maximum of 0.5 mol% of diacrylate.
- the resulting oxaphosphaphenantrene oxide acrylate monomer can be polymerized in a manner known per se, e.g. by means of free-radical emulsion, suspension or bulk polymerization, with (meth) acrylate monomers and, if necessary, further comonomers.
- the monomers are mixed and a radical starter such as azobis (isobutyronitrile) (AIBN for short) or benzoyl peroxide is added.
- oxaphosphaphenantrene oxide acrylate monomer Usable proportions of oxaphosphaphenantrene oxide acrylate monomer depend on the desired or necessary flame retardancy and are normally in the range from 10 to 30 mol%, preferably from 20 to 25 mol%, of oxaphosphaphenantrene oxide acrylate monomer, based on the mixture of all monomers.
- additives known per se such as thiols, can be added during the polymerization.
- the quantities that can be used are usually very small and are known in the prior art.
- the (meth) acrylate polymers according to the invention can contain further additives in a manner known per se, for example, but not exclusively, one or more flame retardants, surface-active agents, nucleating agents, coupling agents, fillers, plasticizers, impact enhancers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants , Light stabilizers, compatibilizers, inorganic additives, antistatic agents, pigments, dyes, etc. and combinations thereof.
- the additives can be added independently during the polymerization and / or during a pellet forming process (extrusion) to be included in the copolymer. The method for this and the amount added are known per se and are not particularly restricted.
- the solid phase in order to further improve the flame retardancy properties of the (meth) acrylate polymer prepared according to the invention, the solid phase also contains copolymerized phosphorus compounds with flame retardancy. These support the effect of the oxaphosphaphenantrenoxide acrylate comonomer, which is active in the gas phase.
- the first connection can be by means of
- Reaction of diethyl chlorophosphate with hydroxyethyl acrylate can be synthesized in the presence of an auxiliary base, see, for example, Nair, CP Reghunadhan; Clouet, G .; European Polymer Journal (1989), 25 (3), 251.
- the second connection is possible by reacting diethyl chlorophosphate with hydroxyethyl methacrylate in the presence of the auxiliary base such as triethylamine and copper (I) chloride as a catalyst, see CPR Nair, G Clouet, J Brossas; Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 26, 1791-1807 (1988).
- the fourth compound is made by reacting diphenyl chlorophosphate (CAS No.
- the fifth and sixth compounds are, for example, by reacting phosphorus oxychloride with neopentyl glycol to give 2-oxo-2-chloro-5,5-di-Me-1, 3,2-dioxa-phosphorinane and reacting the latter with hydroxyethyl acrylate or hydroxyethyl methacrylate available, see Xing, Weiyi; Song, lei; Lv, pin; Jie, Ganxin; Wang, Xin; Lv, Xiaoqi; Hu, Yuan; Materials Chemistry and Physics 123 (2010) 481-486 and CN 104497051 A.
- the seventh compound is accessible analogously to the process according to the invention.
- the amounts of solid-phase active phosphorus-containing (meth) acrylate monomer depend on the flame retardant effect required and are, for example, in the range from 5 to 30 mol%, preferably from 10 to 25 mol%, of phosphorus-containing (meth) acrylate monomer, based on the mixture of all Monomers.
- the combination of oxaphosphaphenatrene oxide acrylate monomer and a monomer with a flame retardant active phosphorus compound in the solid phase allows the amount of the two comonomers to be reduced so that a total of 10 to 20 mol% is contained. For example, 3, 4, or 5 to 10 mol% of the oxaphosphaphenate renoxide acrylate monomer according to the invention are sufficient.
- the amount of solid-phase active phosphorus-containing (meth) acrylate monomer can be reduced to from 3 to 20 mol%, preferably from 5 to 15 mol%.
- the fire behavior is tested according to UL94 "Tests for Flammability of Plastic Materials for Parts in Devices and Appliances" according to IEC / DIN EN 60695-11-10 and -20 of the Underwriters Laboratories .
- the tests are carried out with an open flame (Bunsen burner).
- the ignition source has a power of 50 watts (20 mm high flame) and acts twice for 10 s on the test specimen during the V test and is then removed again.
- the burning time and the falling off of burning parts are evaluated with the aid of a cotton swab, which is located under the test specimen.
- a classification occurs when the following requirements are met:
- V2 Total burning time of the 10 flame applications max. 250 s, self-extinguishing up to 30 seconds at the latest, burning droplets are permitted
- V1 Total burning time of the 10 flame exposures max. 250 s, self-extinguishing up to 30 seconds at the latest, burning drops are not permitted, afterglow maximum 60 seconds
- V0 Total burning time of the 10 flame applications max. 50 s, self-extinguishing up to 10 seconds at the latest, burning droplets are not permitted, afterglow max. 30 seconds.
- the flame-retardant, transparent, thermoplastic (meth) acrylate polymers according to the invention generally achieve ratings of V1, frequently V0.
- Such decorative films include, for example, a colored and / or printed base film, e.g. made of PVC or ( Meth) acrylate polymer.
- the base film can be provided with a primer and / or adhesive on the underside, depending on the material of the base film and the material to be laminated with.
- a protective film made of one or more layers of copolymer according to the invention is attached on the upper side to protect the base film and, if necessary, the print from UV radiation.
- the decorative film can also be made from a copolymer according to the invention, if necessary from several layers thereof.
- PVDF Polyvinylidene fluoride
- a cover film or coating is provided as the outer layer made of particularly scratch-resistant and durable plastic such as polytetrafluoroethylene (PTFE), PVDF, etc., which usually also provides protection Pollution provides.
- PTFE polytetrafluoroethylene
- Such decorative films can be partially or fully coextruded; non-coextruded layers are thermally laminated.
- the surface can be embossed, for example if a wood look is desired. Suitable thicknesses of the decorative film are, for example, from 100 to 300 ⁇ m, preferably from 130 or 150 to 200 ⁇ m.
- the protective layer made of copolymer according to the invention makes up 30 to 40% of the thickness and the cover layer, if present, makes up 3 to 4% of the thickness.
- the term "made of a polymer” means that the said polymer is the main polymer component of the layer. The presence of one or more other polymers is not excluded, but their amount is generally (in each case) less than 50% by weight, mostly less than 30% by weight and often less than 10% by weight, based on all Polymer components.
- the flame-retardant, transparent, thermoplastic (meth) acrylate polymers according to the invention are also suitable for producing transparent and colored sheets. These panels can be used in many ways, e.g. in interior construction.
- the invention also relates to all combinations of preferred configurations, insofar as these are not mutually exclusive.
- the information "about” or “approx.” in connection with a figure means that at least 10% higher or lower values or 5% higher or lower values and in any case 1% higher or lower values are included.
- the oxaphosphaphenantrene oxide acrylate monomers were prepared in Three-necked flasks of various contents, which were equipped with a stirrer, a Claisen attachment with reflux condenser and a nitrogen supply. The temperature was controlled via an oil bath. Before each reaction, the apparatus was dried in vacuo with heating and filled with nitrogen. For the reaction, the ⁇ , w-alkyl diol diacrylate with the solvent (toluene) and the base (triethylamine) were introduced into the flask in a countercurrent of nitrogen. Then 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was added in portions over several hours.
- DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
- the ⁇ , w-alkyldiol diacrylates used contained methoxyhydroquinone (4-methoxyphenol) as a polymerization inhibitor. In order to keep this active during the reaction, around 20 ml of air were injected at intervals of around 20 minutes. The course of the reaction was followed by taking samples and determining 31 P-NMR spectra.
- 1,4-Butanediol diacrylate was reacted with DOPO in a molar ratio of 3.5: 1.
- DOPO 1,4-Butanediol diacrylate
- 1,4-butanediol diacrylate and 14.05 g of DOPO were added.
- 80 ml of toluene and 0.17 mol (approx. 23.56 ml) of triethylamine were then added.
- the mixture was then heated to just below its boiling point with stirring and under a nitrogen atmosphere (approx. 96 ° C., oil bath temperature approx. 107 ° C.).
- Two further DOPO portions were added at 60 minute intervals (11.89 g, 10.81 g, a total of 36.75 g, 0.17 mol).
- the mixture was stirred for a further 60 minutes at the same internal temperature (approx. 96 ° C.).
- An NMR sample was then taken; the NMR indicated complete conversion.
- Toluene and triethylamine were distilled off on a rotary evaporator in vacuo. Vacuum distillation was carried out on the residue. At an oil bath temperature of 90 ° C and a vacuum of 0.063 mbar, distillation was carried out until no more diacrylate condensed in the receiver. The temperature was then increased to 125 ° C. over several steps (vacuum 0.042 mbar). for Another vacuum distillation, the oil bath temperature was slowly increased to 150 ° C (vacuum 0.044 mbar). The distillation was stopped because the reaction product began to polymerize.
- the reaction product obtained (49.91 g) of the formula: was then copolymerized with methyl methacrylate in an approximate molar ratio of 1: 2.7.
- the reaction product was dissolved in 200 ml of toluene and transferred to a three-necked flask. About 33.3 g of destabilized methyl methacrylate were then added and the solution was heated to 97 ° C. under nitrogen. Since the solution must not contain oxygen during the copolymerization because of the 4-methoxyphenol inhibitor, the mixture was stirred for 1.5 hours at the same temperature under nitrogen.
- the polymer product obtained was dried in a vacuum drying cabinet at 100 ° C. for 24 hours. After drying, the product was slightly rubbery and could not be ground into small pieces. It became a thermogravimetric one Analysis (TGA) carried out. The sample was heated from 35 ° C to 800 ° C in a nitrogen stream at a heating rate of 10 K / min. The analysis showed a decomposition temperature of 318 ° C. with a weight loss of 5%.
- a test specimen was produced with the polymer product in a laboratory press at a pressure of 25 bar within 4 minutes. At a temperature of 190 ° C it remained very elastic and rubbery. At a temperature of 225 ° C. or more, the test specimen became solid and brittle, which indicates post-crosslinking, ie not yet complete polymerization.
- test specimen obtained at 225 ° C. was examined in a UL94 chamber.
- the pressed test specimen showed a significantly slower burning behavior compared to pure PMMA, but did not achieve a V1 classification because it was not self-extinguishing.
- Example 2 The procedure was as in Example 1, with the difference that the reaction product was extracted several times with n-hexane after the vacuum distillation (oil bath temperature 140 ° C., vacuum 0.031 mbar). First 3 times with 50 ml of n-hexane each time, then after adding 20 ml of toluene 4 times with 40 ml of n-hexane each time and after adding a further 20 ml of toluene again 4 times with 40 ml of n-hexane each time. The solvents were then removed on a rotary evaporator.
- the reaction product (52.82 g) was dissolved in 200 ml of toluene and transferred to a three-necked flask. Then about 35 g of destabilized methyl methacrylate were added, the solution was heated to 97 ° C. under a nitrogen atmosphere and stirred for 2 hours at the same temperature. Then, with vigorous stirring, 1 ml of the 0.2 M AIBN solution was added dropwise over the course of 2 minutes and the temperature of the oil bath was increased to 117.degree. After 14 minutes, another 1 ml of AIBN was added. The solution began to boil heavily. After 27 minutes the solution became more and more viscous A voluminous gel-like substance separated from the solution for 34 minutes. The reaction was continued for an additional hour.
- the polymer product obtained was dried in a vacuum drying cabinet at 100 ° C. for 24 hours. After drying, the product remained slightly rubbery and could not be ground into small pieces with a mortar.
- the TGA analysis showed a similar decomposition temperature as in Example 1, 312 ° C. with a mass loss of 5%.
- Test specimens were produced with the product in a laboratory press at a pressure of 25 bar within 4 minutes. At 190 ° C the test specimen remained very elastic and rubbery. At a temperature of 225 ° C. or more, the test specimen became solid and brittle. The test specimen showed good transparency.
- the test specimen pressed briefly at 225 ° C, went out immediately after the first flame exposure of 10 seconds and after the second it burned only about 4 seconds, i.e. it achieved a classification V0.
- the oxaphosphaphenantrene oxide acrylate monomer was initially stirred at an internal temperature of about 97 ° C. for 30 minutes. Then 0.4 mol (40.07 g) of destabilized methyl methacrylate were added in a countercurrent of nitrogen. Since the solution must not contain oxygen during the copolymerization because of the 4-methoxyphenol, the mixture was stirred for a further 1.5 hours at the same temperature. Then, with vigorous stirring, 2 ml of the 0.2 molar AIBN solution in toluene were added dropwise over the course of 2 minutes. The solution began to boil strongly and a voluminous gel-like substance separated from the solution after a reaction time of a few minutes. The temperature of the oil bath was raised to 117 ° C and the reaction was continued for 1 hour.
- the polymer product obtained was dried in a vacuum drying cabinet at 100 ° C. for 24 hours and then finely ground. A white powder resulted. Thereafter, a thermogravimetric analysis (TGA) was carried out. The analysis showed a decomposition temperature of 255 ° C with a weight loss of 5%.
- TGA thermogravimetric analysis
- test specimens were produced with the powder in a laboratory press at temperatures of up to 260 ° C. and pressures of up to 25 bar. However, the powder could not be melted and no test specimen could be created.
- the amount of DOPO was increased slightly (45.40 g, 0.21 mol) to reduce the number of unreacted dimethacrylates.
- the amount of base and the time between the DOPO additions were increased to 60 minutes in order to ensure a faster conversion of the DOPO.
- 0.2 mol (45.25 g) of buthylene glycol dimethacrylate and 9.5 g of DOPO were placed in the 500 ml three-necked flask filled with nitrogen. 100 ml of toluene and 0.21 mol (approx. 29.11 ml) of triethylamine were then added. The mixture was then heated to just below its boiling point (approx. 96 ° C, oil bath temperature approx.
- the reaction product was copolymerized as in Comparative Example 1 with methyl methacrylate in a molar ratio of 1: 2.
- the polymer product obtained was dried in a vacuum drying cabinet at 100 ° C. for 24 hours and then finely ground with a ceramic mortar and pestle.
- the TGA analysis showed a decomposition temperature of 275 ° C with a weight loss of 5%.
- no test specimen could be produced with the product.
- ethylene glycol dimethacrylate was reacted with DOPO in a molar ratio of 1.76: 1. 0.25 mol (49.60 g) of ethylene glycol dimethacrylate and 8.65 g of DOPO were placed in the 500 ml three-necked flask filled with nitrogen. Then 70 ml of toluene and 0.10 mol (about 13.7 ml) of triethylamine were added added. The mixture was then heated to just below its boiling point (approx. 96 ° C., oil bath temperature approx. 107 ° C.) while stirring and under a nitrogen atmosphere.
- the reaction product was then copolymerized with 36 g of methyl methacrylate (molar ratio 1: 2).
- the reaction product and 200 ml of toluene and 36 g of destabilized methyl methacrylate were placed in a three-necked flask and the solution was heated to 97 ° C. under a nitrogen atmosphere. Since the solution must not contain oxygen, the mixture was stirred for 1.5 hours at the same temperature. Then, with vigorous stirring, 3 ml of the 0.2 M AIBN solution were added dropwise over the course of 5 minutes. The solution began to boil heavily. After 10 minutes the temperature of the oil bath was increased to 117 ° C. After 10 minutes, a bulky gel-like substance precipitated out of the solution and the reaction was continued for an additional hour.
- the polymer product obtained was dried in a vacuum drying cabinet at 150 ° C. for 24 hours and then finely ground. A yellowish white powder resulted. The drying temperature was possibly too high and the product had partially decomposed. The TGA analysis showed a decomposition temperature of 258 ° C with a mass loss of 5%. A test specimen was created with the powder in the laboratory press. This was yellowish, slightly transparent and very brittle, it could not be removed from the mold without breaking. The degree of networking was still too great.
- the pieces obtained were examined in a UL94 chamber.
- the pressed test specimen showed a greatly slowed down burning behavior compared to pure PMMA, but not the desired self-extinguishing after exposure to the flame.
- Triethylamine and toluene were distilled off in vacuo on a rotary evaporator. Next, it was extracted 3 times with 100 ml of n-hexane. A vacuum distillation was then carried out until no more dimethacrylate condensed in the receiver at an oil bath temperature of 85 ° C., a head temperature of 50 ° C. and a vacuum of 0.05 mbar. The vacuum distillation was repeated twice at an elevated temperature, 95 ° and 105 ° C. oil bath temperature, respectively. However, some of the product solution polymerized spontaneously. The 1 H-NMR showed that dimethacrylates were still contained in the reaction product.
- the reaction product (119 g) was dissolved in 450 ml of toluene and transferred to the three-necked flask. About 36 g of destabilized methyl methacrylate were then added and the solution was heated to 97 ° C. under a nitrogen atmosphere. It was stirred for 1.5 hours at the same temperature. Then, with vigorous stirring, 2 ml of the 0.2 M AIBN solution were added dropwise over the course of 4 minutes, and the temperature of the oil bath was increased to 117.degree. After 10 minutes, another 1 ml of AIBN was added. The solution began to boil heavily. After 15 minutes the solution became more viscous. White flakes could be seen. After 17 minutes, a bulky gel-like substance precipitated from the solution and the reaction was continued for an additional hour.
- the polymer product obtained was dried in a vacuum drying cabinet at 100 ° C. for 24 hours and then finely ground with a ceramic mortar and pestle.
- the TGA analysis showed a decomposition temperature of 241 ° C. with a weight loss of 5%.
- a test specimen was created with the powder in the laboratory press. This was more transparent than in the comparative examples CE1, CE2 and CE3, but still very brittle. It could not be removed from the mold without breaking.
- the excess ethylene glycol dimethacrylate was increased even further to a molar ratio of 3.5: 1.
- 0.7 mol (138.8 g) of ethylene glycol dimethacrylate and 17.3 g of DOPO were placed in the 1 l three-necked flask filled with nitrogen.
- 100 ml of toluene and 0.4 mol (approx. 55.5 ml) of triethylamine were then added.
- the mixture was then stirred under a nitrogen atmosphere until heated to just below their boiling point (approx. 96 ° C, oil bath temperature approx. 107 ° C).
- Two further DOPO portions were added at intervals of 60 minutes each (15.3 g, 10.8 g, a total of 43.24 g, 0.2 mol).
- the mixture was stirred for a further 60 minutes at the same internal temperature (approx. 96 ° C.).
- An NMR sample was then taken which showed complete conversion of DOPO.
- Triethylamine and toluene were distilled off in vacuo on a rotary evaporator and vacuum distillation (oil bath temperature 80 ° C., vacuum 0.04 mbar) was carried out with the residue.
- oil bath temperature 80 ° C., vacuum 0.04 mbar vacuum bath temperature 80 ° C., vacuum 0.04 mbar
- the examples and comparative examples show that a usable acrylate comonomer is obtained neither with approximately equimolar amounts of starting material nor with an excess of oxaphosphaphenantrene oxide. Only if a sufficient excess of diacrylate is used, as provided according to the invention, can a diacrylate which has only simply reacted with oxaphospaphenantrene oxide be obtained.
- thermoplastic (meth) acrylate polymers In addition to the selection of ⁇ , w-alkyl diol diacrylate and an excess thereof, the separation of the unreacted ⁇ , w-alkyl diol diacrylate provided according to the invention is also necessary in order to obtain thermoplastic (meth) acrylate polymers.
- Table 1 gives an overview of the examples and comparative examples. Table 1
- a DOPO acrylate monomer was produced from DOPO and 1,4-butanediol diacrylate, but with a molar ratio of butanediol diacrylate to DOPO of 7: 1.
- 1.25 mol (297.3 g) of distilled butanediol diacrylate, 13.6 g of DOPO and 30 mg of 4-methoxyphenol were placed in a 250 ml three-necked flask filled with nitrogen.
- 35 ml of triethylamine were then added via a syringe through the septum, and the mixture was heated to 85-87 ° C. over the course of 20 minutes (oil bath temperature) with stirring and under a nitrogen atmosphere.
- the product solution obtained was divided into two parts.
- the product was isolated for both parts by first distilling off the triethylamine, a partial vacuum being applied at the beginning and the oil bath being heated to a maximum of 50 ° C.
- the main part of the excess butanediol diacrylate was then distilled (approx. 0.02 mbar), heating up to 105 ° C. in order to avoid spontaneous polymerization.
- 250 ml of cyclohexane were added to the distillation residue and the mixture was then rapidly heated to the boil. After about 5 minutes of intensive stirring under reflux, the oil bath was removed. The contents of the flask were then cooled to approx. 40 ° C.
- the polymer product obtained was dried in a vacuum drying cabinet at 100 ° C. for 24 hours. After drying, the product remained slightly rubbery and could not be ground into small pieces with a mortar.
- the TGA analysis showed a similar decomposition temperature as in Examples 1 and 2, 312 ° C. with a mass loss of 5%.
- Test specimens were produced with the product in a laboratory press at a pressure of 25 bar within 4 minutes. At 190 ° C the test specimen remained very elastic and rubbery. At a temperature of 225 ° C. or more, the test specimen became solid and brittle. The test specimen showed good transparency.
- the test specimen pressed briefly at 225 ° C. went out immediately after the first exposure of 10 seconds and after the second it only burned for about 4 seconds, ie it achieved a classification V0.
- the results of the fire behavior test are listed in Table 2.
- the DOPO monomer of Example 6 was used in various amounts
- Methyl methacrylate and DDPO-HEMA, A converted to a methyl acrylate polymer both with and without the addition of a further monomer, such as methyl acrylate or n-butyl methacrylate.
- a suspension polymerization took place in water with 1-decylthiol as regulator and dibenzoyl peroxide (BPO) as initiator.
- BPO dibenzoyl peroxide
- the liquid monomers were destabilized before the polymerization; DDPO-HEMA (A) was recrystallized from fe / f-butyl methyl ether (melting point 50.5 ° C.).
- the syntheses of the methacrylate polymers were carried out in a reaction apparatus which consisted of a 250 ml three-necked flask, magnetic stirrer, heating bath, a dropping funnel and a reflux condenser to which a three-way stopcock with a bubble counter was attached. Both the dropping funnel and the three-way stopcock on the reflux condenser were connected with a Schlenk line.
- test bars were produced using an oil hydraulic laboratory press of the type HB 20300 (Schmidt Maschinentechnik; Bretten-Bauerbach, Germany).
- the test bars had the following dimensions: 70 mm x 10 mm x 0.8 mm.
- temperatures of 210-245 ° C were used (depending on the melting behavior of the methacrylate polymers).
- the quantities and results of the fire behavior test are listed in Table 2.
- a mixture of 1.35 g of DDPO-HEMA (A), 1.35 g of DOPO monomer, 7.3 g of methyl methacrylate, 34 mg was placed in the dropping funnel Given 1-decyl mercaptan and 67 mg of hydrous BPO. Vacuum was then applied twice briefly and nitrogen was allowed to flow in again in each case. To remove the oxygen, the mixture of water and 1.3 ml of a 2% solution of the suspension stabilizer Kuraray Poval 25-88 (partially hydrolyzed polyvinyl alcohol) was stirred for 30 minutes at 85-90 ° C., with a moderate stream of nitrogen flowing through it the three-way stopcock was fed into the apparatus and to the bubble counter.
- Kuraray Poval 25-88 partially hydrolyzed polyvinyl alcohol
- the temperature was increased by 1 ° C. for 15 minutes until a temperature of 82 ° C. was reached. It was stirred vigorously for four hours. A solution of 65 mg of BPO and 500 mg of methyl methacrylate was then added and the temperature was increased to 87.degree. At this temperature, the reaction mixture was stirred for 12 hours under a nitrogen atmosphere. The result was globules and also somewhat compact material. The supernatant aqueous solution was decanted, then water was added and suction filtered through a paper filter. The methacrylate polymer was dried for 5 hours at 80 ° C. and for one hour at 100 ° C. in a vacuum (approx. 0.02 mbar).
- the 31 P-NMR spectrum of this polymer recorded in deutero-chloroform only contained the signals of the DOPO unit (approx. 36 ppm) and the DDPO unit (-8.2 ppm).
- the ratio of the signal integrals almost corresponded to the expected value of 1.00: 1.50.
- Approx. 9 g of the methacrylate polymer were obtained.
- the reaction flask containing the aqueous solution was also partially evacuated twice and each time refilled with nitrogen.
- the contents of the flask were then heated to 95 ° C. with stirring, a moderate stream of nitrogen being passed through the three-way stopcock into the apparatus and to the bubble counter. After stirring for 30 minutes, the temperature was lowered to about 65 ° C.
- the contents of the dropping funnel were added to the aqueous solution thus deoxygenated.
- the contents of the flask were then heated to 73 ° C. in a gentle stream of nitrogen with stirring over a period of about 20 minutes. The temperature was increased to 83 ° C over the course of two hours. A moderate stream of nitrogen continued to be passed to the bubble counter. After a further hour, a solution of approx.
- the reaction flask containing the aqueous solution was also partially evacuated twice and each time refilled with nitrogen.
- the contents of the flask were then heated to 95 ° C. with stirring, a moderate stream of nitrogen being passed through the three-way stopcock into the apparatus and to the bubble counter. After stirring for 30 minutes, the temperature was lowered to about 65.degree.
- the contents of the dropping funnel were added to the aqueous solution thus freed from oxygen.
- the temperature of the oil bath was then increased to 75 ° C. with vigorous stirring of the reaction mixture, a milky-white suspension being formed. Stirring was continued for 3.5 hours, gradually increasing the temperature of the heating bath up to 84 ° C.
- the 1 H-NMR spectrum of the polymer recorded in deutero-chloroform showed that it contained unreacted monomers.
- the polymer was therefore heated in a fine vacuum (approx. 0.02 mbar) first to approx. 87 ° C. (4 h) and then to 93 ° C. (1 h). Thereafter, the 1 H-NMR spectrum of the methacrylate polymer showed the almost complete disappearance of the acrylate / methacrylate groups.
- the signals of the DOPO unit and the DDPO unit present at approx. 36 ppm or approx. -8 ppm, with the integral ratio roughly corresponding to the expected value of 1.00: 1.66
- the dropping funnel was partially evacuated twice and refilled with nitrogen in order to remove the atmospheric oxygen from the reagent mixture.
- the reaction flask containing the aqueous solution was also partially evacuated twice and each time refilled with nitrogen.
- the contents of the flask were then heated to 95 ° C. with stirring, a moderate stream of nitrogen being passed through the three-way stopcock into the apparatus and to the bubble counter. After stirring for 60 minutes, the temperature was lowered to about 63 ° C.
- the contents of the dropping funnel were added to the aqueous solution thus freed from oxygen.
- the temperature of the heating bath was then increased to 75 ° C. This temperature was maintained for 20 minutes; then the set temperature was increased to 77 ° C. and 30 minutes later increased to 80 ° C.
- the NMR Spectra of the polymer obtained in this way showed an approx. 95% conversion of the acrylate and methacrylate groups.
- the polymer was dried in vacuo (0.02 mbar) for three hours at 87-95 ° C. in order to remove residual water.
- the 1 H-NMR spectrum of the methacrylate polymer showed the almost complete disappearance of the acrylate / methacrylate groups.
- the signals of the DOPO unit and the DDPO unit were present at approx. 36 ppm and approx. -8 ppm, the integral ratio approximately corresponding to the expected value of 1.00: 2.33 .:
- the methacrylate polymer thus obtained was well soluble in organic solvents such as chloroform. It softened at around 160 ° C and melted at around 200 ° C.
- the DOPO monomer of Example 6 was used in various amounts
- a suspension polymerization took place in water with 1-decylthiol as regulator and dibenzoyl peroxide (BPO) as initiator. The monomers were destabilized before the polymerization.
- the syntheses of the methacrylate polymers were carried out in a reaction apparatus which consisted of a 250 ml three-necked flask, magnetic stirrer, heating bath, a dropping funnel and a reflux condenser to which a three-way stopcock with a bubble counter was attached. Both the dropping funnel and the three-way stopcock on the reflux condenser were connected with a Schlenk line.
- the methacrylate polymers obtained were converted into compact test rods and films of various thicknesses using an oil hydraulic laboratory press of the type HB 20300 (Schmidt Maschinentechnik; Bretten-Bauerbach, Germany).
- the test bars had the following dimensions: 70 mm x 10 mm x 0.8 mm.
- temperatures of 220 - 245 ° C were used (depending on the melting behavior of the methacrylate polymers).
- the quantities and results of the fire behavior test are listed in Table 2.
- Example 7c The polymerization was carried out analogously to Example 7c. Most of the methacrylate polymer was obtained in compact pieces that were detached from the glass wall and washed with water. The 1 H-NMR spectrum of this polymer recorded in deutero-chloroform showed that it contained unreacted monomers. Therefore, the polymer was placed in a fine vacuum (approx.
- Example 7c The polymerization was carried out analogously to Example 7c.
- the methacrylate polymer was obtained as relatively large polymer spheres (granules) which were washed twice with water.
- the polymer was dried in vacuo (0.02 mbar) at 87-105 ° C. for 5 hours and then examined by means of NMR spectroscopy.
- the 1 H-NMR spectrum of the methacrylate polymer showed the complete disappearance of the acrylate / methacrylate groups.
- the 31 P-NMR spectrum was also as expected: the signals of the DOPO unit and the diethyl phosphate unit were present at about 36 ppm and -1.3 ppm, respectively, with the integral ratio approaching the expected value of 1.00 : 1.74 corresponded.
- the polymerization was carried out analogously to Example 7c.
- the methacrylate polymer was obtained in compact pieces which were detached from the glass wall and washed with water.
- the 1 H-NMR spectrum of this polymer recorded in deutero-chloroform showed a relatively high proportion of unreacted monomers.
- the polymer was heated in a fine vacuum (approx. 0.02 mbar) first to approx. 87 ° C. (3 h) and then to 97 ° C. (1 h). Thereafter, the 1 H-NMR spectrum of the methacrylate polymer showed the almost complete disappearance of the acrylate / methacrylate groups.
- the methacrylate polymer thus obtained had a phosphorus content of about 4% by weight.
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Abstract
L'invention concerne : un procédé de production de monomères d'acrylate d'oxyde d'oxa-phosphaphénanthrène par addition de phospha-Michael sur des acrylates, dans lequel l'oxyde d'oxa-phosphaphénanthrène est mis à réagir avec un diacrylate de α,ω-alkyldiol dans un rapport molaire de 1:1,5 à 1:10 en présence d'une base et d'un inhibiteur de polymérisation à des températures de 70 à 120 °C et le diacrylate de α,ω-alkyldiol n'ayant pas réagi est éliminé ; des monomères pouvant être obtenus au moyen du procédé et leur utilisation pour produire des polymères thermoplastiques de (méth)acrylate, résistant à la flamme et un procédé de production de polymères thermoplastiques de (méth)acrylate résistant à la flamme, à l'aide des monomères ; des polymères pouvant être obtenus par ce procédé et leur utilisation pour produire des films et des panneaux transparents.
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DE10359269B4 (de) | 2003-12-17 | 2012-05-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verwendung hydroxylgruppenhaltiger Phosphinate als und zur Herstellung von Flammschutzmitteln, die sich zur Einbindung in Polymerharze eignen oder als Bestandteil flammgeschützter Polymere, mit diesen Phosphinaten hergestellte neue Phosphinate mit organisch polymerisierbaren Gruppen, deren Herstellung sowie Verwendung in flammgeschützten Polymerharzen |
WO2008132111A1 (fr) | 2007-04-26 | 2008-11-06 | Basf Se | Matières thermoplastiques à mouler ignifugées |
KR101489953B1 (ko) | 2011-12-19 | 2015-02-04 | 제일모직주식회사 | 난연 아크릴계 공중합체, 이를 포함하는 수지 조성물 및 그 성형품 |
US20140187688A1 (en) | 2012-12-28 | 2014-07-03 | Cheil Industries Inc. | (Meth)Acrylic Copolymer, Method for Preparing the Same and Thermoplastic Resin Composition Comprising the Same |
DE102013101487A1 (de) | 2013-02-14 | 2014-08-14 | Chemische Fabrik Budenheim Kg | Duromer, Herstellungsverfahren, Verwendung und Zusammensetzungen |
EP3087128B1 (fr) | 2013-12-27 | 2019-09-11 | Dow Global Technologies LLC | Copolymères ignifuges de monomères de dialkyl (méth)acryloyloxyalkylphosphate ou de dialkyl (méth)acryloyloxyalkylphosphonate et mousses polymères produites à partir de ceux-ci |
JP6503668B2 (ja) | 2014-09-19 | 2019-04-24 | Dic株式会社 | 硬化性樹脂組成物、その硬化物、及び積層体 |
CN104497051A (zh) | 2014-12-20 | 2015-04-08 | 王树礼 | 一种涂料用反应型无卤阻燃剂的制备方法 |
US9540568B1 (en) | 2015-07-27 | 2017-01-10 | International Business Machines Corporation | Flame-retardant copolymers |
CN105440080A (zh) * | 2015-11-23 | 2016-03-30 | 兰州理工大学 | 一种含磷丙烯酸酯的制备方法 |
CN105294921A (zh) * | 2015-11-23 | 2016-02-03 | 兰州理工大学 | 一种含磷本征阻燃丙烯酸树脂的制备方法 |
CN105669760B (zh) * | 2016-03-07 | 2017-06-06 | 中国科学院化学研究所 | 一种有机磷杂菲衍生物及其制备方法与应用 |
US11059960B2 (en) | 2017-10-16 | 2021-07-13 | International Business Machines Corporation | Cross-linked impact modified polyphosphazenes |
DE102018100984A1 (de) | 2018-01-17 | 2019-07-18 | Chemische Fabrik Budenheim Kg | Phosphorhaltige thermoplastische Polymere |
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