EP2276790A2 - Procede de synthese de materiaux supramoleculaires - Google Patents
Procede de synthese de materiaux supramoleculairesInfo
- Publication number
- EP2276790A2 EP2276790A2 EP09750039A EP09750039A EP2276790A2 EP 2276790 A2 EP2276790 A2 EP 2276790A2 EP 09750039 A EP09750039 A EP 09750039A EP 09750039 A EP09750039 A EP 09750039A EP 2276790 A2 EP2276790 A2 EP 2276790A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- ester
- denotes
- process according
- polyamine
- 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- Withdrawn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
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 150000001875 compounds Chemical group 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 27
- 229930195729 fatty acid Natural products 0.000 claims description 27
- 239000000194 fatty acid Substances 0.000 claims description 27
- 150000004665 fatty acids Chemical class 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 19
- 239000000539 dimer Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 12
- -1 alkyl dicarboxylic acid Chemical compound 0.000 claims description 11
- 150000001735 carboxylic acids Chemical group 0.000 claims description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 4
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004831 Hot glue Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000012212 insulator Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 2
- PODSUMUEKRUDEI-UHFFFAOYSA-N 1-(2-aminoethyl)imidazolidin-2-one Chemical compound NCCN1CCNC1=O PODSUMUEKRUDEI-UHFFFAOYSA-N 0.000 claims description 2
- KSWGKCLICMFFFL-UHFFFAOYSA-N 1-[2-(2-aminoethylamino)ethyl]imidazolidin-2-one Chemical compound NCCNCCN1CCNC1=O KSWGKCLICMFFFL-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005700 Putrescine Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 claims description 2
- 235000020669 docosahexaenoic acid Nutrition 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000020673 eicosapentaenoic acid Nutrition 0.000 claims description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 2
- 150000004702 methyl esters Chemical group 0.000 claims description 2
- LOTBYPQQWICYBB-UHFFFAOYSA-N methyl n-hexyl-n-[2-(hexylamino)ethyl]carbamate Chemical compound CCCCCCNCCN(C(=O)OC)CCCCCC LOTBYPQQWICYBB-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 claims 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 2
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 claims 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims 2
- BITHHVVYSMSWAG-KTKRTIGZSA-N (11Z)-icos-11-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCC(O)=O BITHHVVYSMSWAG-KTKRTIGZSA-N 0.000 claims 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- ATNNLHXCRAAGJS-QZQOTICOSA-N (e)-docos-2-enoic acid Chemical compound CCCCCCCCCCCCCCCCCCC\C=C\C(O)=O ATNNLHXCRAAGJS-QZQOTICOSA-N 0.000 claims 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims 1
- LHRIUKSRPHFASO-UHFFFAOYSA-N 6-methyl-1h-pyrimidin-4-one Chemical compound CC1=CC(=O)N=CN1 LHRIUKSRPHFASO-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- 235000021319 Palmitoleic acid Nutrition 0.000 claims 1
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 claims 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229940090949 docosahexaenoic acid Drugs 0.000 claims 1
- 229960005135 eicosapentaenoic acid Drugs 0.000 claims 1
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 claims 1
- 229940108623 eicosenoic acid Drugs 0.000 claims 1
- BITHHVVYSMSWAG-UHFFFAOYSA-N eicosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCC(O)=O BITHHVVYSMSWAG-UHFFFAOYSA-N 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- 229960004488 linolenic acid Drugs 0.000 claims 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims 1
- 229960002969 oleic acid Drugs 0.000 claims 1
- 235000021313 oleic acid Nutrition 0.000 claims 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims 1
- 229960003656 ricinoleic acid Drugs 0.000 claims 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims 1
- 229960002703 undecylenic acid Drugs 0.000 claims 1
- 239000003607 modifier Substances 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 19
- 239000013638 trimer Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000002537 cosmetic Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 238000000113 differential scanning calorimetry Methods 0.000 description 2
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- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
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- AOWYBKNZZJZXTN-UHFFFAOYSA-N 1-(6-aminohexyl)-3-(6-methyl-4-oxo-1h-pyrimidin-2-yl)urea Chemical compound CC1=CC(=O)N=C(NC(=O)NCCCCCCN)N1 AOWYBKNZZJZXTN-UHFFFAOYSA-N 0.000 description 1
- DUHQIGLHYXLKAE-UHFFFAOYSA-N 3,3-dimethylglutaric acid Chemical compound OC(=O)CC(C)(C)CC(O)=O DUHQIGLHYXLKAE-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
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- 102000011782 Keratins Human genes 0.000 description 1
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- 240000006240 Linum usitatissimum Species 0.000 description 1
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- 240000008042 Zea mays Species 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
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- 150000001350 alkyl halides Chemical class 0.000 description 1
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- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DVSZKTAMJJTWFG-UHFFFAOYSA-N docosa-2,4,6,8,10,12-hexaenoic acid Chemical class CCCCCCCCCC=CC=CC=CC=CC=CC=CC(O)=O DVSZKTAMJJTWFG-UHFFFAOYSA-N 0.000 description 1
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- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
Definitions
- the present invention relates to a new method of synthesis of supramolecular materials, as well as the materials obtained and their applications.
- the so-called supramolecular materials are materials consisting of compounds associated by non-covalent bonds, such as hydrogen, ionic and / or hydrophobic bonds.
- An advantage of these materials is that these physical bonds are reversible, especially under the influence of temperature or by the action of a selective solvent. It is thus possible to envisage using them in fields of application such as coatings (paints, cosmetics, etc.), adhesives, hot melt adhesives and powder coatings or as an additive in thermoplastics or in bitumens. .
- these materials also have elastomeric properties. Unlike conventional elastomers, these materials have the advantage of being able to be fluidized above a certain temperature, which facilitates their implementation, in particular the good filling of the molds, as well as their recycling. Although they are not composed of crosslinked polymers but small molecules, these materials, like elastomers, are capable of exhibiting dimensional stability over very long times and recovering their initial shape after large deformations. They can be used to make seals, thermal or acoustic insulators, tires, cables, sheaths, shoes, packaging, patches (cosmetics or dermo-pharmaceuticals), dressings, elastic hose clamps, vacuum tubes, or tubes and hoses for transporting fluids.
- polyamines in particular diethylene triamine, DETA, triethylene tetramine, TETA or tetraethylene pentamine, TEPA
- polyamines in particular diethylene triamine, DETA, triethylene tetramine, TETA or tetraethylene pentamine, TEPA
- associative groups for example imidazolidone functional groups
- DETA or TETA DETA or TETA with a polyacid such as dimers and trimers of fatty acids or polyacrylic acid.
- This material does not have elastomeric properties.
- a self-healing elastomeric supramolecular material is further disclosed in WO 2006/087475. It comprises molecules containing at least three associative functional groups, such as imidazolidone groups, capable of forming several physical bonds and which can be obtained by reacting urea on the product of the reaction of a polyamine with triacids. It is stated that this Alternatively, the product can be obtained by reaction of the triacids with the condensation product of urea with a polyamine such as diethyl triamine (DETA).
- DETA diethyl triamine
- This method also makes it possible to easily adjust the architecture of the materials obtained, and consequently their properties, by modifying the quantity and the nature of the reagents involved. It is thus possible in particular to obtain a material having the properties of a thermoplastic elastomer, or even such an elastomer self-healing, that is to say capable, once cut, torn or scratched, to repair by simply bringing the fractured surfaces into contact without the need to heat up or apply significant pressure or to carry out any reaction chemical, the repaired material retaining elastomeric properties.
- the subject of the present invention is a process for synthesizing a supramolecular material comprising:
- the subject of the invention is also the material that can be obtained by this method.
- the dicarboxylic acid used in the first step of the process according to the invention advantageously comprises from 5 to 100, preferably from 12 to 100 and more preferably from 24 to 90 carbon atoms. It can be a linear alkyldicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, thapsic acid, octadecanedioic or branched acid such as 3,3-dimethylglutaric acid.
- a linear alkyldicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid,
- the diacid may also be mixed with other compounds such as mono- or tri-carboxylic acids. It is thus possible to use a mixture of mono-, di- and trimeric fatty acids.
- dimers oligomers of 2 identical or different monomers
- mixtures of dimers and trimers of fatty acids of vegetable origin are preferred.
- Oligomerization of unsaturated fatty acids such as undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic and docosenoic acids, which are commonly found in pine oils (TaIl oil fatty acids), rapeseed, corn, sunflower, soy, grape seeds, linseed, jojoba, as well as the eicosapentaenoic and docosahexaenoic acids found in fish oils.
- unsaturated fatty acids such as undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic and docosenoic acids, which are commonly found in pine oils (TaIl oil fatty acids), rapeseed, corn, sunflower, soy, grape seeds, lins
- fatty acid oligomers containing dimers, trimers and monomers of linear or cyclic Cis fatty acids, said mixture being predominant in dimers and trimers and containing a small percentage (usually less than 5% ) of monomers.
- said mixture comprises:
- 0.1 to 40% by weight preferably 0.1 to 5% by weight of identical or different fatty acid monomers, 0.1 to 99% by weight, preferably 18 to 85% by weight of dimers of the same or different fatty acids, and
- dimeric / trimeric mixtures of fatty acids are:
- Pripol® 1017 from Uniqema, a mixture of 75-80% of dimers and 18-22% of trimers with about 1-3% of monomeric fatty acids
- Arizona Chemical Unidyme® 14 a mixture of 94% of dimers and less than 5% of trimers and other higher oligomers with about 1% of monomeric fatty acids
- Empol® 1008 from Cognis, a mixture of 92% of dimers and 3% of higher oligomers, essentially trimers, with about 5% of monomeric fatty acids,
- Empol® 1016 from Cognis, a mixture of 80% dimers, 4% monomers and 16% fatty acid trimers
- Empol® 1018 from Cognis, a mixture of 81% dimer and 14% d higher oligomers, including essentially trimers, with about 5% of monomeric fatty acids.
- Pripol® products, Unidyme®, Empol® and Radiacid® comprise fatty acid monomers Cis and oligomers of fatty acids corresponding to multiples of C 8.
- the dicarboxylic acid may be partially or completely replaced by a diacid derivative (s), this diacid derivative being chosen from an acid ester and an acid chloride.
- an ester As an example of an ester, mention may be made of a methyl, ethyl or isopropyl ester of a fatty acid as defined above.
- a preferred fatty acid ester is a fatty acid methyl ester, and particularly a fatty acid dimer methyl ester or a mixture of fatty acid oligomers as defined above.
- fatty acid chloride mention may be made of sebacoyl chloride.
- the dicarboxylic acid or the ester derivative or acid chloride is reacted with a modifying compound bearing both associative groups and reactive functions capable of reacting with the carboxylic acid functions.
- the acid ester or acid chloride of the dicarboxylic acid or derivative used in a molar ratio of reactive functions to carboxylic acid functions (respectively ester or acid chloride) of between 0.10 and 0.50, preferably between 0.10 and 0.30.
- associative groups groups capable of associating with each other by hydrogen bonds, advantageously by 1 to 6 hydrogen bonds.
- examples of associative groups that can be used according to the invention are the imidazolidonyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups.
- the imidazolidonyl group is preferred.
- the reactive functions can in particular be chosen from primary or secondary amine functions or alcohol.
- the modifying compound carries at least one primary amine function.
- the modifying compound can thus satisfy any one of the formulas (B1) to (B5):
- R denotes a unit containing at least one reactive function
- R 'de notes a hydrogen atom
- R ", Ri and R2 denote any groups
- A denotes an oxygen or sulfur atom or an -NH group, preferably an oxygen atom.
- Preferred examples of modifying compounds are 2-aminoethylimidazolidone (UDETA), 1- (2 - [(2-aminoethyl) amino] ethyl) imidazolidone (UTETA), 1- (2-
- UDETA [(2-aminoethylamino] ethyl] amino) ethyl] imidazolidone (UTEPA), N- (6-aminohexyl) -N '- (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea ( UPy), 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole.
- UDETA is preferred for use in the present invention.
- UDETA, UTETA and UTEPA can be respectively prepared by reacting urea with diethylene triamine (DETA), triethylene tetramine (TETA) and tetraethylene pentamine (TEPA).
- DETA diethylene triamine
- TETA triethylene tetramine
- TEPA tetraethylene pentamine
- the reaction of the modifying compound with the dicarboxylic acid may, for example, be carried out at a temperature of between 20 and 200 ° C., preferably between 130 and 170 ° C., for a period ranging from 1 to 15 hours, for example from 3 to 9 hours. h, advantageously with stirring and under an inert atmosphere.
- the dicarboxylic acid or its ester derivative or acid chloride is also reacted, in the first step of the process according to the invention, with at least one polyamine, for example in a molar ratio of the amine functions to the acid functions of the dicarboxylic acid of between 0.90 and 0.50, in particular between 0, 90 and 0.70.
- the polyamine may be any compound carrying at least two amine functions, preferably primary amine, and preferably a compound of formula (I):
- Ri, R 2, R 3 and R 4 independently denote a hydrogen atom or an alkyl group C x -C 6 such as methyl group, m, n, p and q independently denote an integer ranging from 1 to 3, x denotes an integer ranging from 1 to 6, y denotes an integer ranging from 0 to 2.
- M + n is 2, 3 or 6, preferably 2,
- P + q is 2, 3 or 6, preferably 2,
- X denotes an integer ranging from 2 to 4,
- y is 0 or 1, preferably 0.
- polyamines of formula (I) are DETA (diethylene triamine), TETA (triethylene tetramine), TEPA (tetraethylene pentamine) and dihexylene triamine.
- the polyamine according to the invention may be a linear alkylene diamine containing 3 to 20 carbon atoms such as cadaverine, putrescine, Hexamethylene diamine or 1,12-diaminododecane or a cyclic alkylene diamine such as isophorone diamine.
- reaction of the polyamine with the dicarboxylic acid or the ester or acid chloride derivative used may, for example, be carried out at a temperature of between 20 and 200 ° C., preferably between 140 and
- the first step of the process according to the invention comprises the reaction of the dicarboxylic acid or its ester derivative or acid chloride, both with the modifying compound and with the polyamine described above. These two reactions can be performed simultaneously or successively. In the case where these reactions are conducted successively, the reaction with the modifier compound will preferably be carried out first but the reverse order is also possible. They may also be carried out either in separate reactors or in the same reactor, without it being necessary to provide a washing or purification step after the first of these reactions.
- the polycondensate obtained at the end of the first step can be semi-crystalline with a melting temperature (Tf) most often between 30 and 150 ° C. and it has a glass transition temperature (T g ) most often between -50 0 C and 20 0 C.
- Tf melting temperature
- T g glass transition temperature
- the product resulting from this first stage is then reacted, in a second stage, with urea, without it being necessary to carry out a washing or a prior purification thereof.
- the reaction may for example be carried out at a temperature of 130 to 170 ° C., preferably 130 to 160 ° C., by carrying out a temperature ramp, for a period ranging from 30 minutes to 8 hours, preferably for a period of 1 hour. at 6 hours, under an inert atmosphere and, advantageously, with stirring.
- this reaction can be carried out in a reactor separate from that or those used in the first stage, or in the same reactor. It is therefore understood that all the steps of the process according to the invention can be implemented in the same reactor, by successive addition of reagents, which makes the process particularly simple and economical.
- the function of urea is to create additional associative groups, for example according to the following reaction schemes:
- the reagents (dicarboxylic acid or derivative, modifying compound, polyamine and urea) described above can be introduced, in the process according to the invention, in the molten state, in the pulverulent state, or by solvent, for example in aqueous solution. However, it is preferred that they be introduced in powder form or in the molten state to avoid the use of solvents which need to be subsequently removed.
- This material consists of a set of molecules of different lengths, containing a portion soluble in an alcohol and optionally an insoluble part, ie a fraction representing from 0.1 to 90% of the weight of the material and which is not soluble in any solvent.
- the number-average molecular weight of the soluble fraction is preferably from 300 to 300,000 g / mol, as measured by GPC.
- the average number of associative groups per molecule is at least 1.2, preferably at least 2 or even at least 2.2.
- this material comprises molecules containing binding bridges, preferably amide, formed in the first step of its synthesis process, by reaction of the reactive groups (advantageously primary amine) of the modifying compound with a part of the dicarboxylic acid and by reacting the amine functions of the polyamine with another part (preferably the remainder) of the dicarboxylic acid.
- This material also contains hydrogen bonds between the associative groups carried by the molecules which constitute it, and which are provided by the modifier compound and by the reaction of urea on the polyamine.
- this material also contains intermolecular hydrophobic bonds, advantageously due to interactions between pendant alkyl groups provided by the dicarboxylic acid. Such groups are especially present in fatty acid dimers.
- thermoplastic elastomer properties that is to say the property of being able to be subjected to uniaxial deformation at ambient temperature, possibly at least 20% for 15 minutes, and to recover, once this stress released, its initial dimension, with a remanent deformation less than 5% of its initial dimension, and which can be put and reformed at high temperature.
- It can also be capable of self-healing after a cut and present, after contacting the edges of the cut, elastomeric properties allowing it to undergo, for example, a tensile deformation of at least 100% or at least 200% before breaking and recovering its initial dimensions once the stress is released, with a remanent deformation of less than 10% of its initial dimension.
- a material is generally obtained in the form of a soft solid, which can be extruded or cold ground, for example in a hammer mill, ball mill, ball mill or grinding mill. or knives and then washed, for example with water, and finally shaped, in particular by hot pressing, calendering, thermoforming or any other method.
- the material according to the invention can in particular be used to manufacture gaskets, thermal or acoustic insulators, tires, cables, sheaths, shoe soles, packaging, coatings (paints, films, cosmetic products ), patches (cosmetics or dermopharmaceuticals) or other asset trapping and release systems, dressings, elastic hose clamps, vacuum tubes, fluid tubes and hoses, and in a manner general parts having good resistance to tearing and / or fatigue, rheological additives, additives for bitumen or additives for hot melt adhesives and adhesives.
- the invention therefore also relates to the use of the material according to the invention for the aforementioned purposes.
- the material according to the invention can be used as such or in single-phase or multiphase mixtures with one or more compounds such as petroleum fractions, solvents, mineral and organic fillers, plasticizers, resins and the like.
- tackifiers, antioxidants, pigments and / or dyes for example, in emulsions, suspensions or solutions.
- this material can be used for the manufacture of a cosmetic composition usually comprising a physiologically acceptable medium, that is to say compatible with keratin materials, containing for example at least one oil and / or water and / or an alcohol.
- This cosmetic composition can be used for the care and / or makeup of the skin and / or its integuments (such as eyelashes and nails) and / or lips or for washing, conditioning and / or putting in the form of hair.
- integuments such as eyelashes and nails
- Sub-step a In a reactor with a diameter of 60 mm and a nominal volume of 500 ml equipped with a bottom valve, a thermal fluid temperature regulation, a mechanical stirrer, a dropping funnel, a Dean-Stark and a gas inlet, preheated to 40 0 C, is introduced 76 g of Empol ® 1016 [acid number 194, monomer level (4%), dimer (80%), trimer (16%)] and 6.7g of purified UDETA (52 mmol), which is a ratio [HN 2 ] / [COOH] of 0.2. The bath temperature is brought to 150 ° C. for 8 hours under a flow of nitrogen of 500 ml / minute and stirring of 280 rpm.
- the product of the reaction is stored at 50 ° C. in the reactor.
- the reactor body is heated to 160 ° C. and the amine is slowly added dropwise intermittently over a total period of 3 hours.
- the reaction is allowed to continue for another 4 hours at 160 ° C.
- the same type of evolution is observed by infrared spectroscopy as previously.
- the end of The release of water vapor, again observed, is used as a criterion for stopping the reaction.
- the product is collected by the bottom valve (86 g are collected) and stored at room temperature. It is a highly adhesive viscoelastic liquid on many substrates including glass, metal and paper.
- the glass transition temperature measured by DSC (Differential Scanning Calorimetry) is -11 ° C. Rheological measurements made in plane parallel geometry with an imposed deformation of 1% provided, at the loading frequency of 1 rad / s, the following results:
- the stopping criterion is this time that the product is solid and clings to the axis of the agitator. As soon as this is the case, the product is collected on the stirring rod.
- the pieces obtained are placed in a plastic bag and cold-milled with a hammer. Fragments of size 1 to 2 mm are washed by immersion in water for 72 hours. In the water, the washed fragments tend to stick to each other.
- the sample, previously drained, is redécoupe into pieces of approximately 5 mm in size which is placed in a mold consisting of a 1.6 mm thick brass plate pierced with a rectangular hole, placed between two sheets of release paper. After a first pressing at 120 ° C. for 10 minutes (applied pressure 10 MPa), the film obtained has irregularities in thickness which are corrected by adding material and repressing until a satisfactory appearance is obtained.
- Example 2 Traction test
- 60 mm is cut in half in the middle, left to rest for five minutes, repaired by contacting the rupture surfaces and then left to rest for two hours.
- a tensile test is carried out on the cicatrized ribbon after having drawn two marks 4 cm apart, on each side of the scar. The ribbon is stretched until it reaches 350% of deformation without breaking.
- the ribbon is then left standing at room temperature. After 40 minutes, we see that it has returned to its original size.
- This example shows that the process according to the invention makes it possible, under simple and economical conditions, to obtain materials having the rubber-elastic property and capable of self-repairing in the event of a break.
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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)
- Polyamides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0852981A FR2930777B1 (fr) | 2008-05-05 | 2008-05-05 | Procede de synthese de materiaux supramoleculaires |
PCT/FR2009/050825 WO2009141558A2 (fr) | 2008-05-05 | 2009-05-05 | Procede de synthese de materiaux supramoleculaires |
Publications (1)
Publication Number | Publication Date |
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EP2276790A2 true EP2276790A2 (fr) | 2011-01-26 |
Family
ID=40011199
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP09750039A Withdrawn EP2276790A2 (fr) | 2008-05-05 | 2009-05-05 | Procede de synthese de materiaux supramoleculaires |
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US (1) | US8536281B2 (ja) |
EP (1) | EP2276790A2 (ja) |
JP (1) | JP5254431B2 (ja) |
CN (1) | CN102131846B (ja) |
BR (1) | BRPI0910532A2 (ja) |
FR (1) | FR2930777B1 (ja) |
WO (1) | WO2009141558A2 (ja) |
Families Citing this family (14)
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FR2944025B1 (fr) * | 2009-04-02 | 2011-04-01 | Arkema France | Utilisation en tant qu'absorbeur de chocs, d'un materiau forme de molecules arborescentes comportant des groupes associatifs |
FR2959996B1 (fr) * | 2010-05-11 | 2012-05-11 | Bostik Sa | Hmpsa pour etiquette auto-adhesive decollable |
FR2965408A1 (fr) * | 2010-09-23 | 2012-03-30 | Arkema France | Materiau composite et utilisation pour la fabrication d'une electrode |
FR2966465B1 (fr) * | 2010-10-21 | 2012-11-02 | Arkema France | Composition comprenant un melange de polycondensat thermoplastique et de polymere supramoleculaire, et procede de fabrication |
GB201215100D0 (en) | 2012-08-24 | 2012-10-10 | Croda Int Plc | Polymide composition |
FR3002538B1 (fr) * | 2013-02-25 | 2017-09-01 | Arkema France | Materiaux supramoleculaires a base d'oligo-amides |
US9084735B2 (en) | 2013-08-01 | 2015-07-21 | International Business Machines Corporation | Self-assembling bis-urea compounds for drug delivery |
EP3473672A4 (en) * | 2016-06-16 | 2019-08-14 | Bridgestone Corporation | ADDITIVE FOR RUBBER |
CN108865046B (zh) * | 2017-05-16 | 2021-05-14 | 天津大学 | 自愈合性超分子聚酰胺类粘合剂及其制备方法和应用 |
CN107099137B (zh) * | 2017-05-30 | 2019-08-20 | 华南理工大学 | 一种自愈合弹性体材料及其制备方法 |
DE102017125179A1 (de) | 2017-10-26 | 2019-05-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Modifizierte Härterkomponente für ein Polymer und insbesondere für 2K-Formulierungen mit selbstheilenden Eigenschaften |
DE102017125178B4 (de) | 2017-10-26 | 2022-12-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Elektrisches Bauteil mit selbstheilender Lackeschichtung, Verfahren zu dessen Herstellung, Verfahren zur Selbstheilung des elektrischen Bauteils nach elektrischem Durchschlag sowie Verwendung einer Lackbeschichtung als selbstheilende Beschichtung |
CN110061238B (zh) * | 2018-03-20 | 2021-12-07 | 南方科技大学 | 水溶性自愈合粘结剂及其制备方法和锂离子电池 |
KR102228539B1 (ko) | 2018-10-23 | 2021-03-15 | 주식회사 엘지화학 | 반도체 회로 접속용 접착제 조성물 및 이를 포함한 접착 필름 |
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DE3723941A1 (de) * | 1987-07-20 | 1989-02-02 | Henkel Kgaa | Neue polyamide aus dimerisierten fettsaeuren und polyetherharnstoffdiaminen sowie deren verwendung als klebstoffe |
KR0171994B1 (ko) * | 1995-07-13 | 1999-03-30 | 구광시 | 방향족 폴리아미드, 광학적 이방성 도우프와 성형물, 및 이들의 제조방법 |
JP3345877B2 (ja) | 1997-07-10 | 2002-11-18 | 日本ピー・エム・シー株式会社 | 紙塗工用樹脂及び紙塗工用組成物 |
US6008313A (en) * | 1997-11-19 | 1999-12-28 | Air Products And Chemicals, Inc. | Polyamide curing agents based on mixtures of polyethyleneamines and piperazine derivatives |
JP3551050B2 (ja) | 1998-12-04 | 2004-08-04 | 住友化学工業株式会社 | 熱硬化性樹脂水溶液の製造方法 |
ATE325140T1 (de) | 2002-01-17 | 2006-06-15 | Arkema | Supramolekularpolymere |
EP1778741B1 (fr) * | 2004-07-08 | 2010-01-13 | Arkema France | Materiau polymere contenant des chaines portant des fonctions imidazolidone |
JP2006159636A (ja) * | 2004-12-07 | 2006-06-22 | Toyobo Co Ltd | リン酸カルシウム系化合物層含有複合材料およびその製造法 |
FR2882061B1 (fr) * | 2005-02-15 | 2008-04-18 | Arkema Sa | Materiaux elastiques |
FR2905698B1 (fr) * | 2006-09-08 | 2012-08-31 | Arkema France | Polymeres supramoleculaires semi-cristallins |
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2008
- 2008-05-05 FR FR0852981A patent/FR2930777B1/fr not_active Expired - Fee Related
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2009
- 2009-05-05 US US12/991,181 patent/US8536281B2/en not_active Expired - Fee Related
- 2009-05-05 EP EP09750039A patent/EP2276790A2/fr not_active Withdrawn
- 2009-05-05 CN CN200980116272.5A patent/CN102131846B/zh not_active Expired - Fee Related
- 2009-05-05 JP JP2011507972A patent/JP5254431B2/ja not_active Expired - Fee Related
- 2009-05-05 WO PCT/FR2009/050825 patent/WO2009141558A2/fr active Application Filing
- 2009-05-05 BR BRPI0910532A patent/BRPI0910532A2/pt not_active IP Right Cessation
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WO2009141558A3 (fr) | 2010-04-22 |
JP5254431B2 (ja) | 2013-08-07 |
US8536281B2 (en) | 2013-09-17 |
CN102131846B (zh) | 2014-01-15 |
CN102131846A (zh) | 2011-07-20 |
WO2009141558A2 (fr) | 2009-11-26 |
BRPI0910532A2 (pt) | 2015-09-29 |
JP2011522909A (ja) | 2011-08-04 |
FR2930777B1 (fr) | 2011-07-01 |
US20110059280A1 (en) | 2011-03-10 |
FR2930777A1 (fr) | 2009-11-06 |
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