EP2566914A1 - Polymethacrylimide foam materials having reduced flammability and method for producing same - Google Patents
Polymethacrylimide foam materials having reduced flammability and method for producing sameInfo
- Publication number
- EP2566914A1 EP2566914A1 EP11706249A EP11706249A EP2566914A1 EP 2566914 A1 EP2566914 A1 EP 2566914A1 EP 11706249 A EP11706249 A EP 11706249A EP 11706249 A EP11706249 A EP 11706249A EP 2566914 A1 EP2566914 A1 EP 2566914A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- meth
- poly
- foam
- acrylimide foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 239000006261 foam material Substances 0.000 title abstract 2
- 229920007790 polymethacrylimide foam Polymers 0.000 title description 12
- 239000000203 mixture Substances 0.000 claims abstract description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000006260 foam Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 15
- 238000005187 foaming Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 8
- 239000004604 Blowing Agent Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000004971 Cross linker Substances 0.000 claims description 6
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- YWDFOLFVOVCBIU-UHFFFAOYSA-N 1-dimethoxyphosphorylpropane Chemical compound CCCP(=O)(OC)OC YWDFOLFVOVCBIU-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 12
- 239000003063 flame retardant Substances 0.000 description 21
- 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 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003999 initiator Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 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 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CQCXMYUCNSJSKG-UHFFFAOYSA-N 1-dimethoxyphosphorylethene Chemical compound COP(=O)(OC)C=C CQCXMYUCNSJSKG-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- -1 di-tert-butycarbonat Chemical compound 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 230000003505 mutagenic effect Effects 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- CKSAKVMRQYOFBC-UHFFFAOYSA-N 2-cyanopropan-2-yliminourea Chemical compound N#CC(C)(C)N=NC(N)=O CKSAKVMRQYOFBC-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 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 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
- KYEAGAAZBYGBRM-UHFFFAOYSA-N C(O)(O)=O.C(#N)O.CC(=O)C Chemical compound C(O)(O)=O.C(#N)O.CC(=O)C KYEAGAAZBYGBRM-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- GCNKJQRMNYNDBI-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(2-methylprop-2-enoyloxymethyl)butyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CC)COC(=O)C(C)=C GCNKJQRMNYNDBI-UHFFFAOYSA-N 0.000 description 1
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000000011 acetone peroxide Substances 0.000 description 1
- 235000019401 acetone peroxide Nutrition 0.000 description 1
- CGBYBGVMDAPUIH-UHFFFAOYSA-N acide dimethylmaleique Natural products OC(=O)C(C)=C(C)C(O)=O CGBYBGVMDAPUIH-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- MSZJEPVVQWJCIF-UHFFFAOYSA-N butylazanide Chemical compound CCCC[NH-] MSZJEPVVQWJCIF-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- YDVJBLJCSLVMSY-UHFFFAOYSA-N carbamoyl cyanide Chemical compound NC(=O)C#N YDVJBLJCSLVMSY-UHFFFAOYSA-N 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- WSYCKBNUJPXUDK-UHFFFAOYSA-N di(pentan-2-yl)diazene Chemical compound CCCC(C)N=NC(C)CCC WSYCKBNUJPXUDK-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- CGBYBGVMDAPUIH-ARJAWSKDSA-N dimethylmaleic acid Chemical compound OC(=O)C(/C)=C(/C)C(O)=O CGBYBGVMDAPUIH-ARJAWSKDSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GZXSDYYWLZERLF-UHFFFAOYSA-N ethyl n-ethylcarbamate Chemical compound CCNC(=O)OCC GZXSDYYWLZERLF-UHFFFAOYSA-N 0.000 description 1
- CUICPJOPYVMUPK-UHFFFAOYSA-N ethyl n-tert-butylcarbamate Chemical compound CCOC(=O)NC(C)(C)C CUICPJOPYVMUPK-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- NKVMCSDLYHGDMD-UHFFFAOYSA-N methanetetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)(C(O)=O)C(O)=O NKVMCSDLYHGDMD-UHFFFAOYSA-N 0.000 description 1
- DUVTXUGBACWHBP-UHFFFAOYSA-N methyl 2-(1h-benzimidazol-2-ylmethoxy)benzoate Chemical compound COC(=O)C1=CC=CC=C1OCC1=NC2=CC=CC=C2N1 DUVTXUGBACWHBP-UHFFFAOYSA-N 0.000 description 1
- SURZCVYFPAXNGN-UHFFFAOYSA-N methyl-carbamic acid ethyl ester Chemical compound CCOC(=O)NC SURZCVYFPAXNGN-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- MAIURHHAZPZPGJ-UHFFFAOYSA-N n'-butyloxamide Chemical compound CCCCNC(=O)C(N)=O MAIURHHAZPZPGJ-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- CNPHCSFIDKZQAK-UHFFFAOYSA-N n-prop-2-enylprop-2-enamide Chemical compound C=CCNC(=O)C=C CNPHCSFIDKZQAK-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- AGZPNUZBDCYTBB-UHFFFAOYSA-N triethyl methanetricarboxylate Chemical compound CCOC(=O)C(C(=O)OCC)C(=O)OCC AGZPNUZBDCYTBB-UHFFFAOYSA-N 0.000 description 1
- BNOIMFITGLLJTH-UHFFFAOYSA-N trimethyl methanetricarboxylate Chemical compound COC(=O)C(C(=O)OC)C(=O)OC BNOIMFITGLLJTH-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
Definitions
- the invention relates to compositions for the preparation of polymethacrylimide foams with particular
- the present invention relates to the process for their preparation, processing and use.
- PMI foams Polymethacrylimide foams
- ROHACELL ® Polymethacrylimide foams
- applications include processing
- Laminates composites, foam composites,
- Coating materials are shaped bodies which consist of an outer covering layer and an inner layer
- Core material are constructed.
- the cover layers used are materials that can absorb uniaxial or multiaxial extremely high tensile forces. Examples are glass and glass
- Adhesive resins are fixed on the core material.
- the core materials used are preferably materials with low densities, typically in the range of 30 kg / m 3 and 200 kg / m 3 . Special significance of such materials in lightweight construction, especially in aircraft or vehicle construction. In addition, the flame retardance of the materials is also of great importance in these fields of application. State of the art
- PMI Polymethacrylimide
- DMMP Dimethylmethanphosphonaten
- EP 0 146 892 in which DMMP and functionalized DMMP are disclosed as flame retardants for polymethacrylimide. Meanwhile, however, DMMP has been identified as a mutagen, so there is a great need for DMMP as a
- polymethacrylimide foams represent sensitive systems and are difficult to optimize in terms of the foaming behavior.
- flame retardant stabilizers in such foam formulations reduce or prevent the foamability.
- Flame retardants some of which contain antimony oxides, can also be used phosphorus-containing compounds. Phosphorus compounds are preferred because of lower smoke toxicity in case of fire.
- Phosphorus compounds include phosphines
- Phosphine oxides Phosphine oxides, phosphonium compounds, phosphonates,
- Phosphites and / or phosphates may be organic and / or inorganic in nature. To date, however, no flame retardant is described in the prior art, with respect to comparable
- methacrylic acrylonitrile foams can be stabilized according to CN 101 544 720 with chlorinated flame retardants.
- chlorinated systems are not preferred for various reasons, especially in connection with flame retardancy or for reasons of health protection.
- EP 1 501 891 phosphorus compounds are generally described for the flameproofing of polyurethane foams.
- EP 2 152 834 Alkyldimethylphosphonate to
- DMPP Dimehtylpropylphosphonat
- PAI Polyacrylimide
- the object was to provide a flame-retardant PMI foams, the at least the same flame retardancy, comparable
- the object was that the foams have at least the same good thermomechanical properties and a similar good processability as the known PMI foams.
- novel PMI foams should be just as easy to produce as the PMI foams according to the prior art.
- DMPP Dimethylpropylphosphonate
- the notation poly (meth) acrylimide is in the following also for polymethacrylimide (PMI) and polyacrylimide (PAI).
- Methacrylic acid or acrylic acid is methacrylic acid or acrylic acid
- the poly (meth) acrylimide foam is usually obtained by foaming and crosslinking this mixture.
- the poly (meth) acrylimide foam is polymerized in bulk to a plate which
- Examples of the other vinylically unsaturated monomers mentioned under (A) are: esters of acrylic or
- the proportion of comonomers which can not or only with great difficulty be cyclized to anhydride or imide should not exceed 30% by weight, preferably 20% by weight and more preferably 10% by weight, based on the weight of the monomers.
- blowing agent (C) the following compounds or
- N-butyl oxamide trimethyl methane tricarboxylate, triethyl methane tricarboxylate, and monohydric alcohols of 3-8 carbon atoms such as propanol-1, propanol-2, butanol-1, butanol-2, tert-butanol and iso-butanol.
- crosslinking agents (D) are used for easy crosslinking, which stabilizes the foam during the foaming process and thus enables the production of homogeneous foams.
- crosslinkers can be divided into two groups: covalent crosslinkers (Dl), ie
- dimethacrylate 1,3-butanediol diacrylate or dimethacrylate, 1,4-butanediol diacrylate or dimethacrylate,
- ionic crosslinkers D2
- D2 ionic crosslinkers
- Examples include the acrylates or methacrylates the alkaline earth metals or the zinc. Zn and Mg (meth) acrylates are preferred.
- the (meth) acrylate salts can also be prepared by dissolving, for example, ZnO or MgO in the monomer batch.
- the foam may also be uncrosslinked.
- Initiators (E) are compounds and
- Classes of compounds are peroxides, hydroperoxides, and
- Peroxodisulfates percarbonates, perketals, peroxyesters, hydrogen peroxide and azo compounds.
- Initiators are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxodicarbonate, dilauryl peroxide,
- the initiators are preferred (E) in amounts of from 0.01 to 2% by weight, more preferably from 0.15 to 1.5% by weight, based on the total weight of
- additives can be added to the mixtures.
- additives include, but are not limited to, antistatic agents, antioxidants, mold release agents, lubricants,
- Coating materials can be produced from the poly (meth) acrylimide foams produced according to the invention. Coating materials include one-sided with a solid
- Sandwich materials in which the foam is surrounded on both sides by solid material may be films or plates. These can be made of metal, wood or preferably other polymers
- Consist of materials The connection can be made by gluing, melting or sewing.
- the poly (meth) acrylimide foams according to the invention or the layer materials produced therefrom have a broad field of application. They can be used in motor vehicles, rail vehicles, aircraft, watercraft, Spacecraft, machine parts, antennas, X-ray tables, speakers and pipes are used.
- the density or density was determined according to ISO 845.
- Methacrylonitrile and 5.9 g of allyl methacrylate were added as blowing agents 66 g of water and 69 g of formamide. Furthermore, 2.0 g of tert. Butyl perpivalate, 1.5 g tert. Butyl per-2-ethyl hexanoate, 4.9 g tert-butyl perbenzoate, 4.9 g cumyl perneodecanoate, 35 g zinc oxide and 9.8 g release agent (Moldwiz INT 20E). As a flame retardant 491 g of DMMP were used.
- This mixture was for 68 h at 39 ° C and in one of two glass plates of size 50x50 cm and 28 mm thick
- the subsequent foaming in the hot air process was carried out at 201 ° C for 2 h.
- the resulting foam had a density of 118 kg / m 3 .
- Another sample was foamed for 2 hours at 219 ° C.
- the resulting foam had a density of 76 kg / m 3 .
- the foams have a homogeneous foaming pattern and fully meet the requirements of the fire test.
- This mixture was for 72 h at 40 ° C and in one of two glass plates of size 50x50 cm and 28 mm thick
- the subsequent foaming in the hot air process was 2h at 203 ° C.
- the resulting foam had a
- Example 1 The foams of Example 1 have a homogeneous
- Foaming can be distinguished from Comparative Example 1. Both foams fully met the requirements of the fire test.
- Methacrylonitrile and 590 mg of allyl methacrylate were added as blowing agents 6, 6 g of water and 6, 9 g of formamide. Furthermore, the mixture was 200 mg tert. Butyl perpivalate, 150 mg tert. Butyl per-2-ethyl hexanoate, 49 mg tert-butyl perbenzoate, 49 mg cumyl perneodecanoate, 3.5 g zinc oxide and 980 mg release agent (Moldwiz INT 20E). The flame retardant was 42.7 g of vinylphosphonic acid
- the subsequent foaming in the hot air process was 2h at 220 ° C.
- the resulting foam had a
- the subsequent foaming in the hot air process was 2 hours at 200 ° C.
- the resulting foam had a
Abstract
The invention relates to compositions for producing poly(meth)acrylamide foam materials having particularly reduced flammability. The present invention further relates to a method for the production, the processing and the use thereof.
Description
Polymethacrylimid-Schaumstoffe mit verminderter Polymethacrylimide foams with reduced
Entflammbarkeit sowie Verfahren zur Herstellung dieser Flammability and method of making this
Gebiet der Erfindung Field of the invention
Die Erfindung betrifft Zusammensetzungen zur Herstellung von Polymethacrylimid-Schaumstoffen mit besonders The invention relates to compositions for the preparation of polymethacrylimide foams with particular
verminderter Entflammbarkeit. Darüber hinaus betrifft die vorliegende Erfindung das Verfahren zu deren Herstellung, Verarbeitung und Anwendung. reduced flammability. Moreover, the present invention relates to the process for their preparation, processing and use.
Polymethacrylimid-Schaumstoffe (PMI-Schaumstoffe) sind bereits seit langer Zeit bekannt. Unter dem Handelsnahmen ROHACELL® finden diese Schaumstoffe insbesondere im Bereich der Schichtwerkstoffe viele Anwendungen. Zu diesen Polymethacrylimide foams (PMI foams) have been known for a long time. Under the trademark ROHACELL ® , these foams find many applications, especially in the area of coating materials. To this
Anwendungen zählen beispielsweise die Verarbeitung zu For example, applications include processing
Laminaten, Composits, Schaumstoffverbundkörpern, Laminates, composites, foam composites,
Sandwichkonstruktionen oder Sandwichwerkstoffen. Sandwich constructions or sandwich materials.
Schichtwerkstoffe sind Formkörper, die aus einer außen liegenden Deckschicht und einem innen liegenden Coating materials are shaped bodies which consist of an outer covering layer and an inner layer
Kernwerkstoff aufgebaut sind. Als Deckschichten verwendet man Materialien, die uni- oder multiaxial äußerst hohe Zugkräfte aufnehmen können. Beispiele sind Glas- und Core material are constructed. The cover layers used are materials that can absorb uniaxial or multiaxial extremely high tensile forces. Examples are glass and glass
Kohlefasergewebe oder auch Aluminiumplatten, die mit Carbon fiber fabric or aluminum plates with
Klebeharzen auf dem Kernwerkstoff fixiert werden. Als Kernwerkstoffe werden bevorzugt Materialien mit geringen Raumgewichten, typischerweise im Bereich von 30 kg/m3 und 200 kg/m3 eingesetzt. Besondere Bedeutung haben solche Werkstoffe im Leichtbau, insbesondere im Flugzeug- oder Fahrzeugbau. Gerade in diesen Anwendungsfeldern ist darüber hinaus aber auch die Schwerentflammbarkeit der Werkstoffe von großer Bedeutung.
Stand der Technik Adhesive resins are fixed on the core material. The core materials used are preferably materials with low densities, typically in the range of 30 kg / m 3 and 200 kg / m 3 . Special significance of such materials in lightweight construction, especially in aircraft or vehicle construction. In addition, the flame retardance of the materials is also of great importance in these fields of application. State of the art
Nach Stand der Technik werden Polymerschäume auf The prior art polymer foams on
Polymethacrylimid (PMI) mit Dimethylmethanphosphonaten (DMMP) , insbesondere in einer Konzentration von ca. 10 Gew%, stabilisiert. Siehe dazu die EP 0 146 892, in der DMMP und funktionalisiertes DMMP als Flammschutzmittel für Polymethacrylimid offenbart sind. DMMP ist inzwischen jedoch inzwischen als mutagen identifiziert worden, so dass ein großes Bedürfnis dafür vorliegt, DMMP als Polymethacrylimide (PMI) with Dimethylmethanphosphonaten (DMMP), in particular in a concentration of about 10% by weight, stabilized. See EP 0 146 892, in which DMMP and functionalized DMMP are disclosed as flame retardants for polymethacrylimide. Meanwhile, however, DMMP has been identified as a mutagen, so there is a great need for DMMP as a
Flammschutzmittel, vor allem für PMI-Schäume, zu ersetzen. Flame retardant, especially for PMI foams to replace.
Dem Fachmann ist jedoch allgemein bekannt, dass However, it is well known to those skilled in the art that
insbesondere Polymethacrylimid-Schaumstoffe empfindliche Systeme darstellen und in Bezug auf das Schäumungsverhalten nur schwer optimierbar sind. So vermindern bzw. verhindern eine Reihe handelsüblicher Flammschutzstabilisatoren in solchen Schaumstoffrezepturen die Schäumbarkeit. in particular polymethacrylimide foams represent sensitive systems and are difficult to optimize in terms of the foaming behavior. Thus, a number of commercially available flame retardant stabilizers in such foam formulations reduce or prevent the foamability.
Die Liste der handelsüblichen Flammschutzmittel für andere Anwendungen ist sehr lang. Neben halogenhaltigen The list of commercial flame retardants for other applications is very long. In addition to halogen-containing
Flammschutzmitteln, die teilweise Antimonoxide enthalten, können auch phosphorhaltige Verbindungen eingesetzt werden. Phosphorhaltige Verbindungen sind wegen der geringeren Rauchgastoxizität im Brandfall bevorzugt. Zu den Flame retardants, some of which contain antimony oxides, can also be used phosphorus-containing compounds. Phosphorus compounds are preferred because of lower smoke toxicity in case of fire. To the
Phosphorverbindungen gehören unter anderem Phosphane, Phosphorus compounds include phosphines,
Phosphanoxide, Phosphoniumverbindungen, Phosphonate, Phosphine oxides, phosphonium compounds, phosphonates,
Phosphite und/oder Phosphate. Diese Verbindungen können organischer und/oder anorganischer Natur sein.
Bis dato ist jedoch kein Flammschutzmittel im Stand der Technik beschrieben, das bezüglich vergleichbaren Phosphites and / or phosphates. These compounds may be organic and / or inorganic in nature. To date, however, no flame retardant is described in the prior art, with respect to comparable
Flammschutz und mechanischen Eigenschaften ähnlich gute Eigenschaften des PMI-Schaums ermöglicht. Flame retardancy and mechanical properties similar good properties of PMI foam allows.
Für andere Polymerschäume dagegen sind diverse For other polymer foams, however, are diverse
Flammschutzmittel beschrieben. So können Methacryl- Acrylnitrilschäume gemäß CN 101 544 720 mit chlorierten Flammschutzmitteln stabilisiert werden. Chlorierte Systeme sind aber aus diversen Gründen, gerade auch im Zusammenhang mit Flammschutz oder aus Gründen des Gesundheitsschutzes, nicht bevorzugt einzusetzen. Flame retardant described. Thus, methacrylic acrylonitrile foams can be stabilized according to CN 101 544 720 with chlorinated flame retardants. However, chlorinated systems are not preferred for various reasons, especially in connection with flame retardancy or for reasons of health protection.
In EP 1 501 891 werden Phosphorverbindungen im Allgemeinen für die Flammschutzausrüstung von Polyurethanschäumen beschrieben . In EP 2 152 834 werden Alkyldimethylphosphonate zur In EP 1 501 891 phosphorus compounds are generally described for the flameproofing of polyurethane foams. In EP 2 152 834 Alkyldimethylphosphonate to
Flammschutzverbesserung von Epoxidharzen, Polyestern oder Polyurethanen aufgeführt. Der Einsatz von Flame retardant improvement of epoxy resins, polyesters or polyurethanes listed. The use of
Dimehtylpropylphosphonat (DMPP) im Speziellen für Dimehtylpropylphosphonat (DMPP) in particular for
Polyurethanschäume findet sich in DE 44 183 07 bzw. in CN 101 487 299. (Meth) acrylimide werden in keiner dieser Schriften als Matrixmaterial beschrieben. Polyurethane foams are found in DE 44 183 07 and in CN 101 487 299. (Meth) acrylimides are described in any of these writings as matrix material.
Aufgabe Aufgabe vor dem Hintergrund der Technik war es, ein neues Flammschutzmittel für Polymethacrylimide (PMI) oder Object Task Against the background of the technology was to develop a new flame retardant for polymethacrylimides (PMI) or
Polyacrylimide (PAI), insbesondere für PMI-oder PAI-Schäume zu finden, welches nicht mutagen oder krebserregend ist und gegenüber dem Stand der Technik zu keinem negativen Polyacrylimide (PAI), especially for PMI or PAI foams, which is not mutagenic or carcinogenic and compared to the prior art to no negative
Einfluss auf die Schäumbarkeit führt.
Darüber hinaus bestand die Aufgabe einen flammgeschützten PMI-Schaumstoffen zur Verfügung zu stellen, der mindestens die gleiche Flammschutzwirkung, bei vergleichbaren Influence on the foamability leads. In addition, the object was to provide a flame-retardant PMI foams, the at least the same flame retardancy, comparable
mechanischen Eigenschaften wie der Stand der Technik aufweist. has mechanical properties as the prior art.
Darüber hinaus bestand die Aufgabe, dass die Schaumstoffe zumindest gleich gute thermomechanische Eigenschaften und eine ähnlich gute Verarbeitbarkeit wie die bekannten PMI- Schäume aufweisen. In addition, the object was that the foams have at least the same good thermomechanical properties and a similar good processability as the known PMI foams.
Darüber hinaus sollen die neuartigen PMI-Schaumstoffe genauso einfach herstellbar sein wie die PMI-Schaumstoffe nach Stand der Technik. In addition, the novel PMI foams should be just as easy to produce as the PMI foams according to the prior art.
Weitere nicht explizit genannte Aufgaben ergeben sich aus dem GesamtZusammenhang der nachfolgenden Beschreibung, Ansprüche und Beispiele. Other tasks not explicitly mentioned arise from the overall context of the following description, claims and examples.
Lösung solution
Gelöst wurden die Aufgaben durch Verwendung von The tasks were solved by using
Dimethylpropylphosphonat (DMPP) als Flammschutzmittel für Poly (meth) acrylimid-Schaumstoffe . Überraschend wurde gefunden, dass DMPP als einziges handelsübliche Dimethylpropylphosphonate (DMPP) as a flame retardant for poly (meth) acrylimide foams. Surprisingly, it was found that DMPP was the only commercially available one
Flammschutzmittel geeignet ist, DMMP in Flame retardant is suitable, DMMP in
Poly (meth) acrylimid-Schaumstoffen zu ersetzen. Genauso überraschend wurde gefunden, dass DMPP in anderen, höheren Konzentrationen als DMMP eingesetzt werden muss.
Die Schreibweise Poly (meth) acrylimid steht im Folgenden gleichzeitig für Polymethacrylimid (PMI) und Polyacrylimid (PAI) . To replace poly (meth) acrylimide foams. Equally surprisingly, it has been found that DMPP must be used in concentrations higher than DMMP. The notation poly (meth) acrylimide is in the following also for polymethacrylimide (PMI) and polyacrylimide (PAI).
Insbesondere wurden die Aufgaben durch neuartige geschäumte Poly (meth) acrylamide, die aus folgendem Gemisch hergestellt wurden, gelöst: In particular, the objects were achieved by novel foamed poly (meth) acrylamides, which were prepared from the following mixture:
(A) 30 - 70 Gew%, bevorzugt 40 - 60 Gew% (A) 30-70% by weight, preferably 40-60% by weight
Methacrylsäure oder Acrylsäure, Methacrylic acid or acrylic acid,
30 - 60 Gew%, bevorzugt 30 - 50 Gew% 30-60% by weight, preferably 30-50% by weight
Methacrylnitril oder Acrylnitril, Methacrylonitrile or acrylonitrile,
0 - 30 Gew%, bevorzugt 0 -10 Gew% weitere vinylisch ungesättigte Monomere, 0 to 30% by weight, preferably 0 to 10% by weight, of further vinylically unsaturated monomers,
(B) 8 -18 Gew%, bevorzugt 10 - 15 Gew% (B) 8 to 18% by weight, preferably 10 to 15% by weight
Dirnethylpropylphosphonat, Dirnethylpropylphosphonat,
(C) 0,01 -10 Gew%, bevorzugt 0,1 - 5 Gew% Treibmittel, (C) 0.01-10% by weight, preferably 0.1-5% by weight of blowing agent,
(D) 0 -10 Gew%, bevorzugt 0,1 - 5 Gew% Vernetzer,(D) 0-10% by weight, preferably 0.1-5% by weight of crosslinker,
(E) 0,01 - 2 Gew%, bevorzugt 0,1 - 1 Gew% (E) 0.01-2% by weight, preferably 0.1-1% by weight
PolymerisationsInitiatoren polymerization
(F) 0 - 10 Gew%, bevorzugt 0 - 5 Gew% übliche (F) 0-10% by weight, preferably 0-5% by weight usual
Zusatzstoffe additives
Der Poly (meth) acrylimid-Schaumstoff wird in der Regel durch Schäumen und Vernetzen dieses Gemischs erhalten. The poly (meth) acrylimide foam is usually obtained by foaming and crosslinking this mixture.
Insbesondere wird der Poly (meth) acrylimid-Schaumstoff in Substanz zu einer Platte polymerisiert , welche In particular, the poly (meth) acrylimide foam is polymerized in bulk to a plate which
gegebenenfalls getempert wird. Die Schäumung wird optionally annealed. The foaming will
anschließend bei Temperaturen von 150 bis 250°C subsequently at temperatures of 150 to 250 ° C
durchgeführt .
Beispiele für die unter (A) genannten weiteren vinylisch ungesättigten Monomere sind: Ester der Acryl- oder carried out . Examples of the other vinylically unsaturated monomers mentioned under (A) are: esters of acrylic or
Methacrylsäure mit niedrigen Alkoholen mit 1 - 4 C-Atomen, Styrol, Maleinsäure oder deren Anhydrid, Itakonsäure oder deren Anhydrid, Vinylpyrrolidon, Vinylchlorid und/oderMethacrylic acid with lower alcohols having 1-4 C atoms, styrene, maleic acid or its anhydride, itaconic acid or its anhydride, vinylpyrrolidone, vinyl chloride and / or
Vinylidenchlorid . Der Anteil der Comonomere, die sich nicht oder nur sehr schwer zu Anhydrid oder Imid cyclisieren lassen, soll 30 Gew.T, vorzugsweise 20 Gew.T und besonders bevorzugt 10 Gew.T, bezogen auf das Gewicht der Monomeren, nicht übersteigen. Vinylidene chloride. The proportion of comonomers which can not or only with great difficulty be cyclized to anhydride or imide should not exceed 30% by weight, preferably 20% by weight and more preferably 10% by weight, based on the weight of the monomers.
Als Treibmittel (C) können folgende Verbindungen oder As blowing agent (C), the following compounds or
Gemische daraus verwendet werden: Formamid, Ameisensäure, Harnstoff, Itakonsäure, Zitronensäure, Dicyandiamid, Mixtures thereof are used: formamide, formic acid, urea, itaconic acid, citric acid, dicyandiamide,
Wasser, Monoalkylharnstoffe, Dimethylharnstoff , 5,5λ-Αζο- bis-5-äthyl-l, 3-dioxan, 2, 2 λ -Azo-bis-isobutter- säurebutylamid, 2, 2 λ -Azo-bis-isobuttersäure-N-diethylamid, 2,2λ,4,4,4λ,4 λ -Hexamethyl-2 , 2 ' -azopentan, 2 , 2 λ -Azo-bis-2- methyl-propan, Dimethylcarbonat , Di-tert-butycarbonat , Acetoncyanhydrincarbonat , Oxi-isobuttersäuremethylester- carbonat, N-Methylurethan, N-Ethylurethan, N-tert- butylurethan, Urethan, Oxalsäure, Maleinsäure, Oxi- isobuttersäure, Malonsäure, Cyanformamid, Dimethyl- maleinsäure, Methantetracarbonsäuretetraäthylester , Water, monoalkylureas, dimethylurea, 5,5 λ -Αζο-bis-5-ethyl-l, 3-dioxane, 2, 2 λ -Azo-bis-isobutyric acid butylamide, 2, 2 λ -Azo-bis-isobutyric acid-N -diethylamid, 2.2 λ, λ 4,4,4, 4 λ -hexamethyl 2, 2 '-azopentan, 2, 2 λ azo-bis-2-methyl-propane, dimethyl carbonate, di-tert-butycarbonat, Acetone cyanohydrate carbonate, methyl isobutyrate, N-methyl urethane, N-ethyl urethane, N-tert-butyl urethane, urethane, oxalic acid, maleic acid, oxyisobutyric acid, malonic acid, cyanoformamide, dimethyl maleic acid, tetraacetate of methanetetracarboxylate,
Oxamidsäure-n-butylester , Methantricarbonsäuretrimethyl- ester, Methantricarbonsäuretriäthylester , sowie einwertige Alkohole aus 3-8 Kohlenstoffatomen wie z.B. Propanol-1, Propanol-2, Butanol-1, Butanol-2, tert-Butanol und iso- Butanol .
Für eine leichte Vernetzung, die den Schaum während des Schäumvorgangs stabilisiert und so die Herstellung von homogenen Schäumen ermöglicht, werden Vernetzer (D) N-butyl oxamide, trimethyl methane tricarboxylate, triethyl methane tricarboxylate, and monohydric alcohols of 3-8 carbon atoms such as propanol-1, propanol-2, butanol-1, butanol-2, tert-butanol and iso-butanol. For easy crosslinking, which stabilizes the foam during the foaming process and thus enables the production of homogeneous foams, crosslinking agents (D) are used.
zugesetzt. Gleichzeitig werden die Wärmeformbeständigkeit und das Kriechverhalten des Schaums durch Vernetzer added. At the same time, the heat resistance and the creep behavior of the foam by crosslinking agents
verbessert. Mögliche Vernetzer können in zwei Gruppen unterteilt werden: kovalente Vernetzer (Dl), also improved. Possible crosslinkers can be divided into two groups: covalent crosslinkers (Dl), ie
einpolymerisierbare mehrfach ungesättigte Verbindungen. Als derartige Monomere können z. B. Allylacrylat , copolymerizable polyunsaturated compounds. As such monomers z. B. allyl acrylate,
Allylmethacrylat , Allylacrylamid, Allylmethacrylamid, Allyl methacrylate, allylacrylamide, allylmethacrylamide,
Methylen-bis-acrylamid oder -methacrylamid, Methylene bis-acrylamide or methacrylamide,
Diethylenbis (allylcarbonat ) , Ethylenglykoldiacrylat oder - dimethacrylat , Diethylenglykoldiacrylat oder - dimethacrylat, Triethylenglykoldiacrylat oder Diethylene bis (allyl carbonate), ethylene glycol diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, triethylene glycol diacrylate or
dimethacrylat, etraethylenglykoldiacrylat oder dimethacrylate, ethylene glycol diacrylate or
-dimethacrylat, Tripropylenglykoldiacrylat oder dimethacrylate, tripropylene glycol diacrylate or
-dimethacrylat, 1 , 3-Butandioldiacrylat oder -dimethacrylat, 1 , 4-Butandioldiacrylat oder -dimethacrylat, dimethacrylate, 1,3-butanediol diacrylate or dimethacrylate, 1,4-butanediol diacrylate or dimethacrylate,
Neopentyldioldiacrylat oder -dimethacrylat, Hexandiol-1 , 6- diacrylat oder -dimethacrylat, Trimethylolpropandiacrylat oder -dimethacrylat, Trimethylolpropantriacrylat oder - trimethacrylat , Pentaerythrittriacrylat oder - trimethacrylat , Pentaerythrittetraacrylat oder - tetramethacrylat , die Pentaerythritderivate jeweils ggf. auch als technisches Gemisch aus tri- und Neopentyldioldiacrylat or -dimethacrylat, hexanediol-1, 6-diacrylate or -dimethacrylat, trimethylolpropane diacrylate or dimethacrylate, trimethylolpropane triacrylate or - trimethacrylate, pentaerythritol triacrylate or - trimethacrylate, pentaerythritol tetraacrylate or - tetramethacrylate, the pentaerythritol derivatives in each case possibly also as a technical mixture of tri- and
tetrafunktionellen Verbindungen, sowie Triallylcyanurat oder Triallylisocyanurat verwendet werden. Als weitere Gruppe kommen ionische Vernetzer (D2) in Betracht. Dies sind mehrwertige Metallkationen, die ionische Brücken zwischen den Säuregruppen der Copolymere ausbilden. tetrafunctional compounds, as well as triallyl cyanurate or triallyl isocyanurate. Another group which may be considered are ionic crosslinkers (D2). These are polyvalent metal cations that form ionic bridges between the acid groups of the copolymers.
Beipiele sind unter anderem die Acrylate oder Methacrylate
der Erdalkalimetalle oder des Zinks. Bevorzugt sind Zn- und Mg- (meth) acrylat . Die (Meth) acrylatsalze können auch durch Auflösen z.B. von ZnO oder MgO im Monomeransatz hergestellt werden . Examples include the acrylates or methacrylates the alkaline earth metals or the zinc. Zn and Mg (meth) acrylates are preferred. The (meth) acrylate salts can also be prepared by dissolving, for example, ZnO or MgO in the monomer batch.
Alternativ kann der Schaum auch unvernetzt vorliegen. Alternatively, the foam may also be uncrosslinked.
Als Initiatoren (E) werden Verbindungen und Initiators (E) are compounds and
Initiatorsysteme verwendet, die radikalische Initiator systems used, the radical
Polymerisationen in Gang setzen können. Bekannte Can initiate polymerizations. Known
Verbindungsklassen sind Peroxide, Hydroperoxide, Classes of compounds are peroxides, hydroperoxides,
Peroxodisulfate, Percarbonate, Perketale, Peroxiester, Wasserstoffperoxid und Azoverbindungen . Beispiele für Peroxodisulfates, percarbonates, perketals, peroxyesters, hydrogen peroxide and azo compounds. examples for
Initiatoren sind Wasserstoffperoxid, Dibenzoylperoxid, Dicyclohexylperoxodicarbonat , Dilaurylperoxid, Initiators are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxodicarbonate, dilauryl peroxide,
Methylethylketonperoxid, Acetylacetonperoxid, Di-tert- butylperoxid, tert-Butylhydroperoxid, Cumolhydroperoxid, t-Butylperoctanoat , tert-Butylper-2-ethylhexanoat , tert- Butylperneodecanoat , tert-Amylperpivalat , tert- Butylperpivalat , tert-Butylperbenzoat , Lithium-, Natrium-, Kalium- und Ammoniumperoxodisulfat , Azoisobutyronitril , 2, 2-Azobisiso-2 , 4-dimethylvaleronitril, 2, 2- Azobisisobutyro-nitril , 2, 2 x-Azo-bis (2- amidinopropan) dihydrochlorid, 2- (Carbamoylazo) isobutyronitril und 4,4λ- Azobis (cyanovaleriansäure) . Gleichfalls geeignet sind Methyl ethyl ketone peroxide, acetyl acetone peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroctanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisulfate, azobisisobutyronitrile, 2, 2-Azobisiso-2, 4-dimethylvaleronitrile, 2, 2-azobisisobutyro-nitrile, 2, 2 x-azo-bis (2-amidinopropane) dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4 , 4 λ - azobis (cyanovaleric acid). Likewise suitable
Redoxinitiatoren (H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen, Springer, Heidelberg, 1967 oder Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, Seiten 286 ff, John Wiley & Sons, INew York, 1978) . Es kann günstig sein, Initiatoren und Initiatorsysteme mit Redox initiators (H. Rauch-Puntigam, Th. Völker, acrylic and methacrylic compounds, Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pages 286 ff, John Wiley & Sons, INew York, 1978) , It may be beneficial to use initiators and initiator systems
unterschiedlichen Zerfallseigenschaften bezüglich Zeit und Temperatur zu kombinieren. Bevorzugt werden die Initiatoren
(E) in Mengen von 0,01 bis 2 Gew.T, besonders bevorzugt von 0,15 bis 1,5 GewT bezogen auf das Gesamtgewicht der to combine different decay properties with respect to time and temperature. The initiators are preferred (E) in amounts of from 0.01 to 2% by weight, more preferably from 0.15 to 1.5% by weight, based on the total weight of
Monomere eingesetzt. Monomers used.
Des Weiteren können den Gemischen übliche Zusatzstoffe (F) zugesetzt werden. Hierzu gehören unter anderem Antistatika, Antioxidantien, Entformungsmittel , Schmiermittel, Furthermore, conventional additives (F) can be added to the mixtures. These include, but are not limited to, antistatic agents, antioxidants, mold release agents, lubricants,
Farbstoffe, Fließverbesserungsmittel, Füllstoffe, Dyes, flow improvers, fillers,
Lichtstabilisatoren, Pigmente, Trennmittel, Light stabilizers, pigments, release agents,
Verwitterungsschutzmittel und Weichmacher. Weathering agents and plasticizers.
Aus den erfindungsgemäß hergestellten Poly (meth) acrylimid- Schaumstoffen können Schichtwerkstoffe hergestellt werden. Schichtwerkstoffe umfassen einseitig mit einem festen Coating materials can be produced from the poly (meth) acrylimide foams produced according to the invention. Coating materials include one-sided with a solid
Material versehende Werkstoffe genauso wie Material providing materials as well as
Sandwichmaterialien, bei denen der Schaumstoff beidseitig von festem Material umgeben ist. Bei den festen Materialien kann es sich um Folien oder Platten handeln. Diese können aus Metall, Holz oder bevorzugt anderen polymeren Sandwich materials in which the foam is surrounded on both sides by solid material. The solid materials may be films or plates. These can be made of metal, wood or preferably other polymers
Werkstoffen bestehen. Die Verbindung kann mittels Kleben, Schmelzen oder Nähen erfolgen. Consist of materials. The connection can be made by gluing, melting or sewing.
Alternativ können Fasergebilde, üblicherweise aus Alternatively, fiber structures, usually made
Kohlefasern oder Glasfasern, mit dem Schaum in ein Werkzeug vorgelegt, dieses anschließend mit Harz getränkt und die Vorlage ausgehärtet werden. Carbon fibers or glass fibers, presented with the foam in a tool, this is then soaked with resin and cured the template.
Die erfindungsgemäßen Poly (meth) acrylimid-Schaumstoffe, bzw. die daraus hergestellten Schichtwerkstoffe haben ein breites Anwendungsgebiet. Sie können in Kraftfahrzeugen, Schienenfahrzeugen, Luftfahrzeugen, Wasserfahrzeugen,
Raumfahrzeugen, Maschinenteilen, Antennen, Röntgentischen, Lautsprechern und Rohren eingesetzt werden. The poly (meth) acrylimide foams according to the invention or the layer materials produced therefrom have a broad field of application. They can be used in motor vehicles, rail vehicles, aircraft, watercraft, Spacecraft, machine parts, antennas, X-ray tables, speakers and pipes are used.
Die im Folgenden gegebenen Beispiele werden zur besseren Veranschaulichung der vorliegenden Erfindung gegeben, sind jedoch nicht dazu geeignet, die Erfindung auf die hierin offenbarten Merkmale zu beschränken. The examples given below are given for a better illustration of the present invention, but are not intended to limit the invention to the features disclosed herein.
Beispiele Examples
Das Schäumungsbild wurde optisch bewertet. Dabei wurde ein Vergleich gegenüber dem Stand der Technik gemäß The foaming image was visually evaluated. In this case, a comparison with the prior art according to
Vergleichsbeispiel 1 vorgenommen. Comparative Example 1 made.
Die Brandtests und die Bewertung der Ergebnisse aus den Brandtests erfolgten gemäß Norm FAR 25.853. The fire tests and the evaluation of the results from the fire tests were carried out in accordance with standard FAR 25.853.
Die Dichte, bzw. das Raumgewicht wurde gemäß ISO 845 bestimmt . The density or density was determined according to ISO 845.
Vergleichsbeispiel 1 : DMMP Zu einem Gemisch aus 2800 g Methacrylsäure, 2110 g Comparative Example 1: DMMP To a mixture of 2800 g of methacrylic acid, 2110 g
Methacrylnitril und 5,9 g Allylmethacrylat wurden als Treibmittel 66 g Wasser und 69 g Formamid zugesetzt. Des Weiteren wurden der Mischung 2,0 g tert . -Butylperpivalat , 1,5 g tert . -Butylper-2-ethyl-hexanoat , 4,9 g tert.- Butylperbenzoat , 4,9 g Cumylperneodecanoat , 35 g Zinkoxid und 9,8 g Trennmittel (Moldwiz INT 20E) hinzugefügt. Als Flammschutzmittel wurden 491 g DMMP eingesetzt. Methacrylonitrile and 5.9 g of allyl methacrylate were added as blowing agents 66 g of water and 69 g of formamide. Furthermore, 2.0 g of tert. Butyl perpivalate, 1.5 g tert. Butyl per-2-ethyl hexanoate, 4.9 g tert-butyl perbenzoate, 4.9 g cumyl perneodecanoate, 35 g zinc oxide and 9.8 g release agent (Moldwiz INT 20E). As a flame retardant 491 g of DMMP were used.
Diese Mischung wurde 68 h bei 39°C und in einer aus zwei Glasplatten der Größe 50x50 cm und 28 mm dicken This mixture was for 68 h at 39 ° C and in one of two glass plates of size 50x50 cm and 28 mm thick
Randabdichtung gebildeten Kammer polymerisiert.
Anschließend wurde das Polymerisat zur Endpolymerisation über 32 h bei einer aufsteigenden Temperatur von 32°C bis 115°C getempert. Edge seal formed chamber polymerized. Subsequently, the polymer for final polymerization over 32 h at an increasing temperature of 32 ° C to 115 ° C was annealed.
Die darauffolgende Schäumung im Heißluftverfahren erfolgte über 2 h bei 201°C. Der so erhaltene Schaumstoff wies ein Raumgewicht von 118 kg/m3 auf. Eine weitere Probe wurde für 2h bei 219°C geschäumt. Der so erhaltene Schaumstoff wies ein Raumgewicht von 76 kg/m3 auf. The subsequent foaming in the hot air process was carried out at 201 ° C for 2 h. The resulting foam had a density of 118 kg / m 3 . Another sample was foamed for 2 hours at 219 ° C. The resulting foam had a density of 76 kg / m 3 .
Die Schaumstoffe weisen ein homogenes Schäumungsbild auf und erfüllten die Vorgaben des Brandtests vollständig. The foams have a homogeneous foaming pattern and fully meet the requirements of the fire test.
Beispiel 1 : DMPP Example 1: DMPP
Zu einem Gemisch aus 2400 g Methacrylsäure, 2400 g To a mixture of 2400 g of methacrylic acid, 2400 g
Methacrylnitril und 9,6 g Allylmethacrylat wurden als Treibmittel 144 g Formamid zugesetzt. Des Weiteren wurden der Mischung 1,9 g tert . -Butylperpivalat , 1,4 g tert.- Butylper-2-ethyl-hexanoat , 4,8 g tert . -Butylperbenzoat , 4,8 g Cumylperneodecanoat , 33,5 g Zinkoxid und 9, 6 g Methacrylonitrile and 9.6 g of allyl methacrylate were added as blowing agent 144 g of formamide. Furthermore, the mixture 1.9 g tert. Butyl perpivalate, 1.4 g of tert-butyl per-2-ethyl-hexanoate, 4.8 g of tert. Butyl perbenzoate, 4.8 g Cumylperneodecanoat, 33.5 g of zinc oxide and 9, 6 g
Trennmittel (Moldwiz INT 20E) hinzugefügt. Als Release agent (Moldwiz INT 20E) added. When
Flammschutzmittel wurden 600 g DMPP eingesetzt. Flame retardants were used 600 g of DMPP.
Diese Mischung wurde 72 h bei 40°C und in einer aus zwei Glasplatten der Größe 50x50 cm und 28 mm dicken This mixture was for 72 h at 40 ° C and in one of two glass plates of size 50x50 cm and 28 mm thick
Randabdichtung gebildeten Kammer polymerisiert. Edge seal formed chamber polymerized.
Anschließend wurde das Polymerisat zur Endpolymerisation über 32 h bei einer aufsteigenden Temperatur von 32 °C bis 115°C getempert. Subsequently, the polymer for final polymerization over 32 h at an increasing temperature of 32 ° C to 115 ° C was annealed.
Die darauffolgende Schäumung im Heißluftverfahren erfolgte 2h bei 203°C. Der so erhaltene Schaumstoff wies ein The subsequent foaming in the hot air process was 2h at 203 ° C. The resulting foam had a
Raumgewicht von 108 kg/m3 auf. Eine weitere Probe wurde für
2h bei 219°C geschäumt. Der so erhaltene Schaumstoff wies ein Raumgewicht von 70 kg/m3 auf. Density of 108 kg / m 3 on. Another sample was for 2h foamed at 219 ° C. The resulting foam had a density of 70 kg / m 3 .
Die Schaumstoffe aus Beispiel 1 weisen ein homogenes The foams of Example 1 have a homogeneous
Schäumungsbild auf, das sich nicht erkennbar von der Foam image on, which is not recognizable from the
Schäumung aus Vergleichsbeispiel 1 unterscheiden lässt. Beide Schaumstoffe erfüllten die Vorgaben des Brandtests vollständig . Foaming can be distinguished from Comparative Example 1. Both foams fully met the requirements of the fire test.
Vergleichsbeispiel 2 : Vinylphosphonsäure Comparative Example 2: Vinylphosphonic acid
Zu einem Gemisch aus 280 g Methacrylsäure, 211 g To a mixture of 280 g of methacrylic acid, 211 g
Methacrylnitril und 590 mg Allylmethacrylat wurden als Treibmittel 6, 6 g Wasser und 6, 9 g Formamid zugesetzt. Des Weiteren wurden der Mischung 200 mg tert . -Butylperpivalat , 150 mg tert . -Butylper-2-ethyl-hexanoat , 49 mg tert.- Butylperbenzoat , 49 mg Cumylperneodecanoat , 3,5 g Zinkoxid und 980 mg Trennmittel (Moldwiz INT 20E) hinzugefügt. Als Flammschutzmittel wurden 42,7 g Vinylphosphonsäure Methacrylonitrile and 590 mg of allyl methacrylate were added as blowing agents 6, 6 g of water and 6, 9 g of formamide. Furthermore, the mixture was 200 mg tert. Butyl perpivalate, 150 mg tert. Butyl per-2-ethyl hexanoate, 49 mg tert-butyl perbenzoate, 49 mg cumyl perneodecanoate, 3.5 g zinc oxide and 980 mg release agent (Moldwiz INT 20E). The flame retardant was 42.7 g of vinylphosphonic acid
eingesetzt . used.
Diese Mischung wurde 44 h bei 50°C in Glasampullen This mixture was 44 h at 50 ° C in glass ampoules
polymerisiert . Anschließend wurde das Polymerisat zur Endpolymerisation über 32 h bei einer aufsteigenden polymerized. Subsequently, the polymer was used for final polymerization for 32 h at an ascending
Temperatur von 32°C bis 115°C getempert. Das Polymerisat war inhomogen. Temperature of 32 ° C to 115 ° C annealed. The polymer was inhomogeneous.
Die darauffolgende Schäumung im Heißluftverfahren erfolgte 2h bei 220°C. Der so erhaltene Schaumstoff wies ein The subsequent foaming in the hot air process was 2h at 220 ° C. The resulting foam had a
Raumgewicht von 141 kg/m3 auf. Eine weitere Probe wurde für 2h bei 230°C geschäumt. Der so erhaltene Schaumstoff wies ein Raumgewicht von 102 kg/m3 auf. Beide Proben schäumten ungleichmäßig auf und versagten im Brandtest.
Vergleichsbeispiel 3: Vinylphosphonsäuredimethylester Density of 141 kg / m 3 on. Another sample was foamed for 2 hours at 230 ° C. The resulting foam had a density of 102 kg / m 3 . Both samples foamed unevenly and failed in the burn test. Comparative Example 3: Vinylphosphonic acid dimethylester
Mengen und Durchführung analog zu Vergleichsbeispiel 2. Als Flammschutzmittel wurden 53,8 g Quantities and procedure analogous to Comparative Example 2. As a flame retardant were 53.8 g
Vinylphosphonsäuredimethylester eingesetzt . Vinylphosphonic acid dimethylester used.
Diese Mischung wurde 20 h bei 50°C in Glasampullen This mixture was 20 h at 50 ° C in glass ampoules
polymerisiert . Anschließend wurde das Polymerisat zur polymerized. Subsequently, the polymer was to
Endpolymerisation über 32 h bei einer aufsteigenden Final polymerization for 32 h at an ascending
Temperatur von 32°C bis 115°C getempert. Das Polymerisat war inhomogen. Temperature of 32 ° C to 115 ° C annealed. The polymer was inhomogeneous.
Die darauffolgende Schäumung im Heißluftverfahren erfolgte 2h bei 200°C. Der so erhaltene Schaumstoff wies ein The subsequent foaming in the hot air process was 2 hours at 200 ° C. The resulting foam had a
Raumgewicht von 80 kg/m3 auf. Eine weitere Probe wurde für 2h bei 210°C geschäumt. Der so erhaltene Schaumstoff wies ein Raumgewicht von 58 kg/m3 auf. Beide Proben schäumten ungleichmäßig auf und versagten im Brandtest. Density of 80 kg / m 3 . Another sample was foamed for 2 h at 210 ° C. The resulting foam had a density of 58 kg / m 3 . Both samples foamed unevenly and failed in the burn test.
Vergleichsbeispiel 4: Exolit OP 550 (Fa. Clariant) Comparative Example 4: Exolit OP 550 (Clariant)
Mengen und Durchführung analog zu Vergleichsbeispiel 2. Als Flammschutzmittel wurden 72,2 g Exolit OP 550 eingesetzt. Diese Mischung wurde 41,5 h bei 50°C in Glasampullen polymerisiert. Anschließend wurde das feste aber trübe Polymerisat zur Endpolymerisation über 32 h bei einer aufsteigenden Temperatur von 32°C bis 115°C getempert. Quantities and procedure analogous to Comparative Example 2. As a flame retardant 72.2 g of Exolit OP 550 were used. This mixture was polymerized for 41.5 h at 50 ° C in glass ampoules. Subsequently, the solid but cloudy polymer for final polymerization over 32 h at an increasing temperature of 32 ° C to 115 ° C was annealed.
Die darauffolgende Schäumung im Heißluftverfahren war erfolglos. Die Proben schäumten nicht auf. The subsequent foaming in the hot air process was unsuccessful. The samples did not foam.
Vergleichsbeispiel 5: Exolit OP 560 (Fa. Clariant) Comparative Example 5: Exolit OP 560 (Clariant)
Mengen und Durchführung analog zu Vergleichsbeispiel 2. Als Flammschutzmittel wurden 102,1 g Exolit OP 560 eingesetzt.
Diese Mischung wurde 41,5 h bei 50°C in Glasampullen polymerisiert . Anschließend wurde das trübe und teilweise noch flüssige Polymerisat zur Endpolymerisation über 32 h bei einer aufsteigenden Temperatur von 32°C bis 115°C getempert. Quantities and procedure analogous to Comparative Example 2. 102.1 g of Exolit OP 560 were used as the flame retardant. This mixture was polymerized for 41.5 h at 50 ° C in glass ampoules. Subsequently, the cloudy and partially still liquid polymer for final polymerization over 32 h at an increasing temperature of 32 ° C to 115 ° C was annealed.
Die darauffolgende Schäumung im Heißluftverfahren war erfolglos. Die Proben schäumten nicht auf. The subsequent foaming in the hot air process was unsuccessful. The samples did not foam.
Die hier aufgeführte Auswahl von Flammschutzmittel aus den Vergleichsbeispielen 2 bis 5 zeigt, dass keines der klassisch eingesetzten Flammschutzmittel geeignet ist, einen stabilen, feuerfesten und gleichzeitig homogenen Schaumstoff herzustellen. Einzig das erfindungsgemäß verwendete DMPP führt zu einem mit dem Stand der Technik vergleichbaren Ergebnis. Und das bevorzugt nur, wenn es in einer höheren Konzentration als DMMP eingesetzt wird.
The selection of flame retardants from Comparative Examples 2 to 5 listed here shows that none of the conventionally used flame retardants is suitable for producing a stable, refractory and at the same time homogeneous foam. Only the DMPP used according to the invention leads to a result comparable to the prior art. And this is preferred only when used in a higher concentration than DMMP.
Claims
1. Poly (meth) acrylimid-Schaumstoff, dadurch 1. poly (meth) acrylimide foam, characterized
gekennzeichnet, dass der Schaumstoff characterized in that the foam
Dimethylpropylphosphonat enthält . Dimethylpropylphosphonat contains.
2. Poly (meth) acrylimid-Schaumstoff gemäß Anspruch 1, dadurch gekennzeichnet, dass das geschäumte 2. poly (meth) acrylimide foam according to claim 1, characterized in that the foamed
Poly (meth) acrylamid aus einem Gemisch bestehend aus Poly (meth) acrylamide from a mixture consisting of
(A) 30 bis 70 Gew% Methacrylsäure oder Acrylsäure,(A) 30 to 70% by weight of methacrylic acid or acrylic acid,
30 bis 60 Gew% Methacrylnitril oder Acrylnitril, 0 bis 30 Gew% weiteren vinylisch ungesättigten Monomeren, (B) 8 bis 18 Gew% Dimethylpropylphosphonat, From 30 to 60% by weight of methacrylonitrile or acrylonitrile, from 0 to 30% by weight of further vinylically unsaturated monomers, (B) from 8 to 18% by weight of dimethyl propyl phosphonate,
(C) 0,01 bis 10 Gew% Treibmittel, (C) 0.01 to 10% by weight of blowing agent,
(D) 0 bis 10 Gew% Vernetzer, (D) 0 to 10% by weight of crosslinker,
(E) 0,01 bis 2 Gew% Polymerisationsinitiatoren (E) 0.01 to 2% by weight of polymerization initiators
(F) 0 bis 10 Gew% üblichen Zusatzstoffen hergestellt wurde . (F) 0 to 10% by weight of conventional additives was prepared.
3. Poly (meth) acrylimid-Schaumstoff gemäß Anspruch 2, dadurch gekennzeichnet, dass das Gemisch besteht aus3. poly (meth) acrylimide foam according to claim 2, characterized in that the mixture consists of
(A) 40 bis 60 Gew% Methacrylsäure oder Acrylsäure, 30 bis 50 Gew% Methacrylnitril oder Acrylnitril,(A) 40 to 60% by weight of methacrylic acid or acrylic acid, 30 to 50% by weight of methacrylonitrile or acrylonitrile,
0 bis 10 Gew% weiteren vinylisch ungesättigten Monomeren, 0 to 10% by weight of further vinylically unsaturated monomers,
(B) 10 bis 15 Gew% Dimethylpropylphosphonat, (B) 10 to 15% by weight of dimethylpropyl phosphonate,
(C) 0,1 bis 5 Gew% Treibmittel, (D) 0,1 bis 5 Gew% Vernetzer, (C) 0.1 to 5% by weight of blowing agent, (D) 0.1 to 5% by weight of crosslinker,
(E) 0,1 bis 1 Gew% Polymerisationsinitiatoren und (E) 0.1 to 1% by weight of polymerization initiators and
(F) 0 bis 5 Gew% üblichen Zusatzstoffen. (F) 0 to 5% by weight of conventional additives.
Poly (meth) acrylimid-Schaumstoff, gemäß mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet dass dieser durch Schäumen und Vernetzen des Gemischs nach Anspruch 1 oder 2 erhalten wird. Poly (meth) acrylimide foam, according to at least one of claims 1 to 3, characterized in that it is obtained by foaming and crosslinking of the mixture according to claim 1 or 2.
Poly (meth) acrylimid-Schaumstoff, gemäß mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet dass dieser in Substanz zu einer Platte polymerisiert , welche gegebenenfalls getempert und anschließend bei Temperaturen von 150 bis 250°C geschäumt wird. Poly (meth) acrylimide foam, according to at least one of claims 1 to 4, characterized in that it polymerizes in substance to a plate, which is optionally tempered and then foamed at temperatures of 150 to 250 ° C.
Schichtwerkstoff enthaltend eine Schicht eines Layer material containing a layer of a
Poly (meth) acrylimid-Schaumstoffes gemäß einem der Ansprüche 1 bis 5. Poly (meth) acrylimide foam according to one of claims 1 to 5.
Kraftfahrzeug, Schienenfahrzeug, Wasserfahrzeug, Motor vehicle, rail vehicle, watercraft,
Luftfahrzeug, Raumfahrzeug dadurch gekennzeichnet, das es teilweise aus einem Poly (meth) acrylimid-Schaumstoff gemäß einem der Ansprüche 1 bis 5 besteht. Aircraft, spacecraft characterized in that it partially consists of a poly (meth) acrylimide foam according to one of claims 1 to 5.
Maschinenteil, Antenne, Röntgentisch, Lautsprecher, Rohr, dadurch gekennzeichnet, dass es teilweise aus einem Poly (meth) acrylimid-Schaumstoff gemäß einem der Ansprüche 1 bis 5 besteht. Machine part, antenna, X-ray table, loudspeaker, pipe, characterized in that it partly consists of a poly (meth) acrylimide foam according to one of claims 1 to 5.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102010028695A DE102010028695A1 (en) | 2010-05-06 | 2010-05-06 | Polymethacrylimide foams with reduced flammability and process for the preparation of these |
PCT/EP2011/053138 WO2011138060A1 (en) | 2010-05-06 | 2011-03-03 | Polymethacrylimide foam materials having reduced flammability and method for producing same |
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EP2566914A1 true EP2566914A1 (en) | 2013-03-13 |
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EP11706249A Withdrawn EP2566914A1 (en) | 2010-05-06 | 2011-03-03 | Polymethacrylimide foam materials having reduced flammability and method for producing same |
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US (1) | US20130041056A1 (en) |
EP (1) | EP2566914A1 (en) |
JP (1) | JP2013525580A (en) |
KR (1) | KR20130084226A (en) |
DE (1) | DE102010028695A1 (en) |
RU (1) | RU2012152234A (en) |
SG (1) | SG184531A1 (en) |
TW (1) | TW201213419A (en) |
WO (1) | WO2011138060A1 (en) |
ZA (1) | ZA201208301B (en) |
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DE102013223347A1 (en) | 2013-11-15 | 2015-05-21 | Evonik Industries Ag | Honeycomb filled with poly (meth) acrylimide foam |
DE102013225132A1 (en) | 2013-12-06 | 2015-06-11 | Evonik Industries Ag | Prefoaming of poly (meth) acrylimide particles for subsequent mold foaming in closed tools |
DE102014209425A1 (en) | 2014-05-19 | 2015-11-19 | Evonik Röhm Gmbh | Mold foaming of poly (meth) acrylimide particles in closed tools for the production of hard foam cores |
CN104017127B (en) * | 2014-06-20 | 2016-08-17 | 江苏兆鋆新材料股份有限公司 | A kind of high temperature resistant halogen-free flame-retardant resin addition type AN/MAA copolymer foam and preparation method thereof |
CN104045764B (en) * | 2014-06-23 | 2016-04-13 | 浙江理工大学 | A kind of preparation method of polymethacrylimide plastic foam |
DE102014009338A1 (en) | 2014-06-27 | 2015-12-31 | Evonik Röhm Gmbh | Pressure-dependent foam molding of poly (meth) acrylimide particles in closed tools for the production of rigid foam cores |
DE102014009584A1 (en) | 2014-07-01 | 2016-01-07 | Evonik Röhm Gmbh | One-shot HD-RTM method |
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EP3015256A1 (en) | 2014-10-27 | 2016-05-04 | Evonik Röhm GmbH | Establishing multiple different fibre composite components for mass production in a continuous process |
EP3015255A1 (en) | 2014-10-27 | 2016-05-04 | Evonik Röhm GmbH | Production of locally reinforced fibre composite components for mass production in a continuous process and rigid-foam filled profile |
EP3159129A1 (en) | 2015-10-22 | 2017-04-26 | Evonik Röhm GmbH | Preparation of complex foam or sandwich hollow structures by means of a mould core |
EP3225654A1 (en) | 2016-03-30 | 2017-10-04 | Evonik Röhm GmbH | Shortening the cooling down period in particle foaming by additives increasing the thermal conductivity |
CN107417846A (en) * | 2017-08-31 | 2017-12-01 | 湖南和铸新材料科技有限公司 | Polymethacrylimide plastic foam and preparation method thereof |
CN107629162B (en) * | 2017-10-31 | 2020-04-14 | 浙江中科恒泰新材料科技有限公司 | Method for preparing poly (methyl) acrylimide foam by one-step feeding gel method |
CN109280306B (en) * | 2018-08-25 | 2021-04-13 | 浙江中科恒泰新材料科技有限公司 | Preparation method of polymethacrylimide composite foam conductive wave-absorbing material |
RU2707601C1 (en) * | 2019-02-05 | 2019-11-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный технологический институт (технический университет)" | Method of producing gas-filled polyacrimimides |
CN111040230B (en) * | 2019-12-12 | 2022-05-27 | 浙江中科恒泰新材料科技有限公司 | PMI foam with high elongation at break and preparation method thereof |
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- 2011-03-03 RU RU2012152234/05A patent/RU2012152234A/en unknown
- 2011-03-03 SG SG2012075123A patent/SG184531A1/en unknown
- 2011-03-03 WO PCT/EP2011/053138 patent/WO2011138060A1/en active Application Filing
- 2011-03-03 US US13/640,427 patent/US20130041056A1/en not_active Abandoned
- 2011-03-03 JP JP2013508404A patent/JP2013525580A/en not_active Withdrawn
- 2011-03-03 KR KR1020127028954A patent/KR20130084226A/en not_active Application Discontinuation
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DE102010028695A1 (en) | 2011-11-10 |
RU2012152234A (en) | 2014-06-20 |
KR20130084226A (en) | 2013-07-24 |
ZA201208301B (en) | 2013-07-31 |
SG184531A1 (en) | 2012-11-29 |
JP2013525580A (en) | 2013-06-20 |
US20130041056A1 (en) | 2013-02-14 |
TW201213419A (en) | 2012-04-01 |
WO2011138060A1 (en) | 2011-11-10 |
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