CN112592472A - Continuous preparation method of semi-aromatic polyamide with low oligomer content and semi-aromatic polyamide product - Google Patents
Continuous preparation method of semi-aromatic polyamide with low oligomer content and semi-aromatic polyamide product Download PDFInfo
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- CN112592472A CN112592472A CN202011483888.0A CN202011483888A CN112592472A CN 112592472 A CN112592472 A CN 112592472A CN 202011483888 A CN202011483888 A CN 202011483888A CN 112592472 A CN112592472 A CN 112592472A
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- acid
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- aromatic polyamide
- diamine
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- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000001704 evaporation Methods 0.000 claims abstract description 29
- 230000008020 evaporation Effects 0.000 claims abstract description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005507 spraying Methods 0.000 claims abstract description 23
- 150000004985 diamines Chemical class 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229960001701 chloroform Drugs 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000007605 air drying Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010924 continuous production Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic diamine Chemical class 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- 239000003279 phenylacetic acid Substances 0.000 claims description 2
- 229960003424 phenylacetic acid Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000001577 simple distillation Methods 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 17
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920006122 polyamide resin Polymers 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 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
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 244000125380 Terminalia tomentosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012632 extractable Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a continuous preparation method of semi-aromatic polyamide with low oligomer content, which comprises the following steps: (a) taking water as a solvent, diamine and dibasic as initial feeding materials, adding a catalyst, pulping, heating, dissolving, and neutralizing to form salt; (b) dehydrating and concentrating the salt solution obtained after neutralization and salification, detecting the content of diamine in the steam condensate, adjusting the amine acid molar ratio to be more than 1.0, and then carrying out prepolymerization reaction; (c) carrying out flash evaporation spraying and circulating air drying containing extractant steam on the prepolymerization reaction liquid in sequence, then carrying out melt tackifying on the reaction liquid by an extruder, and carrying out underwater grain cutting to obtain semi-aromatic polyamide particles with low oligomer content; the extractant vapour is selected from dichloromethane and/or trichloromethane vapour. The preparation method disclosed by the invention is simple in process and short in production period; the semi-aromatic polyamide product has the advantages of remarkably reduced oligomer content which is lower than 0.85 percent, narrow molecular weight distribution, no pollution to a mold during molding and processing, and wide application in the fields of electronics, electrics, automobiles and the like.
Description
Technical Field
The invention relates to the technical field of semi-aromatic polyamide, in particular to a continuous preparation method of semi-aromatic polyamide with low oligomer content and a product thereof.
Background
Polyamide is a polymer whose molecular main chain contains a repeating amide group, and has excellent wear resistance, good mechanical properties, chemical resistance and the like, and is widely used in the fields of textile fibers, electronics and electronics, automobiles and the like since the industrialization is realized in 1939. However, as conventional general engineering plastics, such as nylon 6 and nylon 66, have increasingly exposed defects such as high water absorption, poor dimensional stability and insufficient heat resistance, which limit their applications in high and new fields, and thus, the development of polyamide resins with excellent comprehensive properties is urgently needed.
The semi-aromatic polyamide is a polymer prepared by condensation polymerization of aliphatic diamine or diacid and aromatic diacid or diamine, and has excellent heat resistance, good mechanical properties and dimensional stability due to introduction of a rigid aromatic ring structure in a main chain. Particularly, with the development of Surface Mount Technology (SMT), the lead-free reflow process has made higher demands on the heat resistance of the material, and semi-aromatic polyamide has gradually become an ideal material and is very promising in the fields of electronics and the like.
The semi-aromatic polyamide on the market at present generally has the condition of higher oligomer content, and can bring a plurality of adverse effects on production, processing and application: the oligomer is easy to sublimate and escape during high-temperature melt polymerization, deposits on the surface of polymerization equipment, and is easy to block a devolatilization pipeline to influence the continuous and stable operation of the equipment; the low polymer is easy to migrate during downstream processing and molding, or is deposited on the surface of resin, so that the color difference exists in the product, or is deposited on the surface of a mold, so that the cleaning frequency is increased, and the production efficiency is reduced; higher oligomer content can affect the thermal stability, flame retardancy, mechanical properties, etc. of the resin, and reduce the satisfaction of downstream customers. Therefore, the preparation of the semi-aromatic polyamide with lower oligomer content is of great significance.
Chinese patent publication No. CN104619777A discloses a polyamide resin composition comprising 100 parts by mass of a semi-aromatic polyamide prepolymer and 0.1 to 10 parts by mass of a compound acting as a lewis base, wherein the compound acting as a lewis base is at least one selected from the group consisting of an alkali metal oxide, an alkali metal hydroxide, an alkaline earth metal oxide, an alkaline earth metal hydroxide, zinc oxide and zinc hydroxide. The technical scheme aims to prepare the polyamide resin with less mold pollution in the manufacturing process, but the data in the table 1 show that the content of the oligomer in the prepared polyamide resin is still as high as 1.3-2.5%.
Chinese patent publication No. CN1166843A discloses a semi-aromatic polyamide, a method for preparing the same, and a method for preparing a composition, and specifically discloses a method for washing a semi-aromatic polyamide prepolymer with boiling water, selectively transferring unreacted raw material monomers and oligomers into a water phase, drying the prepolymer, and polymerizing the dried prepolymer with a twin-screw extruder to obtain a resin with low content of components dissolved in boiling water. The method reduces the content of the resin oligomer to a certain extent by adding a prepolymer water washing process, but the water extraction process consumes longer time and has higher energy consumption.
Chinese patent publication No. CN104780988A discloses an extraction reactor and method for extracting particulate materials, and specifically discloses the use of a high-temperature extraction liquid to dissolve residual oligomer or monomer components from the particulate materials during the polycondensation reaction. The method provides a post-treatment method for reducing the finished product oligomer, but adds post-drying operation, has high energy consumption and long retention time in the whole process, and is not suitable for industrial mass production.
U.S. patent No. 6525167 discloses a process for the continuous preparation of polyamide resins with a low extractables content by secondary flash evaporation to remove monomers and oligomers from the polyamide resin; EP0989150A1, US20200071463A1 describe the removal of starting materials and oligomers thereof from molten nylon 6 by evaporation under reduced pressure and at elevated temperature.
It can be seen that the current technical solution for controlling the content of semi-aromatic polyamide oligomer from the source, such as the aforementioned CN104619777a, has not ideal effect; the method for removing the oligomer by the simple solvent extraction method has high energy consumption and low efficiency, and is difficult to meet the requirement of industrial mass production. In summary, a method for preparing semi-aromatic polyamide with simple and efficient process, stable product quality and low oligomer content is still lacked in the field at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a continuous preparation method of semi-aromatic polyamide with low oligomer content, which has simple process and short production period; the content of oligomers in the semi-aromatic polyamide product is remarkably reduced to be lower than 0.85%, the molecular weight distribution is narrow, and the semi-aromatic polyamide product does not pollute a mould during forming and processing, and can be widely applied to the fields of electronics, electrics, automobiles and the like.
The specific technical scheme is as follows:
a continuous preparation method of semi-aromatic polyamide with low oligomer content comprises the following steps:
(a) taking water as a solvent, taking diamine and dicarboxylic acid according to a molar ratio of less than 1.0 as initial feeding materials, adding a catalyst, pulping, heating, dissolving, and neutralizing to form salt;
(b) detecting the salt solution obtained after the neutralization and salification in the step (a), then dehydrating and concentrating, detecting the diamine content of the steam condensate, adjusting the molar ratio of amino acid to diamine to be more than 1.0 by using diamine and a molecular weight regulator, and then carrying out prepolymerization reaction;
(c) carrying out flash evaporation spraying and circulating air drying containing extractant steam on the prepolymerization reaction liquid obtained in the step (b), then carrying out melt tackifying on the reaction liquid by an extruder, and carrying out underwater pelletizing to obtain semi-aromatic polyamide particles with low oligomer content;
the extractant vapor is selected from dichloromethane vapor and/or trichloromethane vapor.
On the basis of the existing continuous production process of semi-aromatic polyamide, the invention firstly adopts flash evaporation and spray treatment to the prepolymerization reaction liquid obtained after prepolymerization reaction, atomizes the prepolymer into small molten drops, and extracts and separates the small molten drops by introducing circulating air containing extractant steam on line. Compared with the post-polycondensation process, the molecular weight of the prepolymer in the stage is not very high, the specific surface area is about 30-40 times of that of a finished product, the full contact between the extractant and the prepolymer is easily ensured, the mass transfer effect is optimal, and the extraction of unreacted monomers and oligomers in the prepolymer is facilitated. On the other hand, continuous online operation is most easily realized in the extraction, and the residual heat of the material can be utilized to continuously preserve heat of the extracting agent, so that the energy consumption is saved.
The average particle size of the atomized droplets can be controlled by controlling the pressure of the flash spray. Preferably, the flash evaporation spraying pressure is 1.0-1.4 MPa; and atomizing the prepolymerization reaction solution into small molten drops with the average particle size of 50-200 mu m after the flash evaporation and the spraying. Tests show that the content of oligomer in the semi-aromatic polyamide product can be controlled to be less than 0.85% by adopting the preferable average particle size, and the molecular weight distribution is narrow. Further preferably, the flash evaporation spraying pressure is 1.0-1.2 MPa; and atomizing the prepolymerization reaction solution into small molten drops with the average particle size of 100-200 mu m after the flash evaporation and the spraying. Tests show that if the average particle size of atomized droplets is too small, the bulk density of prepolymer is too low, continuous and stable feeding of an extruder is not facilitated, and the risk of pipeline blockage is caused when the atomized droplets are operated under the operation condition for a long time. Preferably, the circulating air containing the extractant vapor takes nitrogen as a carrier gas. The method reduces the oxygen content of the spray tower by taking nitrogen as carrier gas to avoid the oxidation and yellowing of the prepolymer; and the sprayed prepolymer molten drops are quickly cooled and dried, the aggregation and agglomeration of the molten drops are avoided, and the uniform shape, controllable particle size and stable discharging of an extruder of the prepolymer are ensured. The low polymer carried by the extractant can be pre-polymerized and tackified again to realize the reutilization of the material after being absorbed and collected by a dust remover, and the extractant vapor after condensation can be separated from water and then can be recycled after simple distillation. Compared with the method of using water or water-soluble solvent to carry out low-boiling extraction on the prepolymer, the selected extractant is simpler and more convenient to recover, and the energy consumption is lower.
It has been found through experimentation that the volume flow rate of the extractant vapor and nitrogen as carrier gas in the present invention has a critical effect on the oligomer extraction performance.
Preferably:
the volume flow ratio of the extractant vapor to the nitrogen gas is 1: 40-1: 120 of a solvent; more preferably 1: 40-1: 100. tests show that if the volume flow ratio of the two is too small, the mass ratio of the number average molecular weight of the resin product below 5000 is higher than 4.50%, and the oligomer content is higher than 0.80%.
More preferably, the ratio of the volume flow rate of the two is 1: 40. however, based on the economics and effectiveness of the solvent, the ratio of the two volumetric flow rates is preferably 1: 60-1: 100, respectively; more preferably 1: 60-1: 80.
it has been found through experiments that the kind of the extractant vapor also has a critical influence on the oligomer extraction effect in the present invention. If the extractant steam is not added into the circulating air or the added extractant steam is common ethanol steam in the field, the prepared resin product has the mass percentage ratio of the number average molecular weight of less than 5000 higher than 5.00 percent and the oligomer content higher than 0.90 percent.
It has also been unexpectedly found in experiments that the semi-aromatic polyamide produced using the vapors of methylene chloride and/or chloroform as disclosed in the present invention as extractant vapors has a narrower molecular weight distribution with a PDI of less than 2.00.
Further preferably, the extractant vapor is selected from chloroform vapor, and tests show that compared with dichloromethane vapor, the semi-aromatic polyamide prepared by the method has lower mass ratio of the number average molecular weight below 5000, lower oligomer content and narrower molecular weight distribution.
Preferably, the air temperature of the circulating air containing the extractant steam is 100-130 ℃.
In step (a):
the diamine is selected from aliphatic diamine with 4-14 carbon atoms; preferably one or more of hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonane diamine, decanediamine, 2-methylpentane diamine, undecane diamine and laurel diamine.
The dicarboxylic acid is selected from aromatic dicarboxylic acid and/or aliphatic dicarboxylic acid, and the carbon number is 4-14; preferably one or more of terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and lauric acid. More preferably, the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 100:0 to 40:60, and still more preferably 100:0 to 50: 50.
The catalyst is a phosphorus-containing catalyst and is selected from one or more of phosphate, phosphorous acid, phosphite and hypophosphite; the amount of the catalyst substance is 0.01-2.50% of the amount of the dicarboxylic acid substance; preferably 0.05 to 1.00%.
Preferably, the initial feeding molar ratio of the diamine to the dicarboxylic acid is 0.90-0.99, and more preferably 0.92-0.98.
In step (a):
when the pulping is heated and dissolved, the water content of the system is 20-50%, and the temperature is 60-100 ℃;
the temperature of the neutralization and salt formation is 120-180 ℃, and the pressure is 0.10-1.00 MPa.
In step (b):
detecting the composition of dicarboxylic acid in the salt solution formed by neutralization and salt formation through an online Raman spectrum, and adding corresponding aromatic dibasic acid or aliphatic dibasic acid in the raw materials to keep the composition of the dibasic acid stable.
And the composition of the salt solution and the diamine content of the steam condensate are detected by adopting an online Raman spectrum.
During dehydration and concentration, the liquid phase temperature is 180-240 ℃, the gas phase pressure is 0.80-1.50 MPa, the dehydration time is 10-30 min, and the physical water content of the concentrated system is 8-15%.
Preferably, the first and second liquid crystal materials are,
the molecular weight regulator is monocarboxylic acid selected from one or more of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, benzoic acid and phenylacetic acid; the amount of the molecular weight regulator substance is 0.1-5.0% of the amount of the dicarboxylic acid substance; more preferably 0.5 to 3.0%.
Preferably:
adjusting the molar ratio of amino acid to 1.03-1.07 by using the diamine and the molecular weight regulator; more preferably 1.04 to 1.06.
The temperature of the prepolymerization reaction is 280-350 ℃, the pressure is 10.0-30.0 MPa, and the reaction time is 1-15 min.
In step (c):
carrying out melt tackifying by adopting a double-screw extruder, wherein the reaction temperature is 300-350 ℃, and the reaction time is 0.5-5 min;
and when underwater pelletizing, the temperature of the circulating water tank is 60-90 ℃, and semi-aromatic polyamide particles with the water content of less than 0.15% are obtained after centrifugal drying.
The invention also discloses a semi-aromatic polyamide with low oligomer content prepared according to the method, which comprises the following components:
the content of methanol Soxhlet extraction oligomer is less than 0.85 percent, the mass ratio of the number average molecular weight of the methanol Soxhlet extraction oligomer to the number average molecular weight of the methanol Soxhlet extraction oligomer is less than 4.60 percent, and the polymer dispersibility index PDI is less than 2.00;
the intrinsic viscosity is 0.70-0.95 dL/g, the content of terminal amino groups is lower than 0.10mol/kg, and the content of terminal carboxyl groups is lower than 0.02 mol/kg.
Further preferably:
the content of methanol Soxhlet extraction oligomer is not higher than 0.75 percent, the mass ratio of the number average molecular weight of the polymer which is lower than 5000 is lower than 4.20 percent, and the polymer dispersibility index PDI is not higher than 1.96.
The semi-aromatic polyamide with the performance characteristics has extremely low oligomer content, basically has no deposition during resin molding and processing, has no pollution to a mold, and can be widely applied to the fields of electronics, electrics, automobiles and the like.
Compared with the prior art, the invention has the following advantages:
the invention discloses a continuous preparation method of semi-aromatic polyamide with low oligomer content, which is characterized in that flash evaporation spraying and circulating air drying treatment containing extractant steam are added after prepolymerization reaction on the basis of the existing continuous production process of semi-aromatic polyamide, and the circulating air drying treatment is carried out in a spray tower, so that the continuous preparation of semi-aromatic polyamide is easier to realize. The particle size of small molten drops formed by flash evaporation and spraying and the type and content of an extracting agent in circulating air drying treatment are respectively controlled, so that the content of oligomers in the finally prepared semi-aromatic polyamide is reduced to be below 0.85%, the mass ratio of the number average molecular weight of the semi-aromatic polyamide is lower than 5000 and is lower than 4.60%, and the polymer dispersity index PDI is lower than 2.00.
The preparation method has simple process and short production period; the content of oligomers in the semi-aromatic polyamide product is remarkably reduced, the molecular weight distribution is narrow, and the semi-aromatic polyamide product does not pollute a mould during molding and processing, and can be widely applied to the fields of electronics, electrics, automobiles and the like.
Drawings
FIG. 1 is a schematic diagram of a process for the continuous production of a semi-aromatic polyamide having a low oligomer content according to the present invention, wherein:
1-an aliphatic dibasic acid bin;
2.4, 6-feeding screw conveyor;
a 3-terephthalic acid bin;
a 5-isophthalic acid (or other diacid) silo;
7-a catalyst aqueous solution storage tank;
8. 10, 12, 13, 17, 23, 24, 26, 28, 30, 32-pump;
9-pulping kettle;
11-a molten diamine storage tank;
14-a multi-stage stirring dissolving kettle;
15. 27, 33-heat exchanger;
16. 18, 20-online raman spectroscopy detector;
19-dissolving into a salt kettle;
21-a controller;
22-a molten aliphatic dibasic acid storage tank;
25-isophthalic acid (or other diacid) slurry storage tank;
29-a dehydrator;
31-a reservoir of molten monobasic acid;
34-a prepolymerization reactor;
35-a pressure reducing valve;
36-a flash evaporator;
37-a spray tower;
38-finisher (twin-screw extruder);
39-granulator.
Detailed Description
In order that those skilled in the art will be better able to understand the technical solutions of the present invention, the present invention will be described with reference to specific embodiments. In the production process, all materials are deoxidized by high-purity nitrogen, and all devices in the preparation process are replaced and protected by the high-purity nitrogen. The characteristics of the products in the following examples and comparative examples were measured in the following manner.
1. Intrinsic viscosity
Dissolving a semi-aromatic polyamide sample in a mixed solvent of phenol-tetrachloroethane (mass ratio of 3:2) to obtain solutions with concentrations of 0.1, 0.25 and 0.5g/dL, and measuring the inherent viscosity eta of the sample solution by using an Ubbelohde viscometer in a constant-temperature water bath environment at 30 DEG Cln。
ηln＝[ln(t/t0)]/C(dL/g)；
Wherein, t0The flow time of the solvent (sec), t the flow time of the solution (sec), and C the concentration of the sample solution (g/dL).
Will etalnThe intrinsic viscosity [ eta ] of the sample can be obtained by extrapolating the data to the concentration of 0]。
2. End group content
The amino-and carboxyl-terminated content of the resin was measured using a KEM automated potentiometric titrator AT-710.
Content of terminal amino groups: accurately weighing 0.4g (accurate to 0.0001g) of resin, adding 20mL hexafluoroisopropanol, stirring at 55 ℃ for 1h, adding 2mL deionized water, continuing stirring for 10min to completely dissolve the sample, and testing the content of terminal amino group by using calibrated 0.1 equivalent hydrochloric acid.
Content of terminal carboxyl groups: accurately weighing 0.4g (accurate to 0.0001g) of resin, adding 50mL of melted o-cresol, stirring, heating and refluxing until the sample is dissolved, adding 0.5mL of formaldehyde solution when the solution is cooled to about 50 ℃, and testing the content of terminal carboxyl by using a calibrated 0.1 equivalent KOH-ethanol solution.
3. Molecular weight and distribution curve
The molecular weight and distribution curve of the resin were measured using Gel Permeation Chromatography (GPC). A standard elution curve was prepared using a methyl methacrylate (PMMA) standard sample, and the molecular weight distribution of the polymer was characterized by GPC using hexafluoroisopropanol containing 0.01mol/L sodium trifluoroiso-propionate as a solvent.
4. Thermal stability
The thermal stability of the resin was characterized by melt shear viscosity retention, and the shear viscosity of the resin was measured by using a capillary rheometer of LCR-7000 type, at a cylinder temperature of (Tm +15) DEG C and a shear rate of 1000sec-1The melt viscosity of the melt at 5min and 20min of heat preservation was measured separately and recorded as MV5And MV20The melt viscosity retention is MV20/MV5×100％。
5. Oligomer content
Grinding the prepared semi-aromatic polyamide into powder by using a high-speed rotary grinding instrument, weighing about 10g, and recording the mass as m0(accurate to 0.0001g), pouring into a filter paper cylinder, placing the filter paper cylinder into a Soxhlet extractor, repeatedly refluxing with 200mL of methanol for 8h to extract oligomers, recovering methanol after the experiment is finished, removing the solvent by rotary evaporation to obtain an extract, and recording the mass as m after drying1(to the nearest 0.0001g), oligomer content ═ m1/m0×100％。
6. Contamination of mold
The prepared semi-aromatic polyamide was injection-molded using a curved spline mold under the following conditions, and the mold contamination after 100 times of continuous injection molding was visually observed. The mold fouling evaluation index was represented by "O" indicating the absence of adhering matter and fogging on the mold, "Δ" indicating the presence of fogging on the mold, and "x" indicating the presence of adhering matter on the mold.
Polyamide resin temperature at the time of injection molding: 330-340 ℃; the temperature of the die is 120 ℃; the injection speed is 60 mm/s; injection pressure 80 bar; the cooling time was 15 s.
Example 1
4.57kg/h (27.5mol/h) of terephthalic acid, 3.29kg/h (22.5mol/h) of adipic acid, 5.52kg/h (47.5mol/h) of hexamethylenediamine, 0.05kg/h of 20 wt% sodium hypophosphite aqueous solution and 5.72kg/h of water are added into a pulping kettle 9 according to the proportion of the initial feeding amino acid ratio of 0.95, and the mixture is continuously pulped at 80 ℃ to form pulp. The slurry is conveyed into a multistage stirring dissolving kettle 14 through a pump 10 and is heated to 150 ℃ by steam generated in the dehydration process to be dissolved into salt. According to the composition of the dibasic acid in the salt solution detected by the on-line Raman spectrum 18, the amount of the aliphatic dibasic acid is adjusted by adopting molten adipic acid through a metering pump 23, so that the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid in the salt forming kettle 19 is stabilized at 55: 45. After the salt solution is detected by the online Raman spectrum 20, the salt solution is pressurized to 1.0MPa by the pump 24 and then is conveyed to the heat exchanger 27 of the dehydrator 29, and then is mixed with the material conveyed by the circulating pump 28, the mixture is heated, and is dehydrated in the dehydrator 29, the dehydration temperature is controlled at 200 ℃, the physical water content is controlled at about 13%, and the dehydration retention time is 25 min. The steam from the dehydrator 29 is used as the heat source of the multi-stage stirred tank dissolver 14, after being cooled by the heat exchanger 15, the amine content is detected by the online raman spectroscopy 16, and the amount of the supplementary molten hexamethylene diamine required before the pump 32 is determined by the controller 21 according to the detection results of the raman spectroscopy 16 and 20. The dehydrated qualified material was passed through pumps 17 and 30 respectively to adjust the molar ratio of the amine acid to 1.04 with molten hexamethylenediamine and 0.06kg/h (1mol/h) of acetic acid. Then pressurizing to 10.0MPa by using a pump 32, conveying the materials into a heat exchanger 33, preheating and heating to 290 ℃, carrying out heat preservation reaction for 5min at 320 ℃ in a prepolymerization reactor 34, then carrying out reduced pressure spraying at 1.0-1.2 MPa by using a flash evaporation reactor 36, atomizing into small molten drops with the average particle size of 100-200 mu m, drying by 110 ℃ circulating air containing trichloromethane steam/nitrogen in a spray tower 37 to obtain a prepolymer, wherein the volume flow ratio of the extractant steam to the nitrogen is 1:80, feeding the prepolymer into a double-screw extruder 38 for melt polymerization, exhausting and tackifying, the reaction temperature is 300-320 ℃, the residence time is 5min, carrying out rotary drying under 75 ℃ circulating water, carrying out rotary drying, and centrifuging to obtain a semi-aromatic polyamide product with the concentration of about 12.0 kg/h.
Comparative example 1
And (3) directly feeding small molten droplets of a prepolymer formed after decompression and spraying of the flash evaporation reactor into a double-screw extruder for melt polymerization, wherein other steps and processes are completely the same as those in example 1, and finally obtaining a semi-aromatic polyamide product of about 12.6 kg/h.
Comparative example 2
And (3) drying small molten droplets of a prepolymer formed after decompression and spraying of the flash evaporation reactor in a spray tower by pure nitrogen circulating air at the temperature of 110 ℃, wherein other steps and processes are completely the same as those in example 1, and finally obtaining the semi-aromatic polyamide product of about 12.4 kg/h.
Comparative example 3
And (3) drying small molten drops of a prepolymer formed after decompression and spraying of the flash evaporation reactor in a spray tower by circulating air through ethanol-containing steam and nitrogen at the temperature of 110 ℃ to obtain the prepolymer, wherein the volume flow ratio of the extractant steam to the nitrogen is 1:80, and other steps and processes are completely the same as those in example 1, so that a semi-aromatic polyamide product of about 12.3kg/h is finally obtained.
Example 2
And (3) drying the prepolymer sprayed by the flash evaporation reactor under reduced pressure in a spray tower by using circulating air of nitrogen containing dichloromethane vapor at the temperature of 130 ℃ to obtain the prepolymer, wherein the volume flow ratio of the extracting agent vapor to the nitrogen is 1:80, and other steps and processes are completely the same as those in example 1, so that the semi-aromatic polyamide product of about 12.2kg/h is finally obtained.
Example 3
And (3) drying the prepolymer sprayed by the flash evaporation reactor under reduced pressure in a spray tower by using nitrogen circulating air containing trichloromethane steam at 100 ℃ to obtain the prepolymer, wherein the volume flow ratio of the extracting agent steam to the nitrogen is 1:40, and the other steps and processes are completely the same as those in example 1, so that the semi-aromatic polyamide product of about 11.8kg/h is finally obtained.
Example 4
And (3) drying the prepolymer sprayed by the flash evaporation reactor under reduced pressure in a spray tower by nitrogen circulating air containing trichloromethane steam at 105 ℃ to obtain the prepolymer, wherein the volume flow ratio of the extracting agent steam to the nitrogen is 1:60, and the other steps and processes are completely the same as those in example 1, so that the semi-aromatic polyamide product of about 11.9kg/h is finally obtained.
Example 5
And (3) drying the prepolymer sprayed by the flash evaporation reactor under reduced pressure in a spray tower by using nitrogen circulating air containing trichloromethane steam at 120 ℃ to obtain the prepolymer, wherein the volume flow ratio of the extracting agent steam to the nitrogen is 1:100, and the other steps and processes are completely the same as those in example 1, so that the semi-aromatic polyamide product of about 12.1kg/h is finally obtained.
Example 6
And (3) drying the prepolymer sprayed by the flash evaporation reactor under reduced pressure in a spray tower by nitrogen circulating air containing trichloromethane steam at the temperature of 130 ℃ to obtain the prepolymer, wherein the volume flow ratio of the extracting agent steam to the nitrogen is 1:120, and the other steps and processes are completely the same as those in example 1, so that the semi-aromatic polyamide product of about 12.2kg/h is finally obtained.
Example 7
The reduced pressure spraying pressure of the flash evaporation reactor is controlled to be 1.2-1.4 Mpa, the flash evaporation reactor is atomized into small molten drops with the average grain diameter of 50-100 mu m, other steps and processes are completely the same as those in the embodiment 1, and finally, a semi-aromatic polyamide product with the grain diameter of about 11.6kg/h is obtained.
Comparative example 4
The reduced pressure spraying pressure of the flash evaporation reactor is controlled to be 0.8-1.0 Mpa, the flash evaporation reactor is atomized into the semi-aromatic polyamide with the average grain diameter of 300-500 mu m, other steps and processes are completely the same as those in the embodiment 1, and the semi-aromatic polyamide product with the grain diameter of about 12.2kg/h is finally obtained.
The extraction conditions in the above examples and the properties of the separately prepared products are listed in table 1 below; the extraction conditions in the above respective proportions and the properties of the products prepared separately are listed in table 2 below.
TABLE 1
TABLE 2
| Numbering | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Extracting agent | —— | —— | Ethanol | Trichloromethane |
| Volume flow ratio of extractant to nitrogen | 0:0 | 0:1 | 1:80 | 1:80 |
| Spray pressure/MPa | 1.0～1.2 | 1.0～1.2 | 1.0～1.2 | 0.8～1.0 |
| Number average molecular weight Mn (g. mol)-1) | 16754 | 17873 | 18481 | 18476 |
| Mn<5000 mass ratio (%) | 6.05 | 5.29 | 5.18 | 5.07 |
| PDI value | 2.21 | 2.09 | 2.03 | 2.05 |
| MV20/MV5(％) | 90 | 92 | 92 | 93 |
| Oligomer content (%) | 1.13 | 0.93 | 0.91 | 0.94 |
| Contamination of mold | × | Δ | O～Δ | Δ |
| Intrinsic viscosity (dL g)-1) | 0.87 | 0.88 | 0.88 | 0.87 |
| Terminal amino group (mol. kg)-1) | 0.103 | 0.100 | 0.099 | 0.100 |
| Terminal carboxyl group (mol. kg)-1) | 0.024 | 0.021 | 0.020 | 0.021 |
As shown in tables 1 and 2, the product without the circulating air drying process has oligomer content higher than 1%, the mold has attachments during the injection molding of the sample, the product has wide molecular weight distribution and poor thermal stability; the product obtained by adopting the pure nitrogen circulating air drying process has the advantages that the oligomer content is reduced, the molecular weight distribution is narrowed, but the mold has the fogging condition during sample injection; under the condition of the same volume flow ratio, the chloroform is selected as the extractant with the best effect, the dichloromethane with the second order and the ethanol with the worst effect. Chloroform is used as an extracting agent, and the volume flow ratio of vapor to nitrogen is 1:40 and 1: 60; when the volume flow ratio of the steam to the nitrogen is 1:120, the mass percentage of the resin with the number average molecular weight of less than 5000 is higher than 4.50 percent, and the content of the solvent extraction oligomer is higher than 0.80 percent. In consideration of the economy and effectiveness of the solvent, the volume flow ratio of the trichloromethane steam to the nitrogen is set to be 1: 60-1: 100, the spraying prepolymer is subjected to oligomer extraction under the condition, the mass ratio of the number average molecular weight of polyamide particles obtained after the polyamide particles are subjected to degassing and devolatilization by an extruder and subjected to extraction and centrifugal drying by circulating hot water by a granulator is lower than 4.50%, the oligomer content is lower than 0.80%, the thermal stability is excellent, and the mold pollution is low. When the spraying pressure is increased, molten drops with a small particle size of 50-100 mu m can be obtained, but the bulk density of the prepolymer is about 0.3g/cm3(Normal 0.5-0.7g/cm3) Unfavorable to continuous stable discharge of extruder, and low polymer content andexample 1 is essentially identical, and in addition there is a risk of pipe plugging over long periods of operation under this operating condition; on the other hand, when the spraying pressure is reduced, the small molten drops of the prepolymer have poor dispersibility, are easy to adhere and agglomerate, the extraction effect is poor, the content of the finished oligomer is higher than 0.90 percent, and the extruder has unstable material flow due to wide particle size distribution and more massive materials. Therefore, the spraying pressure is preferably 1.0-1.2 Mpa, the mixture is atomized into small molten drops with the average grain diameter of 100-200 mu m, the content of the finished product oligomer is low, and the continuous and stable operation of production can be ensured.
In order to further verify the extraction effect of different extraction agents on the oligomer in the prepolymer, the following experiment is supplemented.
Experiment: accurately weighing about 5g of prepolymer (marked as m) in the same batch by an analytical balance, placing the prepolymer in a filter paper tube, performing an oligomer extraction experiment by using a Soxhlet extractor, wherein the total volume of a solvent is 120mL, placing the prepolymer in a 250mL flat-bottomed flask with zeolite, and marking the mass of the empty flask and the zeolite as m0Refluxing at 96 deg.C for 8 hr, stopping extraction, removing solvent in flask by rotary evaporation, drying at 100 deg.C for 4 hr to constant weight, weighing, and recording mass as m1Then the solvent extraction oligomer content is (m)1-m0) 100% m, the results are given in Table 3.
TABLE 3
As can be seen from Table 3, chloroform alone is the most effective for oligomer extraction, methylene chloride and chloroform are the second to blend, and methylene chloride alone is the second to blend, and ethanol is the least effective.
Claims (10)
1. A continuous preparation method of semi-aromatic polyamide with low oligomer content is characterized by comprising the following steps:
(a) taking water as a solvent, taking diamine and dicarboxylic acid according to a molar ratio of less than 1.0 as initial feeding materials, adding a catalyst, pulping, heating, dissolving, and neutralizing to form salt;
(b) detecting the salt solution obtained after the neutralization and salification in the step (a), then dehydrating and concentrating, detecting the diamine content in the steam condensate, and adjusting the molar ratio of amino acid to diamine to be more than 1.0 by using diamine and a molecular weight regulator to perform prepolymerization reaction;
(c) carrying out flash evaporation spraying and circulating air drying containing extractant steam on the prepolymerization reaction liquid obtained in the step (b), then carrying out melt tackifying on the reaction liquid by an extruder, and carrying out underwater pelletizing to obtain semi-aromatic polyamide particles with low oligomer content;
the extractant vapor is selected from dichloromethane vapor and/or trichloromethane vapor.
2. The continuous production method of a semi-aromatic polyamide with a low oligomer content according to claim 1, wherein in step (a):
the diamine is selected from aliphatic diamine with 4-14 carbon atoms;
the dicarboxylic acid is selected from aromatic dicarboxylic acid and/or aliphatic dicarboxylic acid, and the carbon number is 4-14;
the catalyst is a phosphorus-containing catalyst and is selected from one or more of phosphate, phosphorous acid, phosphite and hypophosphite;
the amount of the catalyst substance is 0.01-2.50% of the amount of the dicarboxylic acid substance.
3. The continuous production method of a semi-aromatic polyamide having a low oligomer content according to claim 2, characterized in that:
the diamine is selected from one or more of hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonanediamine, decanediamine, 2-methylpentanediamine, undecanediamine and lauryldiamine;
the dicarboxylic acid is selected from one or more of terephthalic acid, isophthalic acid, 2, 6-naphthalene dicarboxylic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and lauric acid;
the initial feeding ratio of the diamine to the dicarboxylic acid is 0.90-0.99.
4. The continuous production method of a semi-aromatic polyamide with a low oligomer content according to claim 1, wherein in step (a):
when the pulping is heated and dissolved, the water content of the system is 20-50%, and the temperature is 60-100 ℃;
the temperature of the neutralization and salt formation is 120-180 ℃, and the pressure is 0.10-1.00 MPa.
5. The continuous production method of a semi-aromatic polyamide with a low oligomer content according to claim 1, wherein in step (b):
during dehydration and concentration, the liquid phase temperature is 180-240 ℃, the gas phase pressure is 0.80-1.50 MPa, the dehydration time is 10-30 min, and the physical water content of the concentrated system is 8-15%;
the molecular weight regulator is monocarboxylic acid selected from one or more of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, benzoic acid and phenylacetic acid;
the amount of the molecular weight regulator substance is 0.1-5.0% of the amount of the dicarboxylic acid substance;
adjusting the molar ratio of amino acid to 1.03-1.07 by using the diamine and the molecular weight regulator;
the temperature of the prepolymerization reaction is 280-350 ℃, the pressure is 10.0-30.0 MPa, and the reaction time is 1-15 min.
6. The continuous production method of a semi-aromatic polyamide with a low oligomer content according to claim 1, wherein in step (c):
the flash evaporation spraying pressure is 1.0-1.4 MPa;
atomizing the prepolymerization reaction solution into small molten drops with the average particle size of 50-200 mu m after the flash evaporation and the spraying;
the circulating air containing the extractant vapor takes nitrogen as carrier gas, and the volume flow ratio of the extractant vapor to the nitrogen is 1: 40-1: 120 of a solvent;
the air temperature of the circulating air containing the extractant steam is 100-130 ℃.
7. The continuous production method of a semi-aromatic polyamide with a low oligomer content according to claim 6, wherein in step (c):
the extractant vapor is selected from chloroform vapor;
the volume flow ratio of the extractant vapor to the nitrogen gas is 1: 40-1: 100.
8. the continuous production method of a semi-aromatic polyamide with a low oligomer content according to claim 6, wherein in step (c):
the flash evaporation spraying pressure is 1.0-1.2 MPa;
atomizing the prepolymerization reaction solution into small molten drops with the average particle size of 100-200 mu m after the flash evaporation and the spraying;
the extractant vapor dried by the circulating air is separated from water and can be recycled by simple distillation.
9. The continuous production method of a semi-aromatic polyamide with a low oligomer content according to claim 1, wherein in step (c):
carrying out melt tackifying by adopting a double-screw extruder, wherein the reaction temperature is 300-350 ℃, and the reaction time is 0.5-5 min;
and when underwater pelletizing, the temperature of the circulating water tank is 60-90 ℃, and semi-aromatic polyamide particles with the water content of less than 0.15% are obtained after centrifugal drying.
10. A semi-aromatic polyamide with a low oligomer content, prepared according to the process of any one of claims 1 to 9, characterized in that the semi-aromatic polyamide:
the content of methanol Soxhlet extraction oligomer is less than 0.85 percent, the mass ratio of the number average molecular weight of the methanol Soxhlet extraction oligomer to the number average molecular weight of the methanol Soxhlet extraction oligomer is less than 4.60 percent, and the polymer dispersibility index PDI is less than 2.00;
the intrinsic viscosity is 0.70-0.95 dL/g, the content of terminal amino groups is lower than 0.10mol/kg, and the content of terminal carboxyl groups is lower than 0.02 mol/kg.
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