EP4225830A1 - Ertragsoptimiertes verfahren zur herstellung einer polyamidpulverzusammensetzung - Google Patents
Ertragsoptimiertes verfahren zur herstellung einer polyamidpulverzusammensetzungInfo
- Publication number
- EP4225830A1 EP4225830A1 EP21807167.8A EP21807167A EP4225830A1 EP 4225830 A1 EP4225830 A1 EP 4225830A1 EP 21807167 A EP21807167 A EP 21807167A EP 4225830 A1 EP4225830 A1 EP 4225830A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- polyamide
- additives
- powder
- acid
- 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 192
- 229920002647 polyamide Polymers 0.000 title claims abstract description 98
- 239000000843 powder Substances 0.000 title claims abstract description 92
- 239000004952 Polyamide Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 16
- -1 PA 1012 Polymers 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229920000571 Nylon 11 Polymers 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 10
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- 150000003951 lactams Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 6
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 claims description 5
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical class OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 5
- 229920000299 Nylon 12 Polymers 0.000 claims description 4
- 229960002684 aminocaproic acid Drugs 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 4
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-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
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 claims description 3
- SWTNRXKFJNGFRF-UHFFFAOYSA-N 14-aminotetradecanoic acid Chemical compound NCCCCCCCCCCCCCC(O)=O SWTNRXKFJNGFRF-UHFFFAOYSA-N 0.000 claims description 3
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 claims description 3
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 claims description 3
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- 229920006152 PA1010 Polymers 0.000 claims description 3
- 229920006144 PA618 Polymers 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007580 dry-mixing Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001962 electrophoresis Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000011185 multilayer composite material Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000003618 dip coating Methods 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 description 14
- 238000005243 fluidization Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- YHNQOXAUNKFXNZ-UHFFFAOYSA-N 13-amino-tridecanoic acid Chemical compound NCCCCCCCCCCCCC(O)=O YHNQOXAUNKFXNZ-UHFFFAOYSA-N 0.000 description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-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
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 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
- 239000011572 manganese Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- SPJXZYLLLWOSLQ-UHFFFAOYSA-N 1-[(1-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CCCCC1(N)CC1(N)CCCCC1 SPJXZYLLLWOSLQ-UHFFFAOYSA-N 0.000 description 1
- 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 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
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- YUXBNNVWBUTOQZ-UHFFFAOYSA-N 4-phenyltriazine Chemical class C1=CC=CC=C1C1=CC=NN=N1 YUXBNNVWBUTOQZ-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001536 azelaic acids Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical class OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 230000010006 flight Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XTBMQKZEIICCCS-UHFFFAOYSA-N hexane-1,5-diamine Chemical compound CC(N)CCCCN XTBMQKZEIICCCS-UHFFFAOYSA-N 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000011160 magnesium carbonates Nutrition 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical class [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G69/04—Preparatory processes
- C08G69/06—Solid state polycondensation
-
- 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
- C08G69/46—Post-polymerisation treatment
-
- 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
- C08G69/04—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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to a method for preparing a powder composition based on polyamide(s) with optimized yield.
- the invention also relates to the powder composition obtained and its use, in particular for the coating of metal substrates by dipping in a fluidized bed.
- a polyamide powder composition can be obtained via a cryogenic grinding process from a polymer in the form of granules, but the process is expensive and has a low yield.
- a polyamide powder composition can be obtained via a manufacturing process in which low-viscosity prepolymers are ground beforehand, followed by a solid-phase polycondensation step so that the polyamide powder reaches the viscosity desired.
- This type of process makes it possible to obtain a raw powder from prepolymers, which are easier to grind, compared to raw powder whose viscosity is generally higher.
- the raw powder as obtained has a relatively wide particle size distribution, and in particular has a large portion of fine particles.
- Fine particles are defined as particles with diameters generally 3 times less than the median diameter by volume (Dv50).
- Dv50 median diameter by volume
- the fine particles are those whose diameter is less than 40 ⁇ m.
- the flight of fine particles during the fluidization of the powder can represent approximately 8% in losses, and/or cause a change in the particle size distribution of the powder by the depletion of fine particles, degrading its applicability, namely making it difficult to control the thickness of the coating and making the quality of fluidization difficult to maintain constant.
- a screening step is often required to remove these fine particles from the powder composition before it is used in a dipping process. This step makes it possible to provide a powder with a narrow particle size by eliminating fine particles but generates a significant quantity of waste, namely unusable fine particles.
- a powder composition with bulk additives means a polymer-based powder composition comprising additives (such as pigments, antioxidants) obtained by a process of mixing in the melting (also called “compounding”), by which the additives are included in the powder particles.
- the object of the invention is to propose a process making it possible to reuse the undesirable fine particles, and thus to improve the yield of the preparation process.
- the invention also seeks to provide a powder composition of controlled and preferably tight particle size, which can be used in a fluidized bed dipping process.
- the invention relates firstly to a method for preparing a powder composition based on polyamide(s) (PA composition) having an inherent viscosity greater than or equal to 0.65 (g/100 g) -1 and less than or equal to 1.40 (g/100 g) -1 , comprising:
- composition (i) based on a polyamide prepolymer having a maximum inherent viscosity of 0.60 (g/100 g)' 1 , where appropriate, with mass additives;
- composition (ii) grinding composition (i) to obtain powder composition (ii);
- composition PA1 having an inherent viscosity greater than or equal to 0.65 (g/100 g) ⁇ 1 and less than or equal to 1.40 (g/100 g) ⁇ 1 , preferably composition PA1 being composition PA.
- the Dv50 of the pre-PAO composition is not satisfactory and the Dv50 of the pre-PA composition is that sought according to a desired final application.
- Composition (i) is in the form of a divided solid, preferably a coarse powder of sizes less than 1 mm.
- composition based on a polyamide prepolymer or a composition based on a polyamide means a composition comprising at least 50% by weight of polyamide or polyamide prepolymer, relative to the total weight of the composition.
- the pre-PAO composition has a Dv50 3 times lower than the Dv50 of the powder composition (ii).
- the pre-PAO composition has a Dv50 of less than 50 ⁇ m.
- the present invention makes it possible to reduce losses by recycling particles of unsatisfactory particle size, within the same manufacturing process when the recycling step occurs in the process for preparing the PA composition or else in a subsequent process of preparation of another composition based on polyamides.
- the process of the invention is particularly interesting for so-called fine or extra-fine prepolymer particles, typically those having a diameter of less than 50 ⁇ m, it goes without saying that all the prepolymers, whatever their particle size, preferably having a inherent viscosity less than 0.60 (g/100 g)' 1 , can be used in the recycling stage.
- the polyamide in the PA composition has a melting point of less than or equal to 300°C.
- the composition has a melting point less than or equal to 250°C, more preferably less than or equal to 200°C, for example less than or equal to 190°C.
- the polyamide in the PA composition according to the invention has an inherent viscosity greater than or equal to 0.65 (g/100 g) ⁇ 1 and less than or equal to 1.40 (g/100 g) ⁇ 1 .
- its inherent viscosity is greater than or equal to 0.70 g/100 g) -1 , in particular 0.75 g/100 g) -1 , in particular 0.80 (g/100 g) -1 and less than or equal to 1.10 (g/100 g) -1 , more preferably 1.05 (g/100 g) -1 , in particular 1.0 (g/100 g) -1 .
- the process of the present invention allows the fine particles to be removed and recycled during manufacture in order to reduce the amount of waste throughout the preparation and application process.
- the step of recycling the pre-PAO composition comprises:
- pre-PA1 composition “pre-PA1 composition”.
- water is added in an amount of 10 to 40%, preferably 20 to 30% by weight relative to the total weight of the mixture.
- the pre-PAO composition can comprise a polyamide prepolymer or a mixture of several polyamide prepolymers.
- the pre-PAO composition comprises a polyamide prepolymer.
- the pre-PAO composition consists of a polyamide prepolymer.
- the pre-PAO composition comprises at least 50% of polyamide(s) prepolymers and one or more additives.
- the inherent viscosity of the prepolymer of the polyamide(s) in the pre-PAO composition is less than 0.60 (g/100 g) -1 , typically comprised in the range going from 0.25 to 0.55, preferably between 0 30 and 0.50 (g/100 g) -1 , even more preferably between 0.40 and 0.50 (g/100 g) -1 .
- the inherent viscosity of the prepolymer of the polyamide(s) in the pre-PA1 composition is less than 0.60 (g/100 g) -1 , typically comprised in the range going from 0.25 to 0.55, preferably between 0 30 and 0.50 (g/100 g) -1 , even more preferably between 0.40 and 0.50 (g/100 g) -1 .
- the pre-PAO composition is a composition based on a prepolymer of PA 11, PA 12, PA 1010, PA 1012, PA 6, PA 610, PA 612, PA 614, PA 618, PA 8, PA 9, PA 10, PA 13, PA 14 and mixtures thereof, preferably a composition consisting of PA 11 polyamide prepolymers.
- the catalyst is chosen from phosphoric acid and/or hypophosphorous acid.
- the catalyst is typically in the form of an aqueous solution.
- one or more monomers are chosen from amino acids, lactams, preferably chosen from aminocaproic acid, amino-7-heptanoic acid, amino-8-octanoic acid, amino-9-nonanoic acid, amino-10-decanoic acid, amino-11-undecanoic acid, amino-12-dodecanoic acid, amino-13-tridecanoic acid, amino- 14-tetradecanoic acid and/or mixtures thereof, preferably amino-11-undecanoic acid.
- one or more monomers is a mixture of diamine monomers and diacid monomers, preferably, a mixture of diamine monomers such as hexamethylenediamine, decanediamine, dodecamethylenediamine, metaxylylenediamine, bis-p aminocyclohexylmethane and trimethylhexamethylene diamine with diacid monomers such as isophthalic, terephthalic, adipic, azelaic, suberic, sebacic, dodecanedioic acids, tetradecanedioic acid, and/or mixtures thereof.
- diamine monomers such as hexamethylenediamine, decanediamine, dodecamethylenediamine, metaxylylenediamine, bis-p aminocyclohexylmethane and trimethylhexamethylene diamine
- diacid monomers such as isophthalic, terephthalic, adipic, azelaic, suberic, sebacic,
- a monomer corresponding to the monomer unit of the polyamide (PA) having an inherent viscosity of less than 0.60 is introduced.
- PA polyamide
- a monomer different from the monomer unit of the polyamide For example, one can provide a mixture of amino-12-dodecanoic as monomers and a PAO-composition based on polyamide 11 prepolymer to obtain a pre-PA1 composition based on copolyamide 11/12.
- the solid phase polycondensation step is carried out at a temperature above the glass transition temperature and below the melting temperature of the polyamide.
- the reaction is carried out under an inert atmosphere, for example under nitrogen or under vacuum.
- the reaction time required to reach the expected inherent viscosity depends on the temperature chosen; it can be established by simple routine tests.
- this step can be carried out in a dryer.
- a particular process is thus proposed, which comprises a step where the prepolymers, in particular those having a fine particle size, are mixed with the monomers as reactants participating in the polycondensation reaction.
- step (iv) may comprise all or at least one of the following steps, successively:
- the cooled pre-PA1 composition is passed through a granulator or a grinder, which reduces it to a coarse powder, typically with an average diameter of less than 5 mm, before the following stages.
- (iv-4) optionally a step of mixing in the molten state so as to add additives, such as pigments, antioxidants, to the pre-PA1 composition, whereby the mass-additive pre-PA1 composition is obtained .
- the melt-mixing step consists of melt-mixing the molten polycondensation product with additives, for example, by means of two screws in a heated barrel. The mixture is then extruded through a die to a cooled rolling mill in which the mixture solidifies or using a calender.
- the temperature applied during the mixing step should slightly exceed the melting temperature of the prepolymer. Typically, the temperature applied is at most 5° C. higher than the melting temperature of the prepolymers.
- the residence time is less than 1 minute.
- a pre-PAO composition preferably those having a fine particle size, typically less than 40 ⁇ m.
- the mass-additive pre-PA1 composition is passed through a granulator or a grinder, which reduces it to a coarse powder, typically with an average diameter of less than 5 mm, before the following steps.
- the grinding is preferably a mechanical grinding, carried out at room temperature.
- the grinding can be carried out in an impact mill, for example a hammer mill, a knife mill, a disk mill, or an air jet mill, preferably equipped with an internal selector.
- the particle size of the pre-PA1 composition is adjusted directly by adjusting the grinding speed, preferably, the adjustment is also carried out by means of a selector integrated into the grinder.
- the optional selection step makes it possible to separate the ground pre-PA1 composition into at least 2 compositions, one of which has a desired Dv 50.
- the composition whose Dv50 is unsatisfactory can be recycled again in the process of the invention.
- the process of the invention makes it possible to recycle unusable materials several times if necessary, making it possible to minimize losses during manufacture.
- the process of the invention may comprise:
- (v) a step of increasing the viscosity of the pre-PA1 composition obtained after one or more steps described above, optionally mixed with the pre-PA composition, until the desired final viscosity of the composition of the powder based on polyamide(s), preferably produced by polycondensation in the solid phase in a dryer.
- step (vi) optionally a step of dry mixing the composition of the powder based on polyamide(s) with additives, such as pigments, antioxidants, the additives preferably having a particle size similar to that of the composition of the powder based on polyamide(s).
- additives such as pigments, antioxidants, the additives preferably having a particle size similar to that of the composition of the powder based on polyamide(s).
- the step of recycling (iv) of the pre-PAO composition comprises a step of mixing in the molten state (also called “compounding") of the pre-PAO composition, if necessary , with bulk additives, as defined above, optionally mixed with a composition of polyamide prepolymers and/or additives, under conditions such that the polycondensation in the melt phase during this step is limited, whereby one obtains a composition based on prepolymer(s) (pre-PA1 composition) with bulk additives.
- the melt-mixing step consists of melt-mixing the pre-PAO composition, optionally with a polyamide prepolymer composition and/or additives, for example, by means of two screws within heated sleeves.
- the mixture is then extruded through a die to a cooled rolling mill in which the mixture solidifies or using a calender.
- the temperature applied during the mixing step should slightly exceed the melting temperature of the prepolymer. Typically, the temperature applied is at most 5°C higher than the melting temperature of the prepolymers.
- the residence time is less than 1 minute.
- the pre-PAT composition can be passed through a granulator or a grinder, which reduces it to a coarse powder, typically with an average diameter of less than 5 mm,
- the recycling step (iv) comprises a step of grinding and optionally of selecting the cooled pre-PAT composition.
- Grinding is a mechanical grinding, which can be cryogenic, or carried out at room temperature
- the grinding can be carried out in an impact mill, for example a hammer mill, a knife mill, a disk mill, or an air jet mill, preferably equipped with an internal selector.
- an impact mill for example a hammer mill, a knife mill, a disk mill, or an air jet mill, preferably equipped with an internal selector.
- the particle size of the pre-PAT composition is set directly by adjusting the grinding speed, preferably by means of a selector integrated into the mill.
- the optional step of selection makes it possible to separate the ground pre-PAT composition into at least 2 compositions, one of which has a desired Dv 50.
- the composition whose Dv50 is unsatisfactory can be recycled again in the process of the invention.
- the process of the invention makes it possible to recycle unusable materials several times if necessary, making it possible to minimize losses during manufacture.
- the method for preparing the polyamide-based powder composition may comprise all or at least one of steps (v) and (vi) as described below.
- the present invention thus makes it possible to reuse the prepolymers or a composition comprising the prepolymers having an unsatisfactory particle size as reagents in a manufacturing process, to greatly limit the losses of raw materials, which can range from production to end use, in particular for application in fluidized bed dip coating.
- the present invention also proposes a powder composition based on polyamide(s) (PA) with a controlled particle size, preferably tighter and more uniform, while reducing the losses of materials during its preparation process.
- PA polyamide(s)
- the invention relates to a powder composition based on polyamide(s) wholly or partly resulting from a process as described above in which the polyamide has an inherent viscosity of 0.65 to 1.40 ( g/100 g) -1 , preferably from 0.70 to 1.10 (g/100 g) -1 , even more preferably from 0.80 to 1.00 (g/100 g) -1 and preferably having a median diameter by volume Dv50 of between 80 and 130 ⁇ m, even more preferably between 90 and 120 ⁇ m, or even between 100 and 110 ⁇ m.
- the powder composition comprises additives, preferably is added in bulk.
- the invention also relates to the use of the composition as defined above in a coating process on a metal substrate by dipping in a fluidized bed.
- composition is particularly suitable for coatings prepared by a fluidized bed dipping process, the composition can also be used in other fields.
- the invention relates to the use of the composition as defined above in paints, anti-corrosion compositions, additives for paper, powder agglomeration technologies by melting or sintering caused by radiation to manufacture objects , electrophoresis gels, multilayer composite materials, packaging industry, toys, textiles, automotive and/or electronics.
- prepolymer means a prepolymer whose inherent viscosity is less than 0.60 (g/100 g)' 1 .
- inherent viscosity means the viscosity of a polymer in solution, determined using Ubbelohde tube measurements. The measurement is carried out on a 75 mg sample at a concentration of 0.5% (m/m) in m-cresol.
- the viscosity of a composition comprising, in addition to the polymer, any additives insoluble in m-cresol is determined by increasing the quantity of the sample so that the solution has a polymer concentration of 0.5% (m/m ).
- melting temperature means the temperature at which an at least partially crystalline polymer changes to the viscous liquid state, as measured by differential scanning calorimetry (DSC) according to standard NF EN ISO 11 357-3 in using a heating rate of 20°C/min.
- glass transition temperature is understood to denote the temperature at which an at least partially amorphous polymer changes from a rubbery state to a glassy state, or vice versa, as measured by differential scanning calorimetry (DSC) according to the standard NF EN ISO 11 357-2 using a heating rate of 20°C/min.
- the term "average diameter by volume” or “Dv” is also understood to mean the average diameter by volume of a pulverulent material, as measured according to standard ISO 9276 - parts 1 to 6: “Representation of data obtained by particle size analysis ".
- the Dv50 designates the median diameter by volume, that is to say that corresponding to the 50th percentile by volume
- the Dv10 and Dv90 respectively designate the average diameters by volume below which 10 or 90% are located. in particle volume.
- the volume average diameter can be measured in particular by means of a laser particle sizer, for example a laser particle sizer (Sympatec Helos). Software (Fraunhofer) then makes it possible to obtain the volumetric distribution of a powder and to deduce the Dv10, the Dv50 and the Dv90.
- the polyamide can be aliphatic, semi-aromatic and cycloaliphatic.
- the polyamide can be chosen from a homopolyamide, a copolyamide, and mixtures thereof.
- It can also be a mixture of polyamide and at least one other polymer, the polyamide forming the matrix and the other polymer(s) forming the dispersed phase.
- polyamide within the meaning of the invention means the condensation products:
- amino acid monomers such as aminocaproic acid, aminocaproic acid, amino-7-heptanoic acid, amino-8-octanoic acid, amino-9-nonanoic acid, amino -10-decanoic acid, amino-11-undecanoic acid, amino-12-dodecanoic acid, amino-13-tridecanoic acid, amino-14-tetradecanoic acid of one or more lactam monomers such as caprolactam , oenantholactam and lauryllactam;
- diamine monomers such as hexamethylenediamine, decanediamine, dodecamethylenediamine, metaxylylenediamine, bis-p aminocyclohexylmethane and trimethylhexamethylenediamine with diacids such as isophthalic, terephthalic, adipic, azelaic acids, suberic, sebacic, dodecanedioic and tetradecanedioic.
- diamine monomers such as hexamethylenediamine, decanediamine, dodecamethylenediamine, metaxylylenediamine, bis-p aminocyclohexylmethane and trimethylhexamethylenediamine with diacids such as isophthalic, terephthalic, adipic, azelaic acids, suberic, sebacic, dodecanedioic and tetradecanedioic.
- the polyamide can be a copolyamide. Mention may be made of the copolyamides resulting from the condensation of at least two different monomers, for example of at least two different alpha omega aminocarboxylic acids or of two different lactams or of a lactam and an alpha omega aminocarboxylic acid of a number of different carbon. Mention may also be made of the copolyamides resulting from the condensation of at least one alpha-omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
- copolyamides resulting from the condensation of an aliphatic diamine with an aliphatic dicarboxylic acid and at least one other monomer chosen from aliphatic diamines different from the previous one and aliphatic diacids different from the previous one.
- a repeating unit of the polyamide consists of the association of a diacid with a diamine is particular. It is considered that it is the association of a diamine and a diacid, that is to say the couple "diaminediacid”, also called “XY”, in equimolar quantity which corresponds to the monomer. This is explained by the fact that individually, the diacid or the diamine is only a structural unit, which is not enough on its own to form a polymer.
- diamine X By way of example of diamine X, mention may be made of aliphatic diamines having from 6 to 12 atoms, the diamine X possibly also being aryl and/or saturated cyclic. Examples include hexamethylenediamine, piperazine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5 diaminohexane, 2,2,4-trimethyl-1,6 -diamino-hexane, diamine polyols, isophorone diamine (IPD), methyl pentamethylenediamine (MPMD), bis(aminocyclohexyl) methane (BACM), bis(3-methyl-4 aminocyclohexyl) methane (BMACM), metaxylyenediamine, bis-p aminocyclohexylmethane and trimethylhexamethylene diamine.
- IPD isophorone diamine
- MPMD methyl pen
- diacid (or dicarboxylic acid) Y By way of example of diacid (or dicarboxylic acid) Y, mention may be made of acids having between 4 and 18 carbon atoms. Mention may be made, for example, of adipic acid, sebacic acid, azelaic acid, suberic acid, dodecanedioic acid, tetradecanedioic acid, isophthalic acid, butanedioic acid, 1 ,4 cyclohexyldicarboxylic acid, terephthalic acid, sodium or lithium salt of 5-sulfoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated).
- lactam or amino acid monomers are said to be of the “Z” type:
- lactams By way of example of lactams, mention may be made of those having from 3 to 12 carbon atoms on the main cycle and which may be substituted. Mention may be made, for example, of P,p-dimethylpropriolactam, ⁇ , ⁇ -dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam.
- alpha-omega amino acids such as aminocaproic, amino-7-heptanoic, amino-11-undecanoic, n-heptyl-11-aminoundecanoic and amino-12-dodecanoic acids.
- the polyamide (PA) according to the invention comprises at least one polyamide or one polyamide block chosen from polyamides and copolyamides comprising at least one of the following monomers: 46, 4T, 54, 59, 510, 512, 513, 514, 516, 518, 536, 6, 64, 66, 69, 610, 612, 613, 614, 616, 618, 636, 6T, 9, 10, 104, 109, 1010, 1012, 1013, 1014, and mixtures thereof.
- the polyamides (PA) comprise at least one polyamide chosen from polyamides and copolyamides comprising at least one of the following XY or Z monomers: 59, 510, 512, 514, 6, 69, 610, 612, 614, 109, 1010, 1012, 1014, 10T, 11, 12, 129, 1210, 1212, 1214, 12T, MXD6, MXD10, MXD12, MXD14, and mixtures thereof; in particular chosen from PA 11, PA 12, PA 1010, PA 1012, PA 6, PA 610, PA 612, PA 614, PA 618 and mixtures thereof.
- copolyamides examples include PA 6/12, PA 6/66, PA 6/12/66, PA 6/69/11/12, PA 6/66/11/12, PA 69/ 12, PA 11/10T.
- the pigment can in principle be freely chosen from the pigments used in the conventional manner. It can in particular be chosen from mineral pigments such as titanium dioxide, carbon black, cobalt oxide, nickel titanate, molybdenum disulphide, aluminum flakes, iron oxides, zinc, zinc phosphate, and organic pigments, such as phthalocyanine and anthraquinone derivatives.
- mineral pigments such as titanium dioxide, carbon black, cobalt oxide, nickel titanate, molybdenum disulphide, aluminum flakes, iron oxides, zinc, zinc phosphate, and organic pigments, such as phthalocyanine and anthraquinone derivatives.
- the dye can also be of any type known to those skilled in the art. Mention may be made in particular of azo dyes, anthraquinone dyes, dyes derived from indigo, triarylmethane dyes, chlorine dyes and polymethine dyes. Mention may also be made of one or more additives which are chosen from the group consisting of anti-crater agents or spreading agents, reducing agents, antioxidants, reinforcing fillers, UV stabilizers, fluidizing agents, corrosion, or mixtures thereof.
- the anti-crater and/or spreading agent can be of any type known to those skilled in the art.
- the anticrater and/or spreading agent is selected from the group consisting of polyacrylate derivatives.
- the UV stabilizer may be of any type known to those skilled in the art.
- the UV stabilizer is selected from the group consisting of resorcinol derivatives, benzotriazoles, phenyltriazines and salicylates.
- the antioxidants can be of any type known to those skilled in the art.
- the antioxidants are selected from the group consisting of copper iodide combined with potassium iodide, phenol derivatives and hindered amines.
- the fluidizing agent may be of any type known to those skilled in the art.
- the fluidizing agent is selected from the group consisting of aluminas and silicas.
- the corrosion inhibitors can be of any type known to those skilled in the art.
- the corrosion inhibitors are selected from the group consisting of phosphosilicates and borosilicates.
- the additives are preferably present in a quantity by mass, relative to the total mass of the composition, of 1 to 30%, more preferably of 2 to 10%, even more preferably of 3 to 5%, for example from 0 to 5 %, or from 5 to 10%, or from 10 to 15%, or from 15 to 20%, or from 20 to 25%, or from 25 to 30%.
- the reinforcing filler can be of any type suitable for the preparation of powders based on polyamides.
- the filler be selected from the group consisting of talc, calcium carbonates, manganese carbonates, potassium silicates, aluminum silicates, dolomite, magnesium carbonates, quartz, boron nitride, kaolin, wollastonite, titanium dioxide, glass beads, mica, carbon black, mixtures of quartz, mica and chlorite, feldspar and dispersed nanoscale fillers such as carbon nanotubes and silica.
- the filler is calcium carbonate.
- the fillers are preferably present in a quantity by mass, relative to the total mass of the composition, of 0 to 50%, more preferably of 0 to 10%, even more preferably of 0 to 5%, for example from 0 to 5 %, or from 5 to 10%, or from 10 to 15%, or from 15 to 20%, or from 20 to 25%, or from 25 to 30%.
- pre-PAO powder polyamide 11 prepolymer
- a monitoring of the amount of vapor removed is carried out until a certain amount of vapor removed, which corresponds to the desired viscosity for the prepolymer.
- the prepolymer of viscosity 0.40 is then drained. At the level of the drain valve, the prepolymer is still in fusion then it cools when there is contact between two cold metal rollers and becomes solidified.
- the solidified prepolymer is then passed through a granulator or a grinder, which reduces it to coarse powder with an average diameter of less than 5 mm. The experiment was repeated 3 times to obtain prepolymers with a viscosity of 0.39/0.42/0.40 (g/100 g)' 1 .
- Example 1.1 The coarse powder obtained in Example 1.1 is ground in a hammer mill equipped with an internal selector. The crushed raw powder thus obtained is separated in a separator cyclone to obtain 2 powders:
- the freeze-ground powder has a much greater proportion of fine particles with a size of less than 50 ⁇ m than the powder of the present invention—approximately 5% for the freeze-ground powder against less than 0.3% for the powder of the present invention.
- the freeze-ground powder also has a much higher proportion of large particles with a size greater than 300 ⁇ m - about 8% for the freeze-ground powder against about 1% for the powder of the present invention.
- the powder of the present invention has two main advantages for use in fluidized bed dipping:
- the low proportion of particles > 250 pm makes it possible to reduce the fluidization speed (see example 4), -
- the low proportion of fines ⁇ 50 ⁇ m, as well as a low fluidization speed makes it possible to limit the flights of fines.
- the powder of the present invention makes it possible to limit this loss to less than 0.1%.
- the [Fig. 2] presents the evolutions of particle size caused by fluidization:
- the evolution of the particle size of a freeze-ground powder is significant, whereas the powder of the present invention is stable. Therefore, the application quality of the present invention is stable.
- This stability in the application quality of the product makes it possible to reuse the powder of the present invention after numerous dipping applications, where the freeze-ground powder must be renewed with virgin powder.
- the present invention makes it possible to reduce the waste rate induced by this product renewal by around 5%.
- FIG. 3 presents the delta P profile as a function of air velocity for a powder bed.
- the "virgin" freeze-ground powder that is to say for a first fluidization, shows that the minimum fluidization speed is approximately 1.8 m/s, where the powder of the present invention requires 1.0 m/ s for its fluidization.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyamides (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR2010338A FR3115042B1 (fr) | 2020-10-09 | 2020-10-09 | Procédé de préparation d’une composition de poudre de polyamides avec rendement optimisé |
PCT/FR2021/051761 WO2022074351A1 (fr) | 2020-10-09 | 2021-10-11 | Procédé de préparation d'une composition de poudre de polyamides avec rendement optimisé |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4225830A1 true EP4225830A1 (de) | 2023-08-16 |
Family
ID=74553915
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21807167.8A Pending EP4225830A1 (de) | 2020-10-09 | 2021-10-11 | Ertragsoptimiertes verfahren zur herstellung einer polyamidpulverzusammensetzung |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230374217A1 (de) |
EP (1) | EP4225830A1 (de) |
JP (1) | JP2023545085A (de) |
KR (1) | KR20230084278A (de) |
CN (1) | CN116507666A (de) |
FR (1) | FR3115042B1 (de) |
WO (1) | WO2022074351A1 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114933850B (zh) * | 2022-06-28 | 2023-08-22 | 万华化学集团股份有限公司 | 一种聚酰胺预聚物水性浆料及其制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1495816A (fr) | 1966-10-04 | 1967-09-22 | Huels Chemische Werke Ag | Procédé pour la préparation de poudres de polyamide de viscosité élevée |
US3636136A (en) * | 1969-11-18 | 1972-01-18 | Du Pont | Method of powdering polyamides with hydrolyzed ethylene/vinyl acetate copolymers |
EP0683199B1 (de) * | 1994-04-22 | 2000-03-15 | Fina Research S.A. | Verfahren zur Wiederverwendung von Pulverbeschichtungsabfällen |
GB2341564A (en) * | 1998-09-16 | 2000-03-22 | Protol Powder Coatings Limited | Recycling powder coating fines |
DE10233344A1 (de) * | 2002-07-23 | 2004-02-12 | Degussa Ag | Polyamid-Wirbelsinterpulver für das Dünnschichtwirbelsintern |
FR2927626B1 (fr) | 2008-02-15 | 2011-02-25 | Arkema France | Poudre fine de polyamide issu de matieres renouvelables et procede de fabrication d'une telle poudre. |
-
2020
- 2020-10-09 FR FR2010338A patent/FR3115042B1/fr active Active
-
2021
- 2021-10-11 CN CN202180075556.5A patent/CN116507666A/zh active Pending
- 2021-10-11 EP EP21807167.8A patent/EP4225830A1/de active Pending
- 2021-10-11 WO PCT/FR2021/051761 patent/WO2022074351A1/fr active Application Filing
- 2021-10-11 JP JP2023521641A patent/JP2023545085A/ja active Pending
- 2021-10-11 US US18/248,259 patent/US20230374217A1/en active Pending
- 2021-10-11 KR KR1020237015671A patent/KR20230084278A/ko unknown
Also Published As
Publication number | Publication date |
---|---|
KR20230084278A (ko) | 2023-06-12 |
JP2023545085A (ja) | 2023-10-26 |
US20230374217A1 (en) | 2023-11-23 |
FR3115042B1 (fr) | 2023-01-06 |
WO2022074351A1 (fr) | 2022-04-14 |
FR3115042A1 (fr) | 2022-04-15 |
CN116507666A (zh) | 2023-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2488572B1 (de) | Verfahren zur herstellung eines recycelbaren polyamidpulvers | |
EP2274363B1 (de) | Verfahren zur erhöhung der differenz zwischen der schmelztemperatur und der kristallisationstemperatur eines polyamidpulvers | |
FR3071840B1 (fr) | Composition de poudre thermoplastique et objet tridimensionnel renforce fabrique par impression 3d d'une telle composition | |
EP2530121B2 (de) | Verfahren zum Erhöhen der Recyclingfähigkeit eines Polyamids, das zum Sintern benutzt wird | |
EP2201059B1 (de) | Polyamid mit hoher fluidität | |
EP2326680A2 (de) | Verstärkte polyamidzusammensetzung | |
EP4225830A1 (de) | Ertragsoptimiertes verfahren zur herstellung einer polyamidpulverzusammensetzung | |
EP2001935A1 (de) | Polyamid mit hoher fluidität | |
EP2451861B1 (de) | Polyamidzusammensetzung | |
EP4103637A1 (de) | Verfahren zur behandlung einer zusammensetzung auf polyamidbasis | |
WO2021160959A1 (fr) | Poudre de polyamide et procédé de préparation correspondant | |
EP3867315A1 (de) | Transparente polymerzusammensetzung | |
EP3712196A1 (de) | Verwendung von copolyamiden für die herstellung von zusammensetzungen mit einer stabilen steifigkeit unter einwirkung von temperatureffekten | |
WO2022074350A2 (fr) | Composition pulverulente pigmentee facilement recyclable pour le revetement de substrats | |
EP4063428B1 (de) | Polyamidzusammensetzung für magnetisches verbundmaterial | |
FR3116058A1 (fr) | Procede de preparation en continu de prepolymeres de polyamides formules | |
EP3712197A1 (de) | Verwendung von copolyamiden für die herstellung von zusammensetzungen mit einer stabilen steifigkeit unter einwirkung von feuchtigkeit |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20230418 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) |