TWI343928B - Heat-resistant polymethacrylimide foams with fine pores - Google Patents
Heat-resistant polymethacrylimide foams with fine pores Download PDFInfo
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- TWI343928B TWI343928B TW093123939A TW93123939A TWI343928B TW I343928 B TWI343928 B TW I343928B TW 093123939 A TW093123939 A TW 093123939A TW 93123939 A TW93123939 A TW 93123939A TW I343928 B TWI343928 B TW I343928B
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- foam
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- agent
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- 239000011148 porous material Substances 0.000 title abstract description 18
- 229920007790 polymethacrylimide foam Polymers 0.000 title abstract description 7
- 239000006260 foam Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- -1 flow improver Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000005187 foaming Methods 0.000 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 5
- 239000003963 antioxidant agent Substances 0.000 claims 2
- 230000003078 antioxidant effect Effects 0.000 claims 2
- 239000002216 antistatic agent Substances 0.000 claims 2
- 239000002738 chelating agent Substances 0.000 claims 2
- 229920006037 cross link polymer Polymers 0.000 claims 2
- 239000000975 dye Substances 0.000 claims 2
- 239000004611 light stabiliser Substances 0.000 claims 2
- 239000000314 lubricant Substances 0.000 claims 2
- 239000000049 pigment Substances 0.000 claims 2
- 239000004014 plasticizer Substances 0.000 claims 2
- 239000003381 stabilizer Substances 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 claims 1
- 239000006082 mold release agent Substances 0.000 claims 1
- 150000002903 organophosphorus compounds Chemical class 0.000 claims 1
- 229960002317 succinimide Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- 239000011162 core material Substances 0.000 description 25
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 239000002253 acid Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920006934 PMI Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 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
- 238000010586 diagram Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-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
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 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
- 238000001721 transfer moulding Methods 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZXQOBTQMLMZFOW-UHFFFAOYSA-N 2-methylhex-2-enamide Chemical compound CCCC=C(C)C(N)=O ZXQOBTQMLMZFOW-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
- PUZQJRBXWOCOQS-UHFFFAOYSA-N C(O)(O)=O.COC(C(C)C)=O Chemical compound C(O)(O)=O.COC(C(C)C)=O PUZQJRBXWOCOQS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 240000007182 Ochroma pyramidale Species 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001298 alcohols 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 1
- KWZZRRIYJVNWDS-UHFFFAOYSA-N carboxy methoxycarbonyl carbonate Chemical compound COC(=O)OC(=O)OC(O)=O KWZZRRIYJVNWDS-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BQBKYSPXQYHTIP-UHFFFAOYSA-N ethyl n-butylcarbamate Chemical compound CCCCNC(=O)OCC BQBKYSPXQYHTIP-UHFFFAOYSA-N 0.000 description 1
- DYWODRJVMZCPDO-UHFFFAOYSA-N ethylammonium formate Chemical compound CC[NH3+].[O-]C=O DYWODRJVMZCPDO-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DVYSFZJKLYKOIF-UHFFFAOYSA-N methylamino formate Chemical compound CNOC=O DVYSFZJKLYKOIF-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-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
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method 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
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- 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
- 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
-
- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
-
- 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
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1343928 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於用於製造具有降低孔洞的耐熱性聚甲基 丙烯醯亞胺發泡體之組成物,其製造方法,以及這些發泡 體之處理與用途。 【先前技術】 聚甲基丙烯醯亞胺發泡體(Ρ Μ I發泡體)已經知道有 很長的時間’商標名稱是R 0 H A C E L L ®之這些發泡體特別 廣泛用在層狀材料部份(層壓製件、合成物、發泡體合成 物、三明治結構、三明治系統),層狀材料是由外部面層 及內部核心材料組成之模製品,使用的面層是由單—或多 重軸之材料組成,可以耐受極高的張力,實例是玻璃織物 及碳纖維織物,或鋁片,其係經由黏著樹脂固定至核心材 料’使用的核心材料較宜由低密度之材料組成,特別是在 30公斤/立方米及2 00公斤/立方米之範圍。 三種核心材料之間有差異性,可以舉例之第一種是巴 賽木(balsa wood),巴賽木之纖維結構使其可以耐受高 張力及壓縮力’尤其是在纖維之方向’但是在其垂直方向 只有很弱的機械性質’巴賽木因此是高度各向異性的材料 ,平均密度是相當高達〜]5 0公斤/立方米,但是雖然如此 仍然足夠I氏用於3午多應用,此種核心材料上市之實例是從 製造涵DIAB之商標名稱Baltec®。 另一種核心材料是以蜂嵩狀結構提供,例如N〇mex<& (2) (2)1343928 蜂嵩體或銘組成之蜂窩體’蜂窩狀結構之特性是有特別低 的密度且在蜂窩體之縱向有高載荷能力,蜂窩體在此方面 優於其他核心材料,但是,如果處理期間或當組件完成時 ’力量從垂直於蜂窩體方向產生時,蜂窩體有較低的適用 性’因爲其結構使得垂直於縱向機械性薄弱,另一個缺點 是用於生產三明治結構之樹脂可移動進入蜂窩體,因而增 加結構之總重量’此點嚴重限制可用於生產蜂窩體基質的 二明治結構之方法選擇,具體地說,蜂窩體不可能使用於 相當低黏性樹脂系統例如在樹脂注射處理中使用者,另---個問題是蜂窩體之處理容易,此係非常複雜且因而昂貴, 尤其是在形狀不是完全簡單的織物之情形。 可以舉例的第三種是密閉孔洞剛性聚合物發泡體,上 述各向同向性的發泡體可以在任何立體方向耐受三明治剪 力,一個優點是容易處理,其可使用一般用於木材之工具 及機械進行,而且’部份剛性發泡體,例如ROHACELL® ,可以因而形成,密閉孔洞剛性發泡體之一個明顯優點是 沒有樹脂可以穿透且因此增加總重量。 以前三明治結構之生產是很複雜,不論是使用核心材 料或面層,且此係指長久以來與價格相關的因素使得這些 結構無法獲得充分的接受,生產三明治結構之傳統方法是 乾式應用面層至核心材料且隨後經由樹脂飽和之層化方 '法 ,另一種方法是建立在使用經部份聚合化的樹脂飽和化之 玻璃墊或碳纖維墊(預浸漬體”PrePregs”),這些樹脂之 黏性通常足夠高至可以防止滴體之任何分離。 -6- (3) (3)1343928 最近,稱爲”樹脂灌注”之新方法經發展用於生產三明 治系統,在密閉模具或氣密小囊內將三明治核心覆蓋乾燥 纖維材料並用相當低黏性的樹脂飽和化,這些方法之優點 首先是更廣的樹脂系統及纖維材料範圍且第二是更容易自 動化’三明治結構可以因此藉由這些方法在較低的成本下 大量生產,樹脂灌注法之實例是RTM (樹脂轉移模塑法 )、RIM (樹脂灌注模塑法)、SCRIMP (Seeman氏樹 脂灌注模塑法™ )及VARI (真空輔助樹脂灌注法),進 —步細節是揭示在”Re sin Transfer Molding,SAMPE® Monograph No. 3” (ISBN 0-938994-83-2),灌注法之一 個問題是相當低黏性的樹脂完全塡入核心材料之開口孔洞 ,使得例如蜂窩體不合適作爲核心材料。 如果密閉孔洞發泡體是機械化,此無法避免在表面產 生開口胞室,這些代表經相當低黏性的樹脂塡入之模槽且 因此得到相當重的組件,因此’在完全密閉孔洞發泡體之 情形下’在核心材料表面之樹脂吸附實質上依賴於胞室之 大小’當大胞室經切開後所得的模槽很深,且大量的樹脂 穿透進入。 幾乎不可能在發泡體核心之表面進行直接量測樹脂吸 附.雖然如此下列方法經發展以便彼此比較樣本:首先, 在最大fra社、度下測量測b式樣本板之密度及重量,然後將測 s式樣本放入配備兩個觸及點之已知體積腔內,並將腔密封 使得可以保持真空,腔內的間隔物保證樣本無實質上的面 櫝與fe壁ί妾觸,測量總重量,經由__個觸及點使腔內真空 1343928 1 ⑷ 至ο.2巴’保持真空下’經由第二個觸及點吸入油並穿透 測試樣本之表面’將腔密封並坪重,增加的重量得到穿透 的油之重量’使用油之密度及重量、腔體積,.以及測試樣 本之密度及重量’可以計算穿透進入測試樣本表面的油之 體積及重量’下表列出選擇的商業化供應的發泡體之油吸 附。 表I :密度範圍在6 0 - 8 0公斤/立方米之部份聚合物發 jg體之油吸附。____ 種類/製造商 根據 密度 油吸附 公斤/立方米 公斤/平方米 R82.60/Airex PEI 60 0.68 R 8 2.8 0 / A i r e X PEI 80 0.3 0 C70.75/Airex PVC 80 0.44 ROHACELL® 71A PMI 72 0.18 ROHACELL® 71 RIST PMJ 7 2 0.23 ROHACELL® 7 ] WF PM] 72 0.4 8 表中的値顯示經由減低核心材料之樹脂吸附,可以明 顯減低重量,大小是 1 000x 1 000x10 立方毫米之 ROHACELL® 7 1 RIST組成之方形片其重量是〇 · 7 2公斤, 但是處理期間吸附0 · 4 6公斤樹脂’ R 〇 H A C t L L - 7 1 W F組 成的對應片吸收高達0.96公斤之樹脂,也就是大於其本 身的重量。 (5) (5)1343928 爲了在三明治結構中減重,因此需要選擇具有特別低 樹脂吸附之發泡體,在表1所列的發泡體之油吸附値中, 先前在ROHACELL® 71 A之情形下達到〇· 1 8公斤/平方米 之低値’但是,需要具有更低樹脂吸附之發泡體,而且, ROHACELL® 7】A不足以酎受固化部份樹脂系統所需之壓 力及溫度,對此經由R 0 H A C E L L ® 7 1 RI S T可以提供幫助 ’但是其有較高的樹脂吸附。 DE 2 72 6260揭示即使在高溫也具有極佳機械性質的 聚甲基丙烯醯亞胺發泡體(PMI發泡體)之製造,該發泡 體是經由澆鑄法生產,也就是在槽內將單體及所需要的添 加物混合並聚合化,第二階段經由加熱將聚合物發泡,揭 示在DE 27 2 62 60的發泡體之缺點是其粗孔洞結構,簡單 經由改變發泡劑可以達到明顯降低孔洞大小,但是仍然太 粗而無法生產用於樹脂注射法之核心材料(比較實例1 ) 並顯現部均勻的孔洞大小分布(圖1 )。 經由使用不溶解的核晶劑可以生產具有更小孔洞之 PM I發泡體(D E 1 〇 2 1 2 2 3 5 · 0 ),但是,在澆鑄法中使用 不溶解的核晶劑伴隨著明顯額外生產成本,要聚合的單體 混合物之密度只有約0.8克/立方公分,可作爲核晶劑使 用之物質例如二氧化矽、硫化鋅、氯化鈉或氯化鉀,具 有高於單體混合物之密度且因此立即沈澱,只有當核晶劑 之沈澱被抑制時才能得到具有均勻孔洞結構之發泡體,對 此’抗沈澱劑例如Aer0Sil及碳黑,或增稠劑例如可溶解 的高分子量聚合物,必須添加至單體混合物,且這些必須 (6) (6)1343928 在複雜的方法下與核晶劑摻混至混合物中。 以PMI爲基質之微細孔洞發泡體還揭示在EP 5 32 023 (比較實例7 ),但是’該文獻揭示的方法具有多種嚴重 缺點’聚合時使用相當局濃度之引發劑,且雖然所得的聚 合物是經由澆鑄法.製備,其重量平均分子量只有在5 0 - 5 0 0 kDa之範圍,而且,沒有交聯劑添加至混合物,對於 這些理由’所得的發泡體只有低耐熱性及不良.的蠕變性能 〇 微細孔洞發泡體是已知且以ROHACELL®的名稱由 R0hm GmbH & Co KG上市販賣,經由改變發泡劑或經由 添加不溶解的核晶劑可以達到微細孔洞的結構,但是,問 題是經由改變發泡劑所得的.微細孔洞結構不是都充分,雖 然相當微細孔洞的材料可以經由使用不溶解的核晶劑生產 ’後者需要使用抗沈澱劑,伴隨著增加生產成本。 【發明內容】 因此本發明之目的是尋找用於生產特別微細孔洞的 PMI發泡體之調製物,在此沒有依靠使用不溶解的核晶劑 ’該發泡體還需要有和已知p Μ丨發泡體.一樣好的熱·機械 性質。 經由下列組成之混合物生產可發泡的交聯聚合狡1之方 法可以達到此目的: (Α ) 30-70重量組份之甲基丙烯酸、3 0-60重量組 份之甲基丙烯腈、〇 - 3 0重量組份含乙烯不飽和度之其他 -10 - (9) (9)1343928 經發現本發明方法由於少量比例之甲基丙嫌酸第三丁 酯或丙烯酸第三丁酯’可以生產高克分子量及極佳熱-機 械性質之發泡體,良好的發泡體是得自使用0 : 0 1 -】5重量 組份之甲基丙烯酸第三丁酯及/或丙烯酸第三丁酯,更大 比例之甲基丙烯酸第三丁酯或丙烯酸第三丁酯軟化聚合物 ,損害熱-機械性質(比較實例7a )’得到克分子量>600 kDa之可發泡的聚合物且可進—步加工而得到非常微細孔 洞的發泡體° 較宜使用〇 . 〇〗-4 · 9 9重量組份Z甲基丙烯酸第三丁酯 及/或丙烯酸第三丁酯,特別較宜是】.0-4.99重量組份之 甲基丙烯酸第三丁酯及/或丙烯酸第三丁酯,對於可以均 勻且控制性發泡之聚合物,必須添加〇. 〇 I -1 〇重量組份, 較宜是0.05-3重量組份之交聯劑,用於良好的發泡,也 需要加入〇·〇 I -1 〇重量組份,較宜是2-8重量組份之發泡 劑。 如此得到的微細孔洞發泡體其密度是在從3 0至3 0 0 公斤/立方米之所要範圍內。 當與DE 1 02 1 22 3 5.0比較時,本發明方法提供不只是 較不複雜的生產’另外的優點是經由省略不均勻的核晶劑 ’發泡體有更微細的孔洞結構,樹脂吸附因此也下降(實 例2及8於表2 )。 具有乙烯不飽和度之其他單體(A )之實例是:丙烯 酸或甲基丙烯酸’以及這些與含】_ 4個碳原子的低碳醇類 之酯類、苯乙稀、馬來酸或其酸酐衣康酸或其酸酐、乙 -13- (10)J343928 0 吡 咯 0 、氣乙燒及/或偏氯乙烯,環化而 得到 酸酐 或 醯 肢 不 可能或非常困難之共蜇體比例是不 超過 30 重 mL 里 組 份 1 較 宜是不超過20重量組份且特別較: 宜是不超3 10 眞 Μ 組 份 ,以單體之重量爲基準。 以 使用下列化合物或混合物作爲發泡劑-( ;c ) ; 甲 醯 肢 、 甲 酸、脲、衣康知、.棒樣酸、雙氰胺 、水 、單 烷 基 胨 ' 二 甲 基脲' 5,5 -偶氮雙(5 _乙基_丨3 -一 哼烷 )、 2:: 2, 偶 氮 雙 ( N -]基異丁醜胺)、2,2,-偶氡雙 (N- 二乙 基 丁 蕋 異 丁 醯 胺)' 2,2 ' 4,4,4 ’,4、六甲基 _ 2.2 ,-偶: 氛戊 院 2, 2, .偶 氮 雙(2 -甲基丙院)' 碳酸二甲醋、 碳酸 二第 ~~~. 丁 酯 丙 酮 合氣化氫碳酸鹽、氧化異丁酸甲酯 碳酸 鹽、 N- 甲 基 胺 基 甲 酸乙醋、N -乙签胺基甲酸'乙衝.、..N _ 第三 丁基 胺 基 甲 酸 乙 酯 、胺基甲酸乙酯、草酸、馬來酸、 氧化 異丁 酸 、 丙 二 酸 氰基甲醯胺' 二甲基馬來酸、甲基 四碳 酸四 乙 酯 ' 胺 酸 N -丁酯、甲基三碳酸三甲酯、甲 基三 碳酸 — 乙 酯 ! 以 及 含3 - 8個碳原子之單元醇類,例如 1 丙 醇、 2- 丙 醇 ' 1 - 丁 i 醇、2 - 丁醇、第三丁醇及異丁醇。 混 合 物中必須加入少量的交聯劑(D ) ,在 發泡 過 程 中 稍 微 交 聯可以安定發泡體且因此可以生產 均勻 的發 泡 體 > 同 時 1 交聯劑改善發泡體之耐熱性及蠕變 行爲 ,可 能 的 交 聯 劑 可 以分成兩種:共價交聯劑(D 1 ) ’ 也 就是 可 共 聚 合 的 多 重不飽和度化合物,這些單體可以 舉例 的是 丙 稀 酸 烯 丙 酯 '甲基丙烯酸烯丙酯、烯丙基丙烯 醯胺 、燒 丙 基 甲 基 丙 烯 酶胺、亞甲基雙(丙烯醯胺)或 (甲 基丙 烯 醯 -14 - (13) (13)1343928 劑是阻燃劑’除了含鹵素之阻燃劑以外,其中部份含氧化 銻:也可使用含磷的化合物,含磷的化合物因爲在火災事 件時之煙霧毒性較低而較佳,磷化合物中特別是磷烷、磷 烷氧化物、鐄化合物、膦酸鹽、亞磷酸鹽及/或磷酸鹽: 這些化合物可以是有機及/或無機特質,實例是磷酸單酯 類、膦酸單酯類、磷酸二酯類、膦酸二酯類及磷酸三酯類 以及多磷酸鹽類。 根據本發明生產之聚(甲基)丙烯醯亞胺發泡體可以 用於生產層狀材料,本發明之聚(甲基)丙烯醯亞胺發泡 體具有廣泛的應用領域,其可用在汽車、火車、飛機、船 、太空船、機械組件' 天線、X -光桌、U剌G八及導管。 本發明具有下列優點超越先前技藝.之方法_ : -聚合方法使用均勻、低黏性的混合物,其可在技術 上簡單的方法下製備及進一步加工。 -該發泡體具有極微細的孔洞結構且因此有極低的樹 脂吸附(表3 )。 -機械性質、耐熱性極蠕變行爲明顯優於比較樣本( 表4 )。 -該發泡體具有特別均勻的孔洞結構(圖2)。 下列提供的實例是提供本發明之較佳說明,而不是要 將本發明限制在其中揭示之特寫。 【實施方式】 發明實例]-7 : -17 - (17) (17)1343928 表3 :選擇的樣本之孔洞大小及樹脂吸附比較 實例 發泡體密度 孔洞大小 樹脂吸附 公斤/立方米 微米 公斤/平方米 2 69 3 5 <0.04 0 a ) 8 77 100-200 0.06 1 9 ΊΊ 沒有測量 0.287 a) 無法測量 表4 :機械數據 Γ 實例 密度 擠壓強度 耐熱性 蠕變 公斤/‘立方米 a ) b ) C ) Μ P a °C % 2 6 9 2.1 224 -0.15 6 68 1 . 8 2 1 5 0.0 5 7 6 6 1.8 2 1 0 0.57 8 6Ί 1 .5 沒有測量 0.3 ' a ) DIN 5 3 4 5 2 b) DIN 53424 c ) DIN 5 3 4 2 5、A STM D62 1 及 D2990: 1 8 0 °C、2 小 時,0.3 5 MPa 【圖式簡單說明】 圖〗:表示實例1孔洞結構之放大圖,影像尺寸I微 米XI微米 -21 - (18) 1343928 圖2 :表示實例3孔洞結構之放大圖,影像尺寸1微 米X 1微米。 -22-
Claims (1)
1343928 附件5A :第093 1 23 9 3 9號申請專利範圍修正本 民國100年3月17日修正 十、申請專利範圍 .I 一種生產可發泡的交聯化聚合物之方法,其特徵是 將下列組成之混合物 (A ) 30-70重量份之甲基丙烯酸、30-60重量份之 甲基丙烯腈、0-30重量份含乙烯不飽和度之其他單體, (B) 0.01-4.99重量份之甲基丙烯酸第三丁酯及/或 丙烯酸第三丁酯, (C) 0.01-10重量份之發泡劑, (D ) 0.01-10重量份之交聯劑, (E) 0.01至2重量份之聚合引發劑,及 (F) 0至20重量份之傳統添加劑,選自抗靜電劑 、抗氧化劑、脫模劑(m 〇 u 1 d - r e 1 e a s e a g e n t )、潤滑劑、 染料、阻燃劑、流動改良劑、塡充劑、光安定劑和有機磷 化合物(選自亞磷酸鹽或膦酸鹽)、顏料、剝離劑( release agent)、氣候安定劑及塑化劑, 整體聚合而得到片層,接著在從150至25 0 °C之溫度 下發泡。 2 · —種可發泡的交聯化聚合物,其包含下列組份: (A ) 3 0-70重量份之甲基丙烯酸、3 0-60重量份之 甲基丙烯腈、0-30重量份含乙烯不飽和度之其他單體, (B ) 0.01-4.99重量份之甲基丙烯酸第三丁酯及/或 丙烯酸第三丁酯, 1343928 (c ) Ο · ο 1 -1 0重量份之發泡劑, (D ) 〇.01-10重量份之交聯劑, (E) 〇.〇1至2重量份之聚合引發劑,及 (F ) 〇至20重量份之傳統添加劑,選自抗靜電劑 、抗氧化劑、脫模劑(m 〇 u 1 d - r e 1 e a s e a g e n t )、潤滑劑、 染料、阻燃劑、流動改良劑、塡充劑、光安定劑和有機磷 化合物(選自亞磷酸鹽或膦酸鹽)、顏料、剝離劑( feleaseagent)、氣候安定劑及塑化劑。 3·—種聚(甲基)丙烯醯亞胺發泡體,其特徵是其係 得自經由發泡如申請專利範圍第2項之聚合物。 4. 一種層狀材料,其包含如申請專利範圍第3項之聚 (甲基)丙烯醯亞胺發泡體層。 5. —種如申請專利範圍第3項之聚(甲基)丙嫌醯亞 胺發泡體的用途,其係用於汽車、火車、船、飛機、太空 船》 6·—種如申請專利範圍第3項之聚(甲基)丙烯醯亞 胺發泡體的用途,其係用於機械元件。 7. —種如申請專利範圍第3項之聚(甲基)丙烯醯亞 胺發泡體的用途,其係用於天線。 8. —種如申請專利範圍第3項之聚(甲基)丙烯醯亞 胺發泡體的用途,其係用於X-光桌。 9. 一種如申請專利範圍第3項之聚(甲基)丙烯醯亞 胺發泡體的用途,其係用於喇叭。 10. —種如申請專利範圍第3項之聚(甲基)丙嫌醯亞 -2- 1343928 胺發泡體的用途,其係用於導管
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DE10350971A DE10350971A1 (de) | 2003-10-30 | 2003-10-30 | Wärmeformbeständige Polymethacrylimid-Schaumstoffe mit feinen Poren |
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CN100390223C (zh) | 2008-05-28 |
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KR101076213B1 (ko) | 2011-10-25 |
CA2544043A1 (en) | 2005-05-26 |
CA2544043C (en) | 2012-05-15 |
WO2005047377A1 (de) | 2005-05-26 |
PT1678244E (pt) | 2008-04-22 |
DK1678244T3 (da) | 2008-05-13 |
JP4996252B2 (ja) | 2012-08-08 |
KR20060130574A (ko) | 2006-12-19 |
TW200514813A (en) | 2005-05-01 |
ATE384095T1 (de) | 2008-02-15 |
HK1096111A1 (en) | 2007-05-25 |
JP2007513213A (ja) | 2007-05-24 |
IL175244A (en) | 2011-01-31 |
PL1678244T3 (pl) | 2008-06-30 |
CN1856531A (zh) | 2006-11-01 |
EP1678244B1 (de) | 2008-01-16 |
DE502004005979D1 (de) | 2008-03-06 |
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DE10350971A1 (de) | 2005-06-02 |
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