WO2005023883A1 - Verfahren zur synthese von copolymeren zur herstellung von polymethacrylimiden - Google Patents
Verfahren zur synthese von copolymeren zur herstellung von polymethacrylimiden Download PDFInfo
- Publication number
- WO2005023883A1 WO2005023883A1 PCT/EP2004/009472 EP2004009472W WO2005023883A1 WO 2005023883 A1 WO2005023883 A1 WO 2005023883A1 EP 2004009472 W EP2004009472 W EP 2004009472W WO 2005023883 A1 WO2005023883 A1 WO 2005023883A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- acid
- monomers
- butyl
- alkyl
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 23
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 150000003926 acrylamides Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000003509 tertiary alcohols Chemical class 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- -1 ethylhexyl Chemical group 0.000 claims description 19
- 239000006260 foam Substances 0.000 claims description 19
- 239000004604 Blowing Agent Substances 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000003379 elimination reaction Methods 0.000 claims description 7
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 7
- 230000008030 elimination Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003453 sulfinic acid esters Chemical group 0.000 claims description 2
- 150000003459 sulfonic acid esters Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 239000012778 molding material Substances 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 10
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 150000003333 secondary alcohols Chemical class 0.000 abstract description 3
- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 abstract 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 25
- 229920000642 polymer Polymers 0.000 description 16
- 239000003999 initiator Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000005187 foaming Methods 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 229920000858 Cyclodextrin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229940097362 cyclodextrins Drugs 0.000 description 5
- ATLPLEZDTSBZQG-UHFFFAOYSA-L dioxido-oxo-propan-2-yl-$l^{5}-phosphane Chemical compound CC(C)P([O-])([O-])=O ATLPLEZDTSBZQG-UHFFFAOYSA-L 0.000 description 5
- 239000012966 redox initiator Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- 229920007790 polymethacrylimide foam Polymers 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 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 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- AKIZPWSPNKVOMT-UHFFFAOYSA-N 1-sulfanylhexan-1-ol Chemical compound CCCCCC(O)S AKIZPWSPNKVOMT-UHFFFAOYSA-N 0.000 description 1
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-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
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- HMHYBQHINBJJGL-UHFFFAOYSA-N 4-[(4-carboxy-4-cyanobutan-2-yl)diazenyl]-2-cyanopentanoic acid Chemical compound N#CC(C(O)=O)CC(C)N=NC(C)CC(C#N)C(O)=O HMHYBQHINBJJGL-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 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
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- XBUFCZMOAHHGMX-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.ON.ON.OP(O)(O)=O XBUFCZMOAHHGMX-UHFFFAOYSA-N 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical group CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 229940097156 peroxyl Drugs 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 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
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920006301 statistical copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- KQYLUTYUZIVHND-UHFFFAOYSA-N tert-butyl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)C KQYLUTYUZIVHND-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Definitions
- the invention relates to copolymers based on (meth) acrylamides and (meth) acrylic esters, which are prepared by radical polymerization in a water-containing diluent. These copolymers can be used as a molding composition for the production of polymethacrylimide foams or molding compositions.
- PMMI poly-N-methyl methacrylimide
- PLEXIMID 0 poly-N-methyl methacrylimide
- PMMI is a highly heat-resistant, transparent plastic with high UV stability.
- PMMI is used as an injection moldable molding compound, for example in the automotive sector.
- PMMI molding compound is produced by a polymer-analogous reaction of polymethyl methacrylate molding compound with methylamine in an extruder.
- the second type of polymethacrylimide available on an industrial scale is the unsubstituted variant, ie there is no N-alkylation. This is therefore simply referred to as polymethacrylimide (PMI).
- PMI polymethacrylimide
- the production takes place in the casting process, which is why PMI, in contrast to PMMI, has high degrees of polymerization and is no longer meltable.
- PMI foam is produced using the casting process (DE 3346060).
- the monomers methacrylic acid and methacrylonitrile are mixed with initiators, blowing agents and optionally other monomers or additives and filled into a chamber made of glass and / or metal plates, which are kept at a certain distance with a sealing cord.
- This chamber is immersed in a water bath at a defined temperature and the copolymer obtained is converted into a polymethacrylimide and simultaneously foamed in a second step by heating to temperatures between 150 ° C. and 250 ° C.
- the problem here is that the rate of polymerization of methacrylic acid is significantly higher than that of methacrylonitrile, which is why the methacrylic acid reacts first during the polymerization, so that a mixture of copolymers with significantly different compositions is obtained.
- JP 04170408 and EP532023 describe the production of PMI foams.
- a copolymer is prepared from tert-butyl methacrylate, methacrylic acid and methacrylonitrile by bulk polymerization.
- This process also has two disadvantages: First, as above, it is a casting process, which brings with it the problems with heat dissipation that have already been discussed. Second, the claimed methacrylonitrile-based compositions do not allow substitution of the imide hydrogen atom by other functional groups.
- monomers are preferably used which ideally provide statistical copolymers (n 1, r 2 1, ri and r 2 are the copolymerization parameters) or even tend to alternate copolymers (r 1, r 2 0).
- n 1, r 2 1, ri and r 2 are the copolymerization parameters
- r 1 r 2 0 the copolymerization parameters
- cyclodextrins should also be avoided.
- the above objects can be achieved by precipitation or suspension polymerization of the monomers in the presence of an aqueous diluent.
- R2 can be an alkyl or aryl radical with up to 36 carbon atoms, which additionally contains oxygen, nitrogen, sulfur and phosphorus atoms in the form of typical organic functionalities, such as ether, alcohol, acid, ester, , Amide, imide, phosphonic acid, phosphonic acid esters, phosphoric acid esters, phosphoric acid, phosphinic acid esters, sulfonic acid, sulfonic acid ester, sulfinic acid, sulfinic acid ester functions, silicon, aluminum and boron atoms or also halogens such as fluorine, chlorine, bromine or iodine can.
- R2 examples include, but are not limited to: methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl, hexyl, ethylhexyl, octyl, dodecyl, octadecyl, -R3-PO (OR4) 2, where R3 is an alkyl radical with up to 12 C atoms and R4 is an alkyl with up to 4 C atoms, Methylene dimethyl phosphonate, methylene diethyl phosphonate, methylene diisopropyl phosphonate. Mixtures of different methacrylamides can also be used.
- the chemical and physical properties of the polymers can be varied by copolymerization with one or more further ethylenically unsaturated monomers.
- the monomers (A) and (B) are polymerized in the manner of a precipitation or suspension polymerization in an aqueous medium (C), preferably in water.
- aqueous medium is to be understood as meaning mixtures of water and thus miscible organic liquids.
- organic liquids are, for example, glycols such as ethylene glycol, propylene glycol, block copolymers of ethylene oxide and propylene oxide, alkoxylated C 1 -C 2 -alcohols, furthermore methanol, ethanol, isopropanol and butanol, acetone, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone or else mixtures.
- the polymerization is carried out in mixtures of water and water-miscible solvents, the proportion of water-miscible solvents in the mixture is up to 45% by weight. However, the polymerization is preferably carried out in water.
- the precipitation or suspension polymerization of the monomers is usually carried out with the exclusion of oxygen at temperatures of 10 to 200 ° C., preferably 20 to 140 ° C.
- the polymerization can be carried out batchwise or continuously.
- at least some of the monomers, initiators and optionally regulators are metered uniformly into the polymer during the polymerization Reaction vessel, wherein the components can also be mixed continuously or batchwise outside the reaction vessel.
- the monomers and the polymerization initiator can be placed in the reactor and polymerized, where appropriate cooling must be used to ensure that the heat of polymerization is dissipated sufficiently quickly.
- Possible polymerization initiators are the compounds which are customarily used in radical polymerizations and which give free radicals under the polymerization conditions, such as, for example, peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxiesters, hydrogen peroxide and azo compounds.
- initiators are hydrogen peroxide, dibenzoyl peroxide, dicyclohexylperoxodicarbonate, dilauryl peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl butyl perodobutyl peroxobutyl peroxobutyl peroxobutyl peroxyl benzoate, ammonium nitrate, sodium, potassium peroxyl benzene, , 2,2'-azo-bis (2-amidinopropane) dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4'-azobis (cyanovaleric acid).
- the initiators are usually used in amounts of up to 15, preferably 0.02 to 10% by weight, based on the monomers to be polymerized.
- Known redox initiators are, for example, salts of transition metals such as iron-II-sulfate, copper-I-chloride, manganese-II-acetate, vanadium-III-acetate.
- Redox initiators which can furthermore be used are reducing sulfur compounds, such as sulfites, bisulfites, thiosulfates, dithionites and tetrathionates of alkali metals and ammonium compounds, or reducing phosphorus compounds in which the phosphorus has an oxidation number of 1 to 4, such as sodium hypophosphite, phosphorous acid and phosphites. Mixtures of the initiators or initiator systems mentioned can also be used. In order to control the molecular weight of the polymers, the polymerization can optionally be carried out in the presence of regulators.
- Suitable regulators include, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, hydroxylammonium sulfate and hydroxylammonium phosphate.
- regulators can be used which contain sulfur in organically bound form, such as SH compounds containing organic compounds such as thioglycol acetic acid, mercaptopropionic acid, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptohexanol, dodecyl mercaptan and tert-dodecyl mercaptan.
- Salts of hydrazine such as hydrazinium sulfate can also be used as regulators.
- the amounts of regulator, based on the monomers to be polymerized, are 0 to 20, preferably 0.5 to 15% by weight.
- isobutene or other volatile elimination products from the alkyl ester units are obtained by thermal syn-elimination from the tert-butyl ester units (I).
- the resulting acid groups partially react further with neighboring amide groups and a copolymer of imide, anhydride, amide and remaining alkyl ester units (II) results.
- the alkenes released by thermal elimination act as blowing agents. If the reaction is carried out in a thin layer, the blowing agent diffuses and bubble-free, colorless films are obtained, cf. Angew. Makromol. Chem., II, 1970, 119, 91-108.
- Foaming can be achieved by extracting from the polymer e.g. produces a block by pressing or by melting the polymer under pressure so that the resulting propellant gas remains dissolved in the polymer. The latter can be achieved, for example, by extrusion or by foam injection molding.
- the polymerization in the diluent water or in aqueous solvent mixtures ensures good dissipation of the heat of reaction at all times, so that the polymerization temperature can be maintained within a narrow range even at high reaction rates.
- the polymerization can be carried out inexpensively under normal pressure, but if necessary also under elevated pressure or in vacuo.
- the polymer can be separated off in a technically simple and inexpensive manner, for example by filtration or by centrifugation. Since the use of cyclodextrins can be dispensed with, further purification steps of the polymer are omitted.
- blowing agent When the copolymers are heated, the secondary or tertiary alcohol esters are thermally syn-eliminated. The resulting alkenes act as foaming agents. Foaming therefore takes place without the additional use of blowing agents. However, additional blowing agents such as azodicarbonamide or urea can be used to regulate the foam density. The amount of blowing agent added is usually 0-20% by weight, but can also be higher.
- (meth) acrylamides as comonomers to the (meth) acrylic esters offers the advantage over the copolymerization of methacrylonitrile and (meth) acrylic esters that N-substituted imides are accessible by substituting a hydrogen atom on the nitrogen of the (meth) acrylamide.
- Polymers produced according to the invention are suitable for the production of foams or PMI molding compositions, including N-substituted ones.
- a 4 L three-necked flask equipped with a KPG stirrer and a nitrogen supply was evacuated three times and aerated with argon.
- 3400 mL of distilled water degassed in the ultrasonic bath were introduced into the flask.
- Argon was bubbled through the solution for 10 hours using an injection needle.
- 24.03 g (0.282 mol) of methacrylamide and 45.83 mL (0.282 mol) of teAt-butyl methacrylate were then added under counter-argon flow.
- the reaction mixture was again degassed several times with vigorous stirring and aerated with argon. After stirring for 1 h, the reaction mixture was heated to 40 ° C.
- the preparation and polymerization were carried out analogously to Example 1. However, only 0.41 g (4.8 mmol) of methacrylamide and 0.68 g (4.8 mmol) of tert-butyl methacrylate were used.
- the reaction was carried out in a 250 mL three-necked flask at a temperature of 50 ° C. The polymerization was stopped after 4 h. The copolymer was obtained in a yield of 30%.
- the amide was incorporated in a proportion of 0.53.
- the weight average molecular weight was 233 100 g / mol, the number average molecular weight 107 900 g / mol and the polydispersity 2.2.
- the glass transition temperature of the copolymer is 122 ° C.
- a 100 mL three-necked flask equipped with a nitrogen supply was evacuated three times and aerated with nitrogen.
- the initiator solutions (redox initiators 0.215 g K 2 S 2 O 8 (0.8 mmol) and 0.15 g Na 2 S 2 O 5 in 23 mL water) were then introduced into the three-necked flask.
- the reaction mixture was stirred under a nitrogen atmosphere and heated to the respective reaction temperature (Table 1). 2.84 g (20 mmol) tert-butyl methacrylate and 1.7 g (20 mmol) methacrylamide were dissolved in 7 mL methanol. This mixture was added dropwise to the initiator solution over 15 minutes while passing a gentle stream of nitrogen through the solution.
- a 100 mL three-necked flask equipped with a nitrogen supply was evacuated three times and aerated with nitrogen.
- 2.55 g (20 mmol) methacrylamide were dissolved in 30 mL degassed, distilled water.
- 2.84 g (30 mmol) of terf-butyl methacrylate were then added with stirring and in countercurrent nitrogen.
- the emulsion was stirred for 10 min under a nitrogen atmosphere and then heated to the respective reaction temperature.
- the copolymerization was initiated by adding the initiators (0.27 g (1 mmol) K 2 S 2 ⁇ 8 and 0.19 g (1 mmol) Na 2 S 2 O 5 ).
- the copolymer from Example 1 was finely pulverized and processed into tablets with a diameter of 12.5 mm (Examples 5, 8, 9) and 40 mm (Examples 6, 7).
- the tablets were foamed by heating under the conditions shown in Table 3.
- the composition of the copolymer foam was determined by NMR and the glass transition temperatures by DSC.
- Table 3 Foaming of the copolymer from Example 1
- the copolymer from Example 2 was finely pulverized and processed into tablets with a diameter of 12.5 mm.
- the tablets were foamed by heating under the conditions shown in Table 4.
- the composition of the copolymer foam was determined by NMR, the molecular weights by volume exclusion chromatography based on PS standards and the glass transition temperatures by DSC.
- This mixture was polymerized for 68 hours at 40 ° C. and in a chamber formed from two glass plates measuring 50 ⁇ 50 cm and an 18.5 mm thick edge seal.
- the polymer was then subjected to an annealing program ranging from 32 ° C. to 115 ° C. for 32 hours.
- the subsequent foaming took place at 205 ° C. for 2 h 25 min.
- the foam thus obtained had a density of 235 kg / m 3 .
- a foam with a density of 71 kg / m 3 was produced in accordance with DE 33 46 060, 10 parts by weight of DMMP being used as the flame retardant.
- 140 g of formamide and 135 g of water were added as a blowing agent to a mixture of equal molar parts of 5620 g of methacrylic acid and 4380 g of methacrylonitrile.
- 10.0 g of tert-butyl perbenzoate, 4.0 g of tert-butyl perpivalate, 3.0 g of tert-butyl per-2-ethylhexanoate and 10.0 g of cumyl perneodecanoate were added as initiators to the mixture.
- DMMP dimethyl methane phosphonate
- the mixture contained 20g release agent (MoldWiz) and 70g ZnO and 0.07g hydroquinone.
- This mixture was polymerized for 92 hours at 40 ° C. in a chamber formed from two glass plates of size 50 * 50 cm and a 2.2 cm thick edge seal. The polymer was then subjected to a tempering program ranging from 40 ° C. to 115 ° C. for 17.25 hours. The subsequent foaming took place at 215 ° C. for 2 hours. The foam thus obtained had a density of 71 kg / m 3 .
- a mixture of 5700 g methacrylic acid and 4300 g methacrylonitrile, 140 g formamide and 135 g water were added as blowing agents. Furthermore, 10.0 g of tert-butyl perbenzoate, 4.0 g of tert-butyl perpivalate, 3.0 g of tert-butyl per-2-ethylhexanoate and 10 g of cumyl perneodecanoate were added to the mixture as initiators. In addition, 1000 g of dimethyl methane phosphonate (DMMP) t were added to the mixture as a flame retardant. Finally, the mixture contained 15 g of release agent (PAT) and 70 g of ZnO and 0.07 g of hydroquinone.
- PAT release agent
- This mixture was polymerized for 92 hours at 40 ° C. in a chamber formed from two glass plates of size 50 * 50 cm and a 2.2 cm thick edge seal.
- the polymer was then subjected to a tempering program ranging from 40 ° C. to 115 ° C. for 17.25 hours.
- the subsequent foaming took place at 220 ° C. for 2 hours.
- the foam thus obtained had a density of 51 kg / m 3 .
- the procedure was essentially the same as in Comparative Example 2, except that the foaming was carried out at 210 ° C. and the density of the foam obtained was then 110 kg / m 3 .
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/568,971 US20070142588A1 (en) | 2003-08-29 | 2004-08-25 | Method for the synthesis of copolymers for producing polymethacrylimides |
CA002529610A CA2529610A1 (en) | 2003-08-29 | 2004-08-25 | Method for the synthesis of copolymers for producing polymethacrylimides |
EP04764449A EP1658318A1 (de) | 2003-08-29 | 2004-08-25 | Verfahren zur synthese von copolymeren zur herstellung von polymethacrylimiden |
JP2006524322A JP2007504289A (ja) | 2003-08-29 | 2004-08-25 | ポリメタクリルイミドを製造するためのコポリマーの合成方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10340330A DE10340330A1 (de) | 2003-08-29 | 2003-08-29 | Verfahren zur Synthese von Copolymeren zur Herstellung von Polymethacrylimiden |
DE10340330.2 | 2003-08-29 |
Publications (1)
Publication Number | Publication Date |
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WO2005023883A1 true WO2005023883A1 (de) | 2005-03-17 |
Family
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PCT/EP2004/009472 WO2005023883A1 (de) | 2003-08-29 | 2004-08-25 | Verfahren zur synthese von copolymeren zur herstellung von polymethacrylimiden |
Country Status (9)
Country | Link |
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US (1) | US20070142588A1 (de) |
EP (1) | EP1658318A1 (de) |
JP (1) | JP2007504289A (de) |
KR (1) | KR20060110861A (de) |
CN (1) | CN1823101A (de) |
CA (1) | CA2529610A1 (de) |
DE (1) | DE10340330A1 (de) |
TW (1) | TW200514794A (de) |
WO (1) | WO2005023883A1 (de) |
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JP4800649B2 (ja) * | 2005-03-25 | 2011-10-26 | 株式会社カネカ | 発泡性樹脂組成物及びこれを用いた発泡体 |
DE102008001695A1 (de) * | 2008-05-09 | 2009-11-12 | Evonik Röhm Gmbh | Poly(meth)acrylimide mit verbesserten optischen und Farbeigenschaften, insbesondere bei thermischer Belastung |
CN102225983B (zh) * | 2011-05-03 | 2013-04-24 | 浙江理工大学 | 一种含有酰亚胺基的聚合物泡沫材料及其制备方法 |
JP2013014743A (ja) * | 2011-05-27 | 2013-01-24 | Rohm & Haas Electronic Materials Llc | 表面活性添加剤およびこれを含むフォトレジスト組成物 |
CN103073672B (zh) * | 2013-01-15 | 2015-01-28 | 浙江理工大学 | 一种原位增强聚甲基丙烯酰亚胺泡沫材料及其制备方法 |
CN103421206B (zh) * | 2013-07-24 | 2016-02-17 | 江苏科技大学 | 一种丙烯腈/甲基丙烯酸共聚物泡沫塑料的制备方法 |
CN103923337B (zh) * | 2014-04-30 | 2016-06-08 | 湖南兆恒材料科技有限公司 | 聚甲基丙烯酰亚胺复合泡沫吸波材料 |
CN106349419B (zh) * | 2016-09-19 | 2019-03-08 | 浙江中科恒泰新材料科技有限公司 | 一种聚甲基丙烯酰亚胺泡沫及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3299010A (en) * | 1962-11-05 | 1967-01-17 | Kendall & Co | Pressure sensitive adhesive polymers and tapes therefrom |
DE10150484A1 (de) * | 2001-10-16 | 2003-05-08 | Roehm Gmbh | Verfahren zur Herstellung von substituierten Polymethacrylimiden aus Poly-Alkylmethacrylamid-co-alkylmethacrylaten unter Verwendung von Cyclodextrinen |
-
2003
- 2003-08-29 DE DE10340330A patent/DE10340330A1/de not_active Withdrawn
-
2004
- 2004-08-18 TW TW093124880A patent/TW200514794A/zh unknown
- 2004-08-25 EP EP04764449A patent/EP1658318A1/de not_active Withdrawn
- 2004-08-25 WO PCT/EP2004/009472 patent/WO2005023883A1/de not_active Application Discontinuation
- 2004-08-25 CA CA002529610A patent/CA2529610A1/en not_active Abandoned
- 2004-08-25 JP JP2006524322A patent/JP2007504289A/ja not_active Withdrawn
- 2004-08-25 CN CNA2004800198854A patent/CN1823101A/zh active Pending
- 2004-08-25 US US10/568,971 patent/US20070142588A1/en not_active Abandoned
- 2004-08-25 KR KR1020067003977A patent/KR20060110861A/ko not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3299010A (en) * | 1962-11-05 | 1967-01-17 | Kendall & Co | Pressure sensitive adhesive polymers and tapes therefrom |
DE10150484A1 (de) * | 2001-10-16 | 2003-05-08 | Roehm Gmbh | Verfahren zur Herstellung von substituierten Polymethacrylimiden aus Poly-Alkylmethacrylamid-co-alkylmethacrylaten unter Verwendung von Cyclodextrinen |
Also Published As
Publication number | Publication date |
---|---|
TW200514794A (en) | 2005-05-01 |
JP2007504289A (ja) | 2007-03-01 |
CN1823101A (zh) | 2006-08-23 |
US20070142588A1 (en) | 2007-06-21 |
DE10340330A1 (de) | 2005-03-24 |
CA2529610A1 (en) | 2005-03-17 |
KR20060110861A (ko) | 2006-10-25 |
EP1658318A1 (de) | 2006-05-24 |
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