EP3941969A1 - Compositions de copolyamides comprenant des fibres de renforts presentant une stabilite de module elevee et leurs utilisations - Google Patents
Compositions de copolyamides comprenant des fibres de renforts presentant une stabilite de module elevee et leurs utilisationsInfo
- Publication number
- EP3941969A1 EP3941969A1 EP20726195.9A EP20726195A EP3941969A1 EP 3941969 A1 EP3941969 A1 EP 3941969A1 EP 20726195 A EP20726195 A EP 20726195A EP 3941969 A1 EP3941969 A1 EP 3941969A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- copolyamide
- composition
- fibers
- xiy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 143
- 239000012783 reinforcing fiber Substances 0.000 title claims abstract description 66
- 150000004985 diamines Chemical class 0.000 claims abstract description 43
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 38
- 150000001413 amino acids Chemical class 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 27
- 150000003951 lactams Chemical class 0.000 claims abstract description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000004609 Impact Modifier Substances 0.000 claims description 38
- 239000003365 glass fiber Substances 0.000 claims description 38
- 239000000654 additive Substances 0.000 claims description 34
- 239000000945 filler Substances 0.000 claims description 28
- 239000012749 thinning agent Substances 0.000 claims description 22
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 claims description 11
- 229920006152 PA1010 Polymers 0.000 claims description 6
- 229920006396 polyamide 1012 Polymers 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 description 46
- 239000011575 calcium Substances 0.000 description 14
- 229920002647 polyamide Polymers 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 10
- 239000001993 wax Substances 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 229920002614 Polyether block amide Polymers 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 230000007717 exclusion Effects 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004760 aramid Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000003750 conditioning effect Effects 0.000 description 4
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 229920006017 homo-polyamide Polymers 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 4
- 229920006260 polyaryletherketone Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920002530 polyetherether ketone Polymers 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 239000004953 Aliphatic polyamide Substances 0.000 description 3
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229920003231 aliphatic polyamide Polymers 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LJOSESICVCVVCK-UHFFFAOYSA-N docosane-1,1-diamine Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)N LJOSESICVCVVCK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000002557 mineral fiber Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920006375 polyphtalamide Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229920006024 semi-aromatic copolyamide Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 3
- ROFWOEQFASWFTK-UHFFFAOYSA-N 1-cyclohexylpropylcyclohexane Chemical compound C1CCCCC1C(CC)C1CCCCC1 ROFWOEQFASWFTK-UHFFFAOYSA-N 0.000 description 2
- GSJAEHIASJBUKQ-UHFFFAOYSA-N 1-methyl-1-[2-(1-methylcyclohexyl)propan-2-yl]cyclohexane Chemical compound CC1(CCCCC1)C(C)(C)C1(CCCCC1)C GSJAEHIASJBUKQ-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 2
- DWHXNKJKNIHNOI-UHFFFAOYSA-N 10-azaniumylundecanoate Chemical compound CC(N)CCCCCCCCC(O)=O DWHXNKJKNIHNOI-UHFFFAOYSA-N 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 2
- LHBHZALHFIQJGJ-UHFFFAOYSA-N 3-hydroxy-2-(4-methoxyphenyl)-3,5-dihydro-2h-1,5-benzothiazepin-4-one Chemical compound C1=CC(OC)=CC=C1C1C(O)C(=O)NC2=CC=CC=C2S1 LHBHZALHFIQJGJ-UHFFFAOYSA-N 0.000 description 2
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- 229920002748 Basalt fiber Polymers 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000271 Kevlar® Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical class OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical class OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
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- GNHLOUIICBHQIT-UHFFFAOYSA-N 11-(heptylamino)undecanoic acid Chemical compound CCCCCCCNCCCCCCCCCCC(O)=O GNHLOUIICBHQIT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
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- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 101100301844 Arabidopsis thaliana RH50 gene Proteins 0.000 description 1
- SPGAJDBZHBLJHP-UHFFFAOYSA-N CCCCCCCCCCCCCCCC(N)N.CCCCCCCCCCCCCC(N)N Chemical compound CCCCCCCCCCCCCCCC(N)N.CCCCCCCCCCCCCC(N)N SPGAJDBZHBLJHP-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 241000761389 Copa Species 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920003317 Fusabond® Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Definitions
- TITLE COMPOSITIONS OF COPOLYAMIDES CONTAINING REINFORCING FIBERS PRESENTING HIGH MODULE STABILITY AND THEIR USES
- the present patent application relates to the use of semi-aromatic copolyamides for the manufacture of compositions exhibiting a high modulus stability under the effect of temperature and humidity, their manufacturing process as well as said compositions.
- modulus polymeric materials for example for televisions, digital cameras, digital games, phone parts, digital tablets, drones, printers or computer parts.
- the modulus of the material is in fact a crucial factor in enabling a reduction in weight, since it allows a reduction in the thickness of the parts while maintaining great rigidity.
- moduli for example tensile modulus, flexural modulus, etc.
- These modules can be impacted by temperature and by the humidity level contained in the sample.
- the rigidity is little affected by changes in temperature or by the water content in the material. Indeed, the stability of the module is also an important factor for subsequent use or for ensuring easy assembly of the parts when this is carried out in places where the temperature and / or humidity may be high.
- polymers are sought whose modulus remains stable in the temperature and / or humidity range to which they are exposed, in particular during the assembly of the parts and the subsequent operation of the devices.
- the modulus would be stable at a temperature ranging from 20 ° C to 40 ° C, especially in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C for compositions having variable water contents (caused by conditioning the compositions in an atmosphere where the humidity could vary from 0 to 100%, or in liquid water)
- polystyrene foams must exhibit moderate molding temperatures and crystallize sufficiently quickly to allow a transformation time, in particular a cycle time, suitable for an industrial process.
- aliphatic polyamides generally exhibit a significant loss of rigidity when the temperature increases, in particular when these polyamides have been packaged in a humid atmosphere beforehand because they contain a certain amount of water.
- copolyamides comprising at least two distinct A / XT units characterized in that said copolyamide has an amine end-of-chain content greater than or equal to 20 peq / g, an end-of-chain content acid less than or equal to 100 peq / g, and a non-reactive chain end content greater than or equal to 20 peq / g.
- the copolyamide can comprise additives, in particular reinforcing fibers, said reinforcing fibers possibly being glass fibers.
- compositions for an electronic mobile device comprising at least 20% of at least one polymer and at least 20% of glass fibers having a non-circular section and an elastic modulus of at least 76 determined GPa. according to ASTM C1557-03.
- the aim of the invention is therefore to provide semi-aromatic copolyamides for the manufacture of compositions exhibiting a high modulus stability under the effect of temperature and humidity.
- a subject of the invention is the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY, in which:
- - A is a repeating unit obtained by polycondensation:
- Cis amino acid preferably C10 to Cis, more preferably C10 to C12, or
- Cis lactam preferably Cio to Cis, more preferably Cio to C12, or
- C4-C36 diamine Ca preferably C6-C18, preferably C6-C12, more preferably C10-C12, with at least one Cb C4-C36 dicarboxylic acid, preferentially C6-C18, preferentially C6-C12, more preferably C10-C12;
- - XiY is a repeating unit obtained from the polycondensation of at least one linear aliphatic diamine (Xi) in C 4 to Cs, preferably from C 4 to C 6 , more preferably from C 6 , and at least one acid aromatic dicarboxylic (Y),
- composition whose modulus does not vary by more than 20% in the temperature range from 20 ° C to 40 ° C, in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C.
- the present invention relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY, as defined above, to prepare a composition whose modulus does not vary. not more than 20% in the temperature range from 20 ° C to 40 ° C, especially in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from - 10 ° C to 40 ° C in comparison with the variation of the modulus of an aliphatic homopolyamide measured under the same conditions.
- the present invention relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY, as defined above, to prepare a composition whose modulus does not vary by more than 20% in the temperature range from 20 ° C to 40 ° C, in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from from -10 ° C to 40 ° C in comparison with the variation of the modulus of an aliphatic homopolyamide having the same unit A, measured under the same conditions.
- the present invention relates to the use of a composition comprising a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to limit the variation of the modulus in the temperature range going from 20 ° C to 40 ° C, in particular in the temperature range going from 0 ° C to 40 ° C, in particular in the 'temperature range ranging from -10 ° C to 40 ° C, said modulus not varying by more than 20% compared to the variation of the modulus of said composition measured under the same conditions in which an aliphatic homopolyamide is used instead of said copolyamide.
- the present invention relates to the use of a composition comprising a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to limit the variation of the modulus in the '' temperature range from 20 ° C to 40 ° C, in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C, said modulus not varying by more than 20% compared to the variation in modulus of said composition measured under the same conditions in which an aliphatic homopolyamide having the same unit A, is used instead of said copolyamide.
- the inventors have unexpectedly found that the selection of a semi-aromatic copolyamide comprising a repeating unit A and a repeating unit XiY based on an aromatic diacid, made it possible to prepare a composition of which not only the modulus exhibits stability under l effect of temperature and humidity, and does not vary by more than 20% in the temperature range from 20 ° C to 40 ° C, especially in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C, but also the implementation of which is facilitated by a low molding temperature, in particular less than 100 ° C, preferably less than 90 ° C, and by a short cycle time during its implementation.
- the 66 / 6T copolyamide is excluded from the definition of the A / XT copolyamides of the invention.
- said at least one Ca diamine is C 7 -Cis, preferably C 7 - C12, more preferably C10-C12, and said at least one Cb dicarboxylic acid is C6-C18, preferably C6-C12, more preferably C10-C12;
- said at least one lactam can be chosen from a C9 to Cis lactam, preferably Cio to Cis, more preferably Cio to C12.
- a C10 to C12 lactam is in particular decanolactam, undecanolactam, and lauryllactam.
- Said unit A is obtained from the polycondensation of at least one lactam and can therefore comprise a single lactam or several lactams.
- said unit A is obtained from the polycondensation of a single lactam and said lactam is lauryllactam.
- said at least one amino acid can be chosen from a C 8 to Cis amino acid, preferably Cio to Cis, more preferably Cio to C12.
- a Cg to C12 amino acid is in particular 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular acid N-heptyl-11-aminoundecanoic.
- Said unit A is obtained from the polycondensation of at least one amino acid and can therefore comprise a single amino acid or several amino acids.
- said unit A is obtained from the polycondensation of a single amino acid and said amino acid is 11-aminoundecanoic acid.
- the repeating unit A of said copolyamide is obtained from the polycondensation of at least one C4-C36 diamine Ca, preferably C6-C18, preferably C6-C12, more preferably C10-C12, with at least one Cb-C4 diacid -C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12 , then said at least one diamine in Ca is a linear or branched aliphatic diamine, in particular linear and said at least one diacid Cb is a linear aliphatic diacid or branched, in particular a linear diacid.
- said at least one diamine is linear aliphatic and said at least one diacid is aliphatic and linear.
- Said at least one C4-C36 diamine Ca can be in particular chosen from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1, 18- octadecamethylenediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.
- said at least one Ca diamine is C6-C18 and chosen from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12- dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1,18-octadecamethylenediamine.
- said at least one C 6 to C u diamine Ca is in particular chosen from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1, 10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.
- the Ca diamine used is C10 to C12, in particular chosen from 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.
- Said at least one Cb C 4 to C36 dicarboxylic acid may be chosen from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid , dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from acids fat.
- said at least one Cb dicarboxylic acid is C 6 to Cis and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.
- said at least one Cb dicarboxylic acid is C 6 to C12 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.
- said at least one Cb dicarboxylic acid is C10 to C12 and is chosen from sebacic acid, undecanedioic acid and dodecanedioic acid.
- Said unit A is obtained from the polycondensation of at least one diamine Ca with at least one dicarboxylic acid Cb and can therefore comprise a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.
- said unit A is obtained from the polycondensation of a single diamine Ca with a single dicarboxylic acid Cb.
- Said unit XiY is a repeating unit obtained from the polycondensation of at least one linear aliphatic diamine (Xi) in C 4 to Cs, preferably in C 4 to more preferably in and at least one aromatic dicarboxylic acid (Y).
- Said linear aliphatic diamine (Xi) is chosen from selected from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine.
- Said linear aliphatic diamine (Xi) can be identical to or different from the aliphatic and linear diamine Ca.
- Said aromatic dicarboxylic acid (Y) can be C 6 Cis, C 6 Cis, preferably Cs to C 8, more preferably Cs to C12.
- T terepthalic acid
- I isophthalic acid
- N naphthalene dicarboxylic acid
- said aromatic dicarboxylic acid (Y) is terepthalic acid.
- the modulus of a composition changes as a function of the temperature and in general, the modulus decreases with the increase in temperature.
- conditioning in a humid atmosphere means after saturation in liquid water at 65 ° C.
- M20 be the modulus measured at 20 ° C
- M T be the modulus measured at a temperature T for a composition conditioned under the same dry or humid atmosphere conditions
- the modulus does not vary by more than 20% in the temperature range going from 0 ° C to 40 ° C and therefore ((Mo - M T ) / Mo) x 100 ⁇ 20, with T varying from 0 at 40 ° C for a composition packaged under the same dry or humid atmosphere conditions.
- the modulus does not vary by more than 20% in the temperature range going from -10 ° C to 40 ° C and therefore ((M-10 - M T ) / M-10) x 100 ⁇ 20, with T varying from -10 to 40 ° C for a composition packaged under the same conditions of a dry or humid atmosphere.
- the modulus does not vary by more than 15% in the temperature range going from 0 ° C to 40 ° C and therefore ((Mo - M T ) / Mo) x 100 ⁇ 15, with T varying from 0 at 40 ° C for a composition packaged under the same humid atmosphere conditions.
- the modulus does not vary by more than 15% in the temperature range going from -10 ° C to 40 ° C and therefore ((M-10 - M T ) / M-10) x 100 ⁇ 15, with T varying from -10 to 40 ° C for a composition packaged under the same humid atmosphere conditions.
- the modulus does not vary by more than 5% in the temperature range going from 0 ° C to 40 ° C and therefore ((Mo - M T ) / Mo) x 100 ⁇ 5, with T varying from 0 at 40 ° C for a composition packaged under the same dry atmosphere conditions.
- the modulus does not vary by more than 5% in the temperature range going from -10 ° C to 40 ° C and therefore ((M-io - M T ) / M-io) x 100 ⁇ 5, with T varying from -10 to 40 ° C for a composition packaged under the same dry atmosphere conditions.
- the modulus is measured as defined above according to the ISO 178: 2010 standard and corresponds to the flexural modulus.
- the modulus is measured as defined above according to the ISO 527-1 and 2: 2012 standard and corresponds to the tensile modulus.
- said unit XiY of said copolyamide defined above is a repeating unit obtained by polycondensation of at least one C 4 to C 8 aliphatic diamine (Xi), more preferably C 4 to especially C 6 and at least one aromatic dicarboxylic acid
- Examples of X 4 Y units are 41, 4T, 4N, 61, 6T, 6N.
- said copolyamide is of formula A / XiT
- said X 4 Y unit of said copolyamide defined above is a repeating unit obtained by polycondensation of at least one C 4 to C 8 aliphatic diamine (Xi), preferably C 4 to CQ, more preferably C 6 .
- Examples of X 4 Y units are 41, 4T, 4N, 61, 6T, 6N,
- X 4 Y is chosen from 4T, 6T, preferably 6T.
- said copolyamide is of formula A / 4T or A / 6T, preferably A / 6T.
- said unit A of said copolyamide defined above is an amino acid or a lactam as defined above.
- said copolyamide is of formula A / XiY in which A is an amino acid or a lactam as defined above and X 4 Y is as defined above.
- said copolyamide is of formula A / XiT in which A is an amino acid or a lactam as defined above.
- said copolyamide is of formula A / 4T or A / 6T, preferably A / 6T in which A is an amino acid or a lactam as defined above.
- said unit A of said copolyamide defined above is an amino acid or a Cn or C 12 lactam respectively.
- said copolyamide is of formula A / XiY in which A is an amino acid or a Cn or C12 lactam and X 4 Y is as defined above.
- said copolyamide defined above is semi-crystalline.
- a semi-crystalline copolyamide within the meaning of the invention, denotes a copolyamide which has a melting point (Tm) in DSC according to standard ISO 11357-3: 2013, and an enthalpy of crystallization during the cooling step at a speed of 20K / min in DSC measured according to standard ISO 11357-3 of 2013 greater than 30 J / g, preferably greater than 35 J / g.
- the molar ratio of the units A and XiY in the copolyamide of the invention is adapted according to the different units so that said copolyamide is semi-crystalline.
- said copolyamide of formula A / XiY consists only of units A and XiY as defined above.
- the copolyamide has only one or more unit (s) A and one or more unit (s) XiY nevertheless, A is a repeating unit obtained by polycondensation of at least one amino acid or at least one lactam or at least one diamine in Ca with at least one dicarboxylic acid in Cb, as defined above, and XiY is a repeating unit obtained from the polycondensation of at least one diamine linear aliphatic (Xi) as defined above, and at least one aromatic dicarboxylic acid (Y) as defined above.
- said copolyamide of formula A / XiY consists only of an A unit and a XiY unit as defined above.
- the copolyamide has only one unit A and only one unit XiY and A is a repeating unit obtained by polycondensation of an amino acid or of a lactam or of a diamine in Ca with a Cb dicarboxylic acid as defined above, and XiY is a repeating unit obtained from the polycondensation of a linear aliphatic diamine (Xi) as defined above, and of an aromatic dicarboxylic acid (Y) as defined above.
- the copolyamide is chosen from PA11 / 4T, PA11 / 6T, PA12 / 4T, PA12 / 6T, PA610 / 4T, PA610 / 6T, PA612 / 4T, PA612 / 6T, PA1010 / 4T, PA1012 / 4T, PA1010 / 6T , PA1012 / 6T, PA1210 / 4T, PA1210 / 6T, PA1210 / 6T, PA1212 / 6T, in particular PA11 / 6T.
- said copolyamide comprises at least a third Z unit, distinct from the A and XiY units, and corresponds to the general formulation A / XiY / Z
- Z is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ce).
- (Cd diacid) with c representing the number of carbon atoms of the diamine and d representing the number of carbon atoms of the diacid, c and d each being between 4 and 36, advantageously between 9 and 18, with the proviso that caprolactam or aminohexanoic acid are excluded from the definition of lactam and amino acid of Z and that when the diamine in Ce is a diamine in CIO, then terepthalic acid is excluded from the definition of diacid in Cd.
- the copolyamide of the invention can comprise one or more A unit (s) and one or more XiY unit (s) and at least a Z pattern.
- the term “distinct” means that even if there are several A and / or XiY units, the Z unit when it is present is different from the A and XiY units present in the copolyamide but that it can however also be of the same type. than for A, namely a repeating unit obtained from the polycondensation of a lactam, or of an amino acid or of a diamine in Ca with a dicarboxylic acid in Cb, or of the same type as XiY, namely a unit repetitive obtained from the polycondensation of at least one linear C 4 to C 8 aliphatic diamine (Xi), and at least one aromatic dicarboxylic acid (Y).
- Z represents a unit obtained from an amino acid
- it can be chosen from 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-acid.
- Z represents a unit obtained from a lactam
- it can be chosen from pyrrolidinone, 2-piperidinone, caprolactam, enantholactam, caprolactam, pelargolactam, decanolactam, undecanolactam, and lauryllactam.
- the Z unit is a unit corresponding to the formula (diamine in Ce).
- (Cd-diacid) the (Cd-diamine) unit is chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and arylaliphatic diamines.
- the diamine When the diamine is aliphatic and branched, it may contain one or more methyl or ethyl substituents on the main chain.
- the Ce diamine can advantageously be chosen from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,3-diaminopentane, 2-methyl-l, 5-pentanediamine, 2-methyl-1,8-octanediamine.
- the C6 diamine is cycloaliphatic, it is chosen from bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3,5-dialkyl) -4- aminocyclo-hexyl) propane, bis (3,5-dialkyl-4-aminocyclo-hexyl) butane, bis- (3-methyl-4-aminocyclohexyl) -methane (BMACM or MACM), p-bis (aminocyclohexyl) -methane (PACM) and isopropylidenedi (cyclohexylamine) (PACP), 1,3-bis (aminomethyl) cyclohexyl (1,3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1,4 BAC) and a mixture of these.
- BMACM or MACM bis-methyl-4
- the C6 diamine is arylaliphatic, it is chosen from 1,3-xylylenediamine and 1,4-xylylenediamine.
- the Cd dicarboxylic acid is chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids.
- the Cd-diacid is aliphatic and linear, it is chosen from succinic acid, glutaric acid, adipic acid, heptanedioic acid, octanedioic acid, azelaic acid, sebacic acid, l 'undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenedioic acid, eicosanedioic acid, docosanedioic acid and fatty acid dimers containing 36 carbons.
- the dimers of fatty acids mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of long-chain hydrocarbon unsaturated monobasic fatty acids (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
- the diacid when it is cycloaliphatic, it may contain the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl), di (methylcyclohexyl) propane.
- the diacid is aromatic, it is chosen from terephthalic acid (denoted T), isophthalic (denoted I) and naphthalenic diacids (denoted N).
- Caprolactam or aminohexanoic acid are excluded from the definition of lactam and amino acid of Z which means that compounds of formula 6 / A / XiY in which A and XiY are as defined above are excluded.
- Ce diamine is a CIO diamine
- terepthalic acid is excluded from the definition of Cd diacid means that the compounds of formula lOT / A / XiY in which A and XiY are as defined above are excluded .
- said copolyamide consists only of three units of formula A / XiY / Z.
- a said copolyamide consists of only three units of formula A / XiY / Z and a single unit A, a single unit XiY and a single unit Z are present in the formula A / XiY / Z.
- the present invention relates to the use of a copolyamide as defined above for preparing a composition as defined above, said composition comprising up to 70% by weight of reinforcing fibers, in particular from 30 to 70% by weight of reinforcing fibers.
- the composition comprises between 35 and 65%, and preferably between 50 and 65% by weight of reinforcing fibers, relative to the total weight of the composition.
- composition according to the invention may comprise short reinforcing fibers or short fibrous reinforcement.
- the fibers are short and of length between 2 and 13 mm, preferably from 3 to 8 mm, before use of the compositions.
- These short reinforcing fibers can be chosen from:
- carbon fibers which includes fibers of carbon nanotubes or nanotubes (CNTs), carbon nanofibers or graphenes; silica fibers such as glass fibers, in particular of type E, R, S2 or T; fibers boron; ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers or basalt-based fibers; fibers or filaments based on metals and / or their alloys; fibers of metal oxides, in particular of alumina (Al203); metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures of the aforementioned fibers.
- CNTs carbon nanotubes or nanotubes
- silica fibers such as glass fibers, in particular of type E, R, S2 or T
- fibers boron ceramic fibers, in particular silicon carbide fibers, boron carbide fibers
- these fibers can be chosen as follows:
- the mineral fibers can be chosen from: carbon fibers, fibers of carbon nanotubes, glass fibers, in particular of type E, R, S2 or T, boron fibers, ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers or the basalt based fibers; fibers or filaments based on metals and / or their alloys, fibers based on metal oxides such as AI203, metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures of the aforementioned fibers, and
- polymer or polymer fibers under the aforementioned condition, are chosen from:
- thermosetting polymers and more particularly chosen from: unsaturated polyesters, epoxy resins, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates and polyimides, such as bis-maleimide resins, aminoplasts resulting from the reaction of an amine such as melamine with an aldehyde such as glyoxal or formaldehyde,
- thermoplastic polymers and more particularly chosen from: polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
- - aramid fibers such as Kevlar ®
- aromatic polyamides such as those corresponding to one of the formulas: PPD.T, MPD.I, PAA and PPA, with PPD and MPD being respectively p- and m- phenylene diamine, PAA being polyarylamides and PPA being polyphthalamides,
- PAEK polyarylether ketones
- PEEK polyetherether ketone
- PEKK polyetherketone ketone
- PEKEKK polyetherketoneetherketone ketone
- the preferred short reinforcing fibers are short fibers chosen from: carbon fibers, including metallized, glass fibers, including metallized type E, R, S2, or T, aramid fibers (such as Kevlar ® ) or aromatic polyamides, polyarylether ketone (PAEK) fibers, such as polyetherether ketone (PEEK), polyetherketone ketone (PEKK) fibers, polyetherketoneetherketone ketone (PEKEKK) fibers or mixtures thereof.
- carbon fibers including metallized, glass fibers, including metallized type E, R, S2, or T
- aramid fibers such as Kevlar ®
- PAEK polyarylether ketone
- PEEK polyetherether ketone
- PEKK polyetherketone ketone
- PEKEKK polyetherketoneetherketone ketone
- the natural fibers are chosen from fibers of flax, castor, wood, sisal, kenaf, coconut, hemp and jute.
- the weight ratio of reinforcing fibers / copolyamide does not exceed 1.75, in particular 1.6.
- glass fiber within the meaning of the invention is meant any glass fiber, in particular as described by Frederick T. Wallenberger, James C. Watson and Hong Li, PPG industries Inc. (ASM Handbook, Vol 21: composites (# 06781G), 2001 ASM International).
- the reinforcing fiber can be:
- L and D can be measured by scanning electron microscopy (SEM).
- the reinforcing fibers are chosen from glass fibers, carbon fibers, and a mixture thereof.
- the reinforcing fiber is chosen from a glass fiber with a non-circular cross section, a glass fiber with a circular section, a carbon fiber and a mixture of these.
- the reinforcing fiber is chosen from a glass fiber with a non-circular cross section, a glass fiber with a circular section and a mixture of these.
- the reinforcing fiber is a glass fiber with a non-circular cross section and having an elastic modulus of less than 76 GPa as measured according to ASTM C1557-03.
- said composition is devoid of at least one of the constituents chosen from polyphenylene ether (PPE), an anti-drip agent, a PA46, a PA66, a PA6, a polyamide based on a unit obtained by polycondensation of caprolactam , a free radical inhibitor, in particular inorganic, a flame retardant, nigrosine, elemental iron, a polyhydric alcohol, a metal oxide chosen from magnesium oxide, zinc oxide, calcium oxide or a mixture thereof, an amino acid heat stabilizer, an amino acid heat stabilizer with at least one hydroxy group and an amorphous polyamide.
- PPE polyphenylene ether
- composition comprises a titanium oxide then it is devoid of a metal oxide selected from magnesium oxide, zinc oxide, calcium oxide or a mixture thereof.
- said composition further comprises copolyamide and reinforcing fibers:
- said composition is devoid of at least one of the constituents excluded above defined.
- the present invention therefore relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to prepare a composition comprising:
- copolyamide the sum of copolyamide, reinforcing fibers, impact modifier, filler, fluidifying agent and additives being equal to 100%
- the present invention therefore relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to prepare a composition comprising:
- the present invention relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to prepare a composition comprising:
- copolyamide, reinforcing fibers, impact modifier, filler, fluidifying agent and additives being equal to 100%, and the modulus of which does not vary by more than 20% in the temperature range going from 20 ° C to 40 ° C , in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C as defined above.
- the present invention relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to prepare a composition comprising:
- copolyamide, reinforcing fibers, impact modifier, filler, fluidifying agent and additives being equal to 100%, and the modulus of which does not vary by more than 20% in the temperature range going from 20 ° C to 40 ° C , in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C as defined above.
- said composition consists of copolyamide, reinforcing fibers, and:
- composition therefore does not comprise said constituents defined above and excluded.
- the present invention relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to prepare a composition consisting of:
- copolyamide, reinforcing fibers, impact modifier, filler, fluidifying agent and additives being equal to 100%, and the modulus of which does not vary by more than 20% in the temperature range going from 20 ° C to 40 ° C , in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C as defined above.
- the present invention therefore relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to prepare a composition consisting of:
- copolyamide, reinforcing fibers, impact modifier, filler, fluidifying agent and additives being equal to 100%, and the modulus of which does not vary by more than 20% in the temperature range going from 20 ° C to 40 ° C , in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C as defined above.
- the present invention relates to the use of a copolyamide comprising at least two distinct units A and XiY of formula A / XiY as defined above, to prepare a composition consisting of: - 35 to 65%, in particular 35 to 50, and more particularly 38 to 50% by weight of at least one copolyamide as defined above,
- copolyamide, reinforcing fibers, impact modifier, filler, fluidifying agent and additives being equal to 100%, and the modulus of which does not vary by more than 20% in the temperature range going from 20 ° C to 40 ° C , in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C as defined above.
- impact modifier is meant a polyolefin-based polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178: 2010 standard (23 ° C RH50) and of Tg less than 0 ° C (measured according to standard 11357-2: 2013 at the inflection point of the DSC thermogram), in particular a polyolefin.
- the impact modifier can also be a block polymer of PEBA (polyether-block-amide) type having a flexural modulus of ⁇ 200 MPa.
- PEBA polyether-block-amide
- the composition can also comprise one or more impact modifiers as defined above.
- the presence of an impact modifier makes it possible to impart greater ductility to the articles made.
- the polyolefin of the impact modifier can be functionalized or non-functionalized or comprise both as a mixture.
- the polyolefins bear a function chosen from carboxylic acid, carboxylic anhydride and epoxide functions.
- the function can in particular be chosen from a copolymer of ethylene and propylene with an elastomeric character (EPR), an ethylene-propylene-diene copolymer with an elastomeric character (EPDM) and an ethylene / (meth) acrylate copolymer, a ethylene-higher alkene copolymer, in particular ethylene-octene copolymer, ethylene-alkyl acrylate-maleic anhydride terpolymer.
- EPR elastomeric character
- EPDM ethylene-propylene-diene copolymer with an elastomeric character
- EPDM ethylene / (meth) acrylate copolymer
- ethylene-higher alkene copolymer in particular ethylene-octene copolymer, ethylene-alkyl acrylate-male
- Peba polyether block amides
- Polyether block amides are copolymers comprising blocks with a polyamide pattern and blocks with a polyether pattern. They can also contain ester functions, in particular resulting from the condensation reaction of terminal carboxylic functions of the polyamide blocks with the hydroxyl functions of the polyether blocks.
- Peba are commercially available, in particular under the Pebax ® brand by the company Arkema.
- the impact modifier is selected from Fusabond ® F493, the Tafmer MFI5020, a Pebax ®, particularly Pebax ® 40R53 SP01, a Lotader ®, the Exxelor ® VA1803 or VA1801, the Orevac ® IM800 or a mixture thereof -Here, in this case they are in a ratio ranging from 0.1 / 99.9 to 99.9 / 0.1.
- the impact modifier can also be a modifier of “core-shell” type, also designated “copolymer of core-shell type”.
- the “core-shell” type modifier is in the form of fine particles having an elastomeric core and at least one thermoplastic shell, the size of the particles is generally less than 1 ⁇ m and advantageously comprised from 150 to 500 nm.
- the “core-shell” core-shell modifier has an acrylic or butadiene base.
- the content of impact modifier relative to the total weight of the composition can vary from 0 to 10% by weight, advantageously from 1 to 10% by weight.
- the composition comprises from 1 to 8%, and in particular from 2 to 5% by weight of impact modifier relative to the total weight of the composition.
- the impact modifier content in the composition can vary from 1 to 2% by weight; or from 2 to 3% by weight; or from 3 to 4% by weight; or from 4 to 5% by weight; or from 6 to 7% by weight; or from 7 to 8% by weight; or from 8 to 9% by weight; or from 9 to 10% by weight.
- the composition can also include fillers.
- the fillers envisaged include conventional mineral fillers, such as kaolin, magnesia, slag, carbon black, expanded or non-expanded graphite, wollastonite, nucleating agents such as silica, alumina, clay or talc, in particular talc, pigments such as titanium oxide and zinc sulphide, antistatic fillers.
- the composition can moreover comprise thinning agents.
- fluidifying agent in particular prepolymers.
- the prepolymer can be chosen from oligomers of aliphatic, linear or branched, cycloaliphatic, semi-aromatic or even aromatic polyamides.
- the prepolymer can also be a copolyamide oligomer or a mixture of polyamide and copolyamide oligomers.
- the prepolymer has a number-average molar mass Mn ranging from 1000 to 10000 g / mol, in particular from 1000 to 5000 g / mol. It can in particular be monofunctional NFh if the chain limiter used is a monoamine for example.
- Mn 100O / fNFh]
- [NH2] being the concentration of amine functions in the copolyamide as determined for example by potentiometry.
- the content of thinning agent relative to the total weight of the composition can vary from 0 to 5% by weight, in particular from 1 to 5% by weight.
- the composition comprises from 1 to 4%, and in particular from 2 to 3% by weight of thinning agent relative to the total weight of the composition.
- the content of thinning agent relative to the total weight of the composition is from 1 to 2% by weight; or from 2 to 3% by weight; or from 3 to 4% by weight; or from 4 to 5% by weight.
- additive is meant dyes, stabilizers, surfactants, brighteners, antioxidants, lubricants, plasticizers, waxes as well as their mixtures.
- dyes such as dyes, stabilizers, surfactants, brighteners, antioxidants, lubricants, waxes as well as their mixtures.
- the stabilizers can be organic or inorganic stabilizers.
- the usual stabilizers used with polymers are, for example, phenols, phosphites, UV absorbers, stabilizers of the HALS (Hindered Amine Light Stabilizer) type, metal iodides. These include Irganox ® 1010, 245, 1098 of BASF, Irgafos ® 168, 126 from BASF, Tinuvin ® 312, 770 from BASF, the Iodide P201 from Ciba, the Nylostab ® S-EED from the company Clariant.
- HALS Hindered Amine Light Stabilizer
- the lubricants can in particular be a stearate or a wax binder.
- the waxes can in particular be an amorphous wax such as beeswax, a silicone wax, a polyethylene wax, an oxidized polyethylene wax, an ethylene copolymer wax, a montane wax and a wax of. polyether.
- amorphous wax such as beeswax, a silicone wax, a polyethylene wax, an oxidized polyethylene wax, an ethylene copolymer wax, a montane wax and a wax of. polyether.
- additives of the same category or of different categories may be present in the composition.
- the additive content is from 0 to less than 2% by weight relative to the total weight of the composition.
- the composition comprises from 0.1 to less than 2%, in particular from 0.5 to less than 2% by weight of additive relative to the total weight of the composition.
- the content of additive in the composition can vary from 0 to 0.5% by weight; or from 0.1 to 0.5% by weight, or from 0.5 to 1% by weight; or from 1 to 1.5% by weight; or from 1.5 to less than 2% by weight.
- the invention relates to a composition, in particular useful for injection molding, comprising:
- the reinforcing fibers / copolyamide mass ratio does not exceed 1.75, in particular 1.6, when the reinforcing fibers have a non-circular section and have a cross-sectional area of from 1.5 to 5 , 0 c 10-6 cm2;
- said composition useful in particular for injection molding comprises:
- said composition useful in particular for injection molding comprises:
- the reinforcing fibers, impact modifiers, thinning agents, fillers and additives are as defined above and all the concentration ranges relating to impact modifiers, fillers, thinning agents and additives defined above are also valid for said composition as that such.
- composition in particular useful for injection molding, consists of:
- the reinforcing fibers / copolyamide mass ratio does not exceed 1.75, in particular 1.6, when the reinforcing fibers have a non-circular section and have a cross-sectional area of from 1.5 to 5 , 0 c 10-6 cm2;
- said composition in particular useful for injection molding, consists of:
- said composition useful in particular for injection molding consists of:
- said copolyamide of said composition is chosen from PA11 / 4T, PA11 / 6T, PA12 / 4T, PA12 / 6T, PA1010 / 4T, PA1012 / 4T, PA1010 / 6T, PA1012 / 6T, in particular PA11 / 6T.
- the reinforcing fibers of said composition are chosen from glass fibers, carbon fibers, and a mixture thereof, in particular glass fibers.
- the glass fibers of said composition are chosen from glass fibers with a non-circular cross section and glass fibers with a circular cross section, carbon fibers, and a mixture of these, in particular glass fibers with non-circular cross section and circular section glass fibers and a mixture thereof, including non-circular cross section glass fibers.
- the glass fibers are as defined above.
- the invention relates to a process for manufacturing the composition as defined above, in which the constituents of said composition are mixed by compounding, in particular in a twin-screw extruder, preferably co-rotating, a co-mixer, or an internal mixer.
- the invention relates to a molded article capable of being obtained from the composition defined above, by injection molding.
- said molded article is for electrical and electronics, and in particular chosen from the group consisting of televisions, digital cameras, digital games, telephone parts, digital tablets, drones, printers or computer parts.
- Example 1 Synthesis of the copolyamides of the invention.
- the monomers aminoundecanoic acid, hexanediamine and terepthalic acid are loaded together into the reactor according to the desired mass ratio.
- the medium is first inerted in order to remove the oxygen which can generate yellowing or side reactions. Water can also be charged to improve heat exchange. Two stages of temperature and pressure rise are carried out. The temperature (T °) and pressure conditions are chosen in order to allow the medium to be in the molten state. After reaching the maintenance conditions, degassing takes place to allow the polycondensation reaction. The medium gradually becomes viscous and the water of reaction formed is entrained by flushing with nitrogen or placed under vacuum. When the stop conditions are reached, in relation to the desired viscosity, the agitation is stopped and the extrusion and the granulation can start. The granules obtained will then be compounded with the glass fibers.
- compositions were prepared by melt blending the polymer granules. This mixture was carried out by compounding on an MC26 type co-rotating twin-screw extruder with a temperature profile (T °) flat at 290 ° C. The screw speed is 250rpm and the flow rate is 20 kg / h.
- the introduction of the glass fibers is carried out by lateral force-feeding.
- the additives and charges are added during the compounding process in the main hopper.
- Irganox ® 245 and irgafos ® 168 are anti-oxidants
- Fiber with a circular section CSX 451J and with a non-circular section CSG 3PA820 are marketed by the company Nittobo
- Plates of 100 * 100 * 1 mm3 were prepared by injection of the different compositions: - Injection temperature: 300 ° C
- the cycle time is adjusted as a function of the compositions to allow injection of the compositions and is less than 50 seconds.
- the flexural modulus of test pieces of the compositions obtained was measured on an Instron 5966 machine manufactured by the Instron company.
- the compositions are dried compositions and compositions saturated in water at 65 ° C beforehand.
- the tests were carried out at different temperatures, from -10 ° C to 60 ° C.
- the tensile modulus of test pieces of the compositions obtained was measured on an Instron 5966 machine manufactured by the company Instron dried compositions and compositions saturated in water at 65 ° C beforehand.
- the tests were carried out at different temperatures, from -10 ° C to 60 ° C.
- test pieces were cut to dimensions according to the ISO 527 standard, but with a thickness of 1 mm.
- Tables 2 to 4 and Example 3 show that the compositions of the invention exhibit a higher modulus stability than that of the comparative CEI and CE2 compositions, in flexion or in tension.
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- Polymers & Plastics (AREA)
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1902918A FR3094011B1 (fr) | 2019-03-21 | 2019-03-21 | Compositions de copolyamides comprenant des fibres de renforts presentant une stabilite de module elevee et leurs utilisations |
PCT/FR2020/050539 WO2020188204A1 (fr) | 2019-03-21 | 2020-03-13 | Compositions de copolyamides comprenant des fibres de renforts presentant une stabilite de module elevee et leurs utilisations |
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EP3941969A1 true EP3941969A1 (fr) | 2022-01-26 |
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EP20726195.9A Pending EP3941969A1 (fr) | 2019-03-21 | 2020-03-13 | Compositions de copolyamides comprenant des fibres de renforts presentant une stabilite de module elevee et leurs utilisations |
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EP (1) | EP3941969A1 (fr) |
CN (1) | CN113811575A (fr) |
FR (1) | FR3094011B1 (fr) |
WO (1) | WO2020188204A1 (fr) |
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GB9018144D0 (en) | 1990-08-17 | 1990-10-03 | Unilever Plc | Polymerisation process |
DE19725617A1 (de) * | 1997-06-17 | 1998-12-24 | Inventa Ag | Schlagzähe transparente Polyamidlegierungen |
US7388048B2 (en) * | 2003-08-05 | 2008-06-17 | Arkema France | Flexible semiaromatic polyamides with a low moisture uptake |
CN101356236B (zh) * | 2006-01-13 | 2012-02-29 | 三菱工程塑料株式会社 | 便携电子机器用聚酰胺树脂组合物和便携电子机器用成型品 |
FR2921069B1 (fr) * | 2007-09-18 | 2010-07-30 | Rhodia Operations | Composition polyamide |
FR2934865B1 (fr) | 2008-08-08 | 2010-08-27 | Arkema France | Copolyamide semi-aromatique et son procede de preparation |
FR2934864B1 (fr) | 2008-08-08 | 2012-05-25 | Arkema France | Polyamide semi-aromatique a terminaison de chaine |
FR2976946B1 (fr) * | 2011-06-24 | 2014-01-24 | Arkema France | Composition comprenant un polyamide semi-aromatique et ses utilisations, notamment pour un reflecteur a diode electroluminescente |
FR2981357B1 (fr) * | 2011-10-13 | 2013-10-25 | Arkema France | Composition souple a base de polyamide semi-aromatique, son procede de preparation et ses utilisations |
CN105308110A (zh) | 2013-06-05 | 2016-02-03 | 索尔维特殊聚合物美国有限责任公司 | 用于移动电子装置的填充聚合物组合物 |
FR3057572A1 (fr) | 2016-10-19 | 2018-04-20 | Arkema France | Utilisation d'un polyamide semi-aromatique dans un melange de polyamide aliphatique comprenant des fibres de verre a section circulaire pour limiter le gauchissement |
FR3057573A1 (fr) | 2016-10-19 | 2018-04-20 | Arkema France | Utilisation de fibres de verre a section circulaire dans un melange comprenant un polyamide semi-aromatique et un polyamide aliphatique pour ameliorer les proprietes mecaniques dudit melange |
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2019
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2020
- 2020-03-13 CN CN202080032810.9A patent/CN113811575A/zh active Pending
- 2020-03-13 EP EP20726195.9A patent/EP3941969A1/fr active Pending
- 2020-03-13 WO PCT/FR2020/050539 patent/WO2020188204A1/fr active Application Filing
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FR3094011A1 (fr) | 2020-09-25 |
FR3094011B1 (fr) | 2021-10-01 |
CN113811575A (zh) | 2021-12-17 |
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