CN101463130B - Semi-aromatic polyamide and low wastewater discharge preparation thereof - Google Patents
Semi-aromatic polyamide and low wastewater discharge preparation thereof Download PDFInfo
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- CN101463130B CN101463130B CN2008100293524A CN200810029352A CN101463130B CN 101463130 B CN101463130 B CN 101463130B CN 2008100293524 A CN2008100293524 A CN 2008100293524A CN 200810029352 A CN200810029352 A CN 200810029352A CN 101463130 B CN101463130 B CN 101463130B
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- diamine
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- 239000002351 wastewater Substances 0.000 title claims abstract description 81
- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000004985 diamines Chemical class 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 39
- 239000007790 solid phase Substances 0.000 claims description 24
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 13
- 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 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 12
- 238000013022 venting Methods 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 claims description 7
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical group NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 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 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 2
- KSQSUDDRZLCKSW-UHFFFAOYSA-N 2,4-dimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)CCN KSQSUDDRZLCKSW-UHFFFAOYSA-N 0.000 claims description 2
- LMOSYFZLPBHEOW-UHFFFAOYSA-N 2,5-dichloroterephthalic acid Chemical compound OC(=O)C1=CC(Cl)=C(C(O)=O)C=C1Cl LMOSYFZLPBHEOW-UHFFFAOYSA-N 0.000 claims description 2
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 claims description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005819 Potassium phosphonate Substances 0.000 claims description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical group NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 2
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims description 2
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 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
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000013589 supplement Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 238000013019 agitation Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- 125000003368 amide group Chemical group 0.000 description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 150000001408 amides Chemical class 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 238000007599 discharging Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 230000008878 coupling Effects 0.000 description 10
- 238000010168 coupling process Methods 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000004448 titration Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 4
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical group CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 229920006119 nylon 10T Polymers 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- PIJBVCVBCQOWMM-UHFFFAOYSA-N 5-acetyloxypentyl acetate Chemical compound CC(=O)OCCCCCOC(C)=O PIJBVCVBCQOWMM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
The invention relates to a semi-aromatic polyamide and a preparation method producing low wastewater discharge. The semi-aromatic polyamide is prepared by the following steps: adding aromatic dicarboxylic acid, aliphatic diamine containing 4-14 carbon atoms and wastewater produced in a last prepolymerization process to a pressure pan for a prepolymerization reaction; and then further performing a tackification reaction on the prepolymer to obtain the semi-aromatic polyamide. In the preparation method, the wastewater produced in the polymerization process is recycled, which greatly reduces wastewater discharge; and raw materials in the wastewater are recovered effectively, which improves the utilization ratio of the raw materials; meanwhile, the diamine in the wastewater supplements the diamine which runs off along with the water during the prepolymerization process, which ensures balance of mol ratio of monomer dicarboxylic acid and monomer diamine.
Description
Technical field
The present invention relates to the polyamide resin technical field, specifically, relate to a kind of semiaromatic polyamide composition preparation method of low wastewater discharge.
Background technology
Fatty polyamide, as PA6, PA66, have excellent physical strength, thermotolerance, chemical proofing, wearability and self lubricity, and frictional coefficient is low, its Application Areas comprises electronic apparatus, trolley part, furniture, building materials and fiber, has become one of most important engineering plastics.
Semiaromatic polyamide composition is diamines or dicarboxylic acid and the aliphatic dicarboxylic acid or the diamines of band aromatic nucleus, through the prepared polyamide resin of polycondensation, is a kind of in the aromatic polyamide.Owing in the polymeric amide molecular backbone chain, imported aromatic nucleus, thereby thermotolerance and mechanical property have been improved, reduced water-intake rate, and more suitable P/C ratio is arranged, be the high resin of thermotolerance between general engineering plastic nylon and thermostability engineering plastic PEEK, be mainly used in automobile and electric and electronic industry.Develop rapidly along with high-tech, its application has new breakthrough and progress, and the market requirement is in rising trend.The semiaromatic polyamide composition product mainly contains polymeric amide MXD6,6T/66,6T/6I, 6T/6I/66,6T/M-5T and 9T at present.
Patent JP57200420, JP58111829, EP1074585A1, CN1624021A disclose the preparation method of polymeric amide MXD6.In the method that is proposed, in batch reactor aromatic diamine is added drop-wise in the fused aliphatic dicarboxylic acid, the water that the system temperature that raises is simultaneously removed the condensation generation carries out polyreaction.CN1451677A has described the solid-phase tack producing method of a kind of polymeric amide MXD6, preserves polymeric amide under given conditions, even initial polymeric amide is from preparing the back to spending 20 days solid-phase tack producing or the longer time, the polymeric amide MXD6 Huang degree that makes is also very low.
Because the fusing point of polyamide 6 T has exceeded its decomposition temperature, must add the 3rd monomer to reduce fusing point.Polyamide 6 T multipolymer is that the diamine components polycondensation of 6-hexanediamine composition obtains by the dicarboxylic acid component who mainly is made up of terephthalic acid and m-phthalic acid or hexanodioic acid with mainly by 1.The amide group concentration of polyamide 6 T multipolymer is higher, can cause chemical proofing, water absorption resistance, the melt-processed less stable of polymkeric substance.Add the 3rd a large amount of monomers and reduced crystallinity of polymer, also can cause thermotolerance, chemical proofing, water absorption resistance and the dimensional stability of polymkeric substance to descend.
Patent US5516882, US5981692 and US962628 have described with terephthalic acid, m-phthalic acid, 1,6-hexanodioic acid, 1,6-hexanediamine and 2-methyl isophthalic acid, 5-pentamethylene diamine are main raw material, the method for coming synthesizing polyamides 6T multipolymer by the high-temperature fusion polymerization more than 300 ℃.Patent US6140459 has described with terephthalic acid, 1, and 6-hexanediamine and another kind of aliphatic long-chain di-carboxylic acid are raw material, come synthesizing polyamides 6T multipolymer by melt polymerization.Yet when adopting the melt polymerization process semiaromatic polyamide composition, the secondary polymerization reaction temperature can surpass the fusing point of polymkeric substance, and overstand at high temperature, the DeR of various side reactions and polymkeric substance is violent, the phenomenon that causes polymkeric substance tone variation, physical strength reduction and formability to degenerate easily.
Patent US5663284 discloses a kind of method for preparing polyamide 6 T/66 polymkeric substance, earlier carry out first-stage polymerization having under the condition that water exists, temperature of reaction is lower than melting point polymer, keep pressure by make up water in autoclave when discharging, prepolymer obtains the high viscosity polymkeric substance by exhaust twin screw extruder fusion tackify.But in order to obtain satisfying the prepolymer of fusion tackify requirement, the prepolymerization temperature is near the fusing point of polymkeric substance, to improve the limiting viscosity of prepolymer.
In the prior art, patent US6133406 has proposed a kind of polymerization technique of semiaromatic polyamide composition: earlier under the condition that has water to exist, prepolymer at the synthetic low limiting viscosity of lower temperature, through the prepolymer of the higher limiting viscosity of solid-phase tack producing prepared in reaction, melt extrude the polymkeric substance that tackify obtains high limiting viscosity through twin screw more then.This route relates to prepolymerization reaction, solid-phase tack producing, fusion tackify polystep reaction, requires complicated production stage and equipment.
Among the patent US6156869, after obtaining prepolymer, can obtain polymeric amide 9T resin by long solid-phase tack producing, this technical requirements prepolymer has higher limiting viscosity.Polymeric amide 9T has higher degree of crystallinity, dimensional stability and lower water-intake rate.
In the prior art, obtain the semiaromatic polyamide composition prepolymer of higher limiting viscosity, can realize by the water that improves the prepolymerization temperature or discharge in the prepolymerization reaction system.Raising prepolymerization temperature can cause the generation of side reaction, also can improve reaction pressure, to the also corresponding raising of the requirement of equipment.The water of discharging in the reaction system can vapor away unreacted diamine, and the result causes the monomeric unit ratio of prepolymer greatly different with the initial monomers ratio that joins reactor, can not guarantee the molar ratio balance of monomer di-carboxylic acid and diamine.
Earlier monomer is made salt, be synthesized by polycondensation the loss that semiaromatic polyamide composition just can be avoided diamine by salt again.Patent US5663284 judges the terminal point of salt-forming reaction by measuring pH value, uses salt to prepare semiaromatic polyamide composition.Yet, there is such problem in the prior art: when preparing semiaromatic polyamide composition salt as solvent with water or alcohol, because aromatic binary carboxylic acid and the solubleness of semiaromatic polyamide composition salt in these solvents are very little, purification semiaromatic polyamide composition salt becomes very difficult, be difficult to obtain purified semiaromatic polyamide composition salt, then can not control the mol ratio of di-carboxylic acid and diamine exactly, influence the quality of end product semiaromatic polyamide composition; When preparing semiaromatic polyamide composition salt,, improved the cost of solvent recuperation though can obtain highly purified semiaromatic polyamide composition salt with other organic solvent.
In above all patents, do not relate to treatment process wastewater produced in the semiaromatic polyamide composition building-up process.
Summary of the invention
The objective of the invention is to problem, a kind of preparation method of semi-aromatic polyamide of low wastewater discharge is provided at the prior art existence.This preparation method has carried out recycle to the waste water that produces in the polymerization process, greatly reduces discharged waste water; And the raw material in the waste water has been carried out effective recycling, improved utilization ratio of raw materials; Simultaneously, the diamine in the waste water has compensated the diamine that runs off along with the discharge of water in the pre-polymerization process, has guaranteed the molar ratio balance of monomer di-carboxylic acid and diamine.
Another object of the present invention provides the semiaromatic polyamide composition that utilizes above-mentioned preparation method to prepare.
Above-mentioned purpose of the present invention solves by the following technical programs:
A kind of preparation method of semi-aromatic polyamide may further comprise the steps:
(1) aromatic binary carboxylic acid, the aliphatic diamine that contains 4 to 14 carbon atoms and water are joined carries out prepolymerization reaction in the autoclave pressure;
(2) the above-mentioned prepolymer that obtains is promptly got semiaromatic polyamide composition by solid-phase tack producing reaction or the reaction of fusion tackify.
Carbonatoms in the above-mentioned steps (1) is that 4～14 aliphatic diamine comprises straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.Wherein, the straight chain aliphatic diamine comprises 1,4-butanediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 carbon diamines or 1,12-12 carbon diamines.The side chain aliphatic diamine comprises the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine.Cycloalphatic diamine comprises cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.Semiaromatic polyamide composition can contain these aliphatic diamines of one or more types, and preferred aliphatic diamine is 1,6-hexanediamine, 1,9-nonamethylene diamine, 1,2-methyl isophthalic acid, 5-pentamethylene diamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, the 9-nonamethylene diamine.Best aliphatic diamine is 1,6-hexanediamine, 1,9-nonamethylene diamine or 1.
Aromatic binary carboxylic acid in the above-mentioned steps (1) comprises terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-is dioctyl phthalate, 1 how, and 4-is dioctyl phthalate, 4 how, 4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid.Semiaromatic polyamide composition can contain these aromatic binary carboxylic acids of one or more types.Preferred aromatic binary carboxylic acid is terephthalic acid, m-phthalic acid or 4,4 '-biphenyl dicarboxylic acid.Most preferred aromatic binary carboxylic acid is a terephthalic acid.
Water described in the above-mentioned steps (1) also can be the waste water that produced in the pre-polymerization process last time.The aliphatic diamine that contains 4 to 14 carbon atoms that contains 0.1～5 weight % in the waste water.
Prepolymerization in the above-mentioned steps (1) is aromatic binary carboxylic acid, the aliphatic diamine, water, end-capping reagent, the catalyzer that contain 4 to 14 carbon atoms to be joined in the autoclave react, prepolymerized temperature of reaction is 200～280 ℃, reaction system pressure 1～5MPa, reaction times is 1～6 hour, the reaction later stage keep-ups pressure stable by the water in the discharge system, after reaction finishes with the prepolymer dried for standby, the wastewater collection that separates out when the waste water that reacts later stage discharge system is finished the after drying prepolymer with reaction is used during for next polymerization together.Wherein, preferred temperature of reaction is 220～250 ℃; The preferred reaction times is 2～4 hours; Preferred reaction system pressure is 1.5～3Mpa.By the prepolymerization reaction, the limiting viscosity [η] that can obtain measuring in 25 ℃ 96% sulfuric acid is 0.06～0.3dl/g, the prepolymer in preferred 0.08～0.2dl/g scope.
Wherein catalyzer comprises phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or its salt or its ester, and preferably phosphoric acid is received, sodium phosphite, sodium hypophosphite, potassium phosphite.The amount of catalyzer is raw-material 0.01～2 weight % (starting material refers to aromatic binary carboxylic acid, contains the gross weight of aliphatic diamine, end-capping reagent and the catalyzer of 4 to 14 carbon atoms), preferred 0.05～1 weight %.
End-capping reagent comprises monocarboxylic acid or monoamine or its mixture.Wherein preferred monocarboxylic acid, because with respect to monoamine, monocarboxylic acid toxicity is little, and is not volatile, is convenient to handle; Monocarboxylic acid comprises aliphatics monocarboxylic acid such as acetate, propionic acid, butyric acid, valeric acid, caproic acid, PIVALIC ACID CRUDE (25), isopropylformic acid, enanthic acid, sad, n-nonanoic acid, lauric acid, stearic acid etc.; Alicyclic monocarboxylic acid such as cyclopropane-carboxylic acid, pentamethylene acetate, hexahydrobenzoic acid etc.; Aromatic series monocarboxylic acid such as phenylformic acid, p-methylbenzoic acid, o-toluic acid, p-tert-butyl benzoic acid, Whitfield's ointment, anisic acid, toluylic acid, styracin etc.End-capping reagent can be one or more in them.Wherein Zui Jia monocarboxylic acid is acetate, propionic acid, butyric acid, lauric acid, stearic acid, phenylformic acid or toluylic acid.Monoamine comprises aliphatics monoamine such as ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, sec-butylamine, isobutylamine, n-amylamine, n-Decylamine, n-Laurylamine, stearylamine etc.; Alicyclic monoamine such as hexahydroaniline etc.; Aromatic series monoamine such as aniline, para-totuidine, Ortho Toluidine, 2,6-xylidine, 3,4-xylidine, o ethyl aniline etc.End-capping reagent can be one or more in them.Best monoamine is ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, aniline or para-totuidine.The molar weight of end-capping reagent is 0.2～10% of an aromatic binary carboxylic acid, preferred 0.5～5%.Because when the amount of end-capping reagent is too high, can cause the molecular weight of polymkeric substance less than normal; The amount of end-capping reagent is crossed when hanging down, and can cause the molecular weight active end group content bigger than normal or polymkeric substance of polymkeric substance bigger than normal.
The water yield that the prepolymerization initial stage adds in the above-mentioned steps (1) is 15～35 weight %.Because if the water yield that adds is very few, material will solidify in the polymeric process so, and reaction can't be carried out, and product can't be discharged in reactor; If the water yield that adds is excessive, the speed of polyreaction can reduce, the prepolymer limiting viscosity that obtains also can reduce, can't carry out the tackify reaction smoothly, and in order to improve the limiting viscosity of speed of response and prepolymer, in polymerization process, to discharge a large amount of water, will inevitably cause the serious loss of diamine, destroy monomeric molar ratio.
The water that is added in the above-mentioned steps (1) can not participated in the prepolymerization reaction, and can generate a spot of water in the prepolymerization reaction, can collect the waste water of slightly Duoing than add-on after pre-polymerization process finishes, and these waste water can join again in the next prepolymerization reaction.So move in circles, the prepolymerization reaction does not need to use new water, and does not almost have the discharging of waste water.Because contain a spot of diamine in the waste water that produces in the pre-polymerization process, the words of discharging can cause the loss of diamine, and waste water is carried out recycle, have also just improved the utilization ratio of raw material diamine.Simultaneously, the diamine that the prepolymerization initial stage adds in the waste water has compensated the diamine that runs off along with the discharge of water in the pre-polymerization process, guarantee the molar ratio balance of monomer di-carboxylic acid and diamine, helped carrying out smoothly of polyreaction, obtained the semiaromatic polyamide composition of high limiting viscosity.
The tackify of prepolymer can react by solid-phase tack producing reaction or fusion tackify and realize in the above-mentioned steps (2), wherein solid-phase tack producing method preferably.Solid-phase tack producing melting point polymer with under carry out, preferred temperature of reaction is 220～280 ℃, the solid-phase tack producing reaction times is 3～20 hours, preferred 5～15 hours; In order to prevent the polymkeric substance oxidation, the solid-phase tack producing reaction is carried out under nitrogen atmosphere or under the vacuum condition, preferably carries out under nitrogen atmosphere.The advantage of solid-phase tack producing is that temperature of reaction is low, and DeR is few, and the polymeric amide tone, dimensional stability, the thermotolerance that obtain are better.The fusion tackify is to carry out on the extrusion equipment of band venting port; Fusion tackify temperature is higher than the fusing point of prepolymer, and preferred temperature of reaction is 290～350 ℃; The fusion tackify reaction times is 1～8 minute, preferred 2～6 minutes.The advantage of fusion tackify is that the reaction times is shorter.After the tackify reaction, obtain the end product semiaromatic polyamide composition.
The semiaromatic polyamide composition that the present invention obtains, its limiting viscosity [η] is 0.8～2.5dl/g, preferred 1.0～2.0dl/g; Content of carboxyl end group is 15～80mol/t, preferred 15～50mol/t; Terminal amino group content is 15～80mol/t, preferred 15～60mol/t; Fusing point is 270～330 ℃, preferred 290～330 ℃.The reason of preferred this scope is, crosses when low when fusing point, and the thermotolerance of polymeric amide does not reach requirement of the present invention; And DeR can take place when too high in fusing point when hot-work.
Compared with prior art, the present invention has following beneficial effect: 1. semiaromatic polyamide composition preparation method of the present invention has carried out recycle to the waste water that produces in the polymerization process, greatly reduces discharged waste water; And the raw material in the waste water has been carried out recycling effectively, improved the utilization ratio of raw material diamine; Simultaneously, the diamine that the prepolymerization initial stage adds in the waste water has compensated the diamine that runs off along with the discharge of water in the pre-polymerization process, has guaranteed the molar ratio balance of monomer di-carboxylic acid and diamine.2. the semiaromatic polyamide composition of the present invention's preparation has higher degree of crystallinity, limiting viscosity and heat resisting temperature, and form and aspect are good, and active end group content is low, and good processing stability is not corroded mould.As required, can add oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor; Also can strengthen by adding glass fibre, carbon fiber, mineral filler; Can also prepare polymer alloy with other polymer blending simultaneously.
Embodiment
Present invention is described for mode that will be by embodiment, but do not limit the invention.All characteristics are all measured by the following method in embodiment and Comparative Examples.
1. limiting viscosity [η]
In 25 ℃ the vitriol oil, measure concentration and be 0.05,0.1,0.3 and the logarithm reduced viscosity η of the polymeric amide of 1g/dl
Inh
η
inh＝[ln(t
1/t
0)]/C
Wherein, η
InhExpression logarithm reduced viscosity (dl/g), t
0The flushing time (sec) of expression solvent, t1 represents the flushing time (sec) of sample solution, C represents the concentration (g/dl) of sample solution.
With η
InhData to be extrapolated to concentration be 0, with the limiting viscosity [η] that obtains sample.
2. hold amido content
With full-automatic current potential titration apparatus titration sample end amido content.Get the 0.5g polymkeric substance, add phenol 45ml and anhydrous methanol 3ml, reflux after the observation sample dissolves fully, is chilled to room temperature, with the hydrochloric acid standard solution titration end amido content of having demarcated.
3. content of carboxyl end group
With full-automatic current potential titration apparatus titration sample content of carboxyl end group.Get the 0.5g polymkeric substance, add ortho-cresol 50ml, the dissolving that refluxes is put cold back and is added 400 μ L formaldehyde solutions rapidly, with the KOH-ethanolic soln titration content of carboxyl end group of having demarcated.
4. diamine content in the waste water
With diamine content in the waste water of full-automatic current potential titration apparatus titration prepolymerization generation.Get 100ml waste water, with the hydrochloric acid standard solution titration diamine content of having demarcated.
5. fusing point and melting heat
Adopt the fusing point and the melting heat of Perkin Elmer DSC-6 analyser specimen, nitrogen atmosphere, flow velocity are 40mL/min.Earlier be warming up to 340 ℃ during test with 10 ℃/min, keep 2min at 340 ℃, be cooled to 50 ℃ with 10 ℃/min then, be warming up to 340 ℃ with 10 ℃/min again, the endotherm peak temperature of this moment is made as fusing point Tm, by the heat absorption calculated by peak area melting heat Δ Hm of this moment.
6. degree of crystallinity
Measure crystallinity of polymer with X-ray diffraction method.The fused polymkeric substance is prepared amorphous sample with the liquid nitrogen quenching, and the X-ray diffraction peak area of amorphous sample and polymer samples is respectively S
1And S
2, calculate degree of crystallinity by following formula.
X
c＝(S
2-S
1)/S
2×100
Wherein, X
cExpression degree of crystallinity (%), S
1The X-ray diffraction peak area of expression amorphous sample, S
2The X-ray diffraction peak area of expression polymer samples.
Comparative Examples 1
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 3323g (20mol) terephthalic acid, 3446g (20mol) 1,10-decamethylene diamine, 73.27g (0.6mol) phenylformic acid, 6.85g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 2283g (counting 25 weight % based on the gross weight of reaction system) deionized water heat up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.14dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 2361g in the pre-polymerization process altogether, the diamine content in the waste water is 1.7 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the PA10T resin, and fusing point is 319 ℃, melting heat 67.5J/g, and limiting viscosity [η] is 1.02dl/g, and end amido content is 14mol/t, and content of carboxyl end group is 107mol/t.The results are shown in the table 1.
Embodiment 1
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 3323g (20mol) terephthalic acid, 3446g (20mol) 1, waste water in 10-decamethylene diamine, 73.27g (0.6mol) phenylformic acid, 6.85g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 2283g (counting 25 weight % based on the gross weight of the reaction system) Comparative Examples 1 heats up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.15dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 2339g in the pre-polymerization process altogether, the diamine content in the waste water is 1.8 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the PA10T resin, and fusing point is 320 ℃, melting heat 73.5J/g, and limiting viscosity [η] is 1.38dl/g, and end amido content is 35mol/t, and content of carboxyl end group is 43mol/t.The results are shown in the table 1.
Embodiment 2
Repeat the preparation process of embodiment 1, different is the waste water of waste water for collecting in embodiment 1 polymerization process that is added.The results are shown in the table 1.
Embodiment 3
Repeat the preparation process of embodiment 1, different is the waste water of waste water for collecting in embodiment 2 polymerization processes that is added.The results are shown in the table 1.
Embodiment 4
Repeat the preparation process of embodiment 1, different is the waste water of waste water for collecting in embodiment 3 polymerization processes that is added.The results are shown in the table 1.
Table 1
| Comparative Examples 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Terephthalic acid (mol) | 20 | 20 | 20 | 20 | 20 |
| 1 (mol) | 20 | 20 | 20 | 20 | 20 |
| Deionized water add-on (g) | 2283 | ||||
| Waste water add-on (g) | 2283 | 2283 | 2283 | 2283 | |
| Wastewater collection amount (g) | 2361 | 2339 | 2415 | 2396 | 2357 |
| Diamine content (weight %) in the waste water | 1.7 | 1.8 | 1.6 | 1.9 | 1.7 |
| Prepolymer limiting viscosity [η] (dl/g) | 0.14 | 0.15 | 0.14 | 0.15 | 0.16 |
| Polymeric amide limiting viscosity [η] (dl/g) | 1.02 | 1.38 | 1.41 | 1.45 | 1.34 |
| End amido content (mol/t) | 14 | 35 | 37 | 41 | 39 |
| Content of carboxyl end group (mol/t) | 107 | 43 | 41 | 38 | 50 |
| Fusing point (℃) | 319 | 320 | 320 | 321 | 320 |
| ΔHm(J/g) | 67.5 | 73.5 | 69.6 | 71.4 | 75.2 |
| Degree of crystallinity (%) | 23 | 26 | 25 | 27 | 24 |
Comparative Examples 2
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 2824g (17mol) terephthalic acid, 498g (3mol) m-phthalic acid, 3446g (20mol) 1,10-decamethylene diamine, 73.27g (0.6mol) phenylformic acid, 6.85g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 2283g (counting 25 weight % based on the gross weight of reaction system) deionized water heat up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.13dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 2356g in the pre-polymerization process altogether, the diamine content in the waste water is 1.5 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the semiaromatic polyamide composition resin, and fusing point is 291 ℃, melting heat 38.7J/g, and limiting viscosity [η] is 0.97dl/g, and end amido content is 19mol/t, and content of carboxyl end group is 112mol/t.The results are shown in the table 2.
Embodiment 5
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 2824g (17mol) terephthalic acid, 498g (3mol) m-phthalic acid, 3446g (20mol) 1, waste water in 10-decamethylene diamine, 73.27g (0.6mol) phenylformic acid, 6.85g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 2283g (counting 25 weight % based on the gross weight of the reaction system) Comparative Examples 2 heats up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.15dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 2386g in the pre-polymerization process altogether, the diamine content in the waste water is 1.8 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the semiaromatic polyamide composition resin, and fusing point is 292 ℃, melting heat 45.3J/g, and limiting viscosity [η] is 1.27dl/g, and end amido content is 43mol/t, and content of carboxyl end group is 51mol/t.The results are shown in the table 2.
Embodiment 6
Repeat the preparation process of embodiment 5, different is the waste water of waste water for collecting in embodiment 5 polymerization processes that is added.The results are shown in the table 2.
Embodiment 7
Repeat the preparation process of embodiment 5, different is the waste water of waste water for collecting in embodiment 6 polymerization processes that is added.The results are shown in the table 2.
Embodiment 8
Repeat the preparation process of embodiment 5, different is the waste water of waste water for collecting in embodiment 7 polymerization processes that is added.The results are shown in the table 2.
Table 2
| Comparative Examples 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Terephthalic acid (mol) | 17 | 17 | 17 | 17 | 17 |
| M-phthalic acid (mol) | 3 | 3 | 3 | 3 | 3 |
| 1 (mol) | 20 | 20 | 20 | 20 | 20 |
| Deionized water add-on (g) | 2283 | ||||
| Waste water add-on (g) | 2283 | 2283 | 2283 | 2283 | |
| Wastewater collection amount (g) | 2356 | 2386 | 2325 | 2334 | 2406 |
| Diamine content (weight %) in the waste water | 1.5 | 1.8 | 1.8 | 1.9 | 1.7 |
| Prepolymer limiting viscosity [η] (dl/g) | 0.13 | 0.15 | 0.14 | 0.13 | 0.16 |
| Polymeric amide limiting viscosity [η] (dl/g) | 0.97 | 1.27 | 1.36 | 1.32 | 1.43 |
| End amido content (mol/t) | 19 | 43 | 36 | 35 | 44 |
| Content of carboxyl end group (mol/t) | 112 | 51 | 47 | 39 | 54 |
| Fusing point (℃) | 291 | 292 | 292 | 291 | 292 |
| ΔHm(J/g) | 38.7 | 45.3 | 39.6 | 42.9 | 47.2 |
| Degree of crystallinity (%) | 11 | 14 | 15 | 13 | 16 |
Comparative Examples 3
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 3323g (20mol) terephthalic acid, 2929g (17mol) 1,10-decamethylene diamine, 517g (3mol) 5-methyl isophthalic acid, 9-nonamethylene diamine, 73.27g (0.6mol) phenylformic acid, 6.85g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 2283g (counting 25 weight % based on the gross weight of reaction system) deionized water heat up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.13dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 2317g in the pre-polymerization process altogether, the diamine content in the waste water is 1.6 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the semiaromatic polyamide composition resin, and fusing point is 294 ℃, melting heat 41.2J/g, and limiting viscosity [η] is 1.07dl/g, and end amido content is 16mol/t, and content of carboxyl end group is 96mol/t.The results are shown in the table 3.
Embodiment 9
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 3323g (20mol) terephthalic acid, 2929g (17mol) 1,10-decamethylene diamine, 517g (3mol) 5-methyl isophthalic acid, waste water in 9-nonamethylene diamine, 73.27g (0.6mol) phenylformic acid, 6.85g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 2283g (counting 25 weight % based on the gross weight of the reaction system) Comparative Examples 3 heats up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.15dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 2395g in the pre-polymerization process altogether, the diamine content in the waste water is 1.7 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the semiaromatic polyamide composition resin, and fusing point is 294 ℃, melting heat 48.3J/g, and limiting viscosity [η] is 1.29dl/g, and end amido content is 34mol/t, and content of carboxyl end group is 50mol/t.The results are shown in the table 3.
Comparative Examples 4
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 1994g (12mol) terephthalic acid, 1329g (8mol) m-phthalic acid, 2324g (20mol) 1,6-hexanediamine, 73.27g (0.6mol) phenylformic acid, 5.73g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 1909g (counting 25 weight % based on the gross weight of reaction system) deionized water heat up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.14dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 1960g in the pre-polymerization process altogether, the diamine content in the waste water is 1.4 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the semiaromatic polyamide composition resin, and fusing point is 312 ℃, melting heat 34.8J/g, and limiting viscosity [η] is 0.96dl/g, and end amido content is 17mol/t, and content of carboxyl end group is 92mol/t.The results are shown in the table 3.
Embodiment 10
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 1994g (12mol) terephthalic acid, 1329g (8mol) m-phthalic acid, 2324g (20mol) 1, waste water in 6-hexanediamine, 73.27g (0.6mol) phenylformic acid, 5.73g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 1909g (counting 25 weight % based on the gross weight of the reaction system) Comparative Examples 4 heats up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.15dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 2053g in the pre-polymerization process altogether, the diamine content in the waste water is 1.4 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the semiaromatic polyamide composition resin, and fusing point is 312 ℃, melting heat 33.4J/g, and limiting viscosity [η] is 1.32dl/g, and end amido content is 33mol/t, and content of carboxyl end group is 39mol/t.The results are shown in the table 3.
Comparative Examples 5
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 3323g (20mol) terephthalic acid, 1394g (12mol) 1,6-hexanediamine, 930g (8mol) 2-methyl isophthalic acid, 5-pentamethylene diamine, 73.27g (0.6mol) phenylformic acid, 5.73g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 1909g (counting 25 weight % based on the gross weight of reaction system) deionized water heat up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.15dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 2023g in the pre-polymerization process altogether, the diamine content in the waste water is 1.3 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the semiaromatic polyamide composition resin, and fusing point is 316 ℃, melting heat 34.2J/g, and limiting viscosity [η] is 1.11dl/g, and end amido content is 19mol/t, and content of carboxyl end group is 87mol/t.The results are shown in the table 3.
Embodiment 11
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 3323g (20mol) terephthalic acid, 1394g (12mol) 1,6-hexanediamine, 930g (8mol) 2-methyl isophthalic acid, waste water in 5-pentamethylene diamine, 73.27g (0.6mol) phenylformic acid, 5.73g (counting 0.1 weight % based on raw-material gross weight) sodium hypophosphite, 1909g (counting 25 weight % based on the gross weight of the reaction system) Comparative Examples 5 heats up behind the nitrogen purging.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2Mpa and proceed 2 hours, keep-up pressure constant by removing formed water, discharging after reaction is finished, prepolymer is the prepolymer of 0.15dl/g in 80 ℃ of following vacuum-dryings 24 hours thereby obtain limiting viscosity [η].Collect waste water 1987g in the pre-polymerization process altogether, the diamine content in the waste water is 1.5 weight %.Prepolymer solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres obtains the semiaromatic polyamide composition resin, and fusing point is 317 ℃, melting heat 35.7J/g, and limiting viscosity [η] is 1.43dl/g, and end amido content is 40mol/t, and content of carboxyl end group is 49mol/t.The results are shown in the table 3.
Table 3
| Comparative Examples 3 | Embodiment 9 | Comparative Examples 4 | Embodiment 10 | Comparative Examples 5 | Embodiment 11 | |
| Terephthalic acid (mol) | 20 | 20 | 12 | 12 | 20 | 20 |
| M-phthalic acid (mol) | 8 | 8 | ||||
| 1 (mol) | 17 | 17 | ||||
| The 5-methyl isophthalic acid, 9-nonamethylene diamine (mol) | 3 | 3 | ||||
| 1,6-hexanediamine (mol) | 20 | 20 | 12 | 12 | ||
| The 2-methyl isophthalic acid, 5-pentamethylene diamine (mol) | 8 | 8 | ||||
| Deionized water add-on (g) | 2283 | 1909 | 1909 |
| Waste water add-on (g) | 2283 | 1909 | 1909 | |||
| Wastewater collection amount (g) | 2317 | 2395 | 1960 | 2053 | 2023 | 1987 |
| Diamine content (weight %) in the waste water | 1.6 | 1.7 | 1.4 | 1.4 | 1.3 | 1.5 |
| Prepolymer limiting viscosity [η] (dl/g) | 0.13 | 0.15 | 0.14 | 0.15 | 0.15 | 0.15 |
| Polymeric amide limiting viscosity [η] (dl/g) | 1.07 | 1.29 | 0.96 | 1.32 | 1.11 | 1.43 |
| End amido content (mol/t) | 16 | 34 | 17 | 33 | 19 | 40 |
| Content of carboxyl end group (mol/t) | 96 | 50 | 92 | 39 | 87 | 49 |
| Fusing point (℃) | 294 | 294 | 312 | 312 | 316 | 317 |
| ΔHm(J/g) | 41.2 | 48.3 | 34.8 | 33.4 | 34.2 | 35.7 |
| Degree of crystallinity (%) | 12 | 14 | 10 | 9 | 8 | 11 |
Claims (7)
1. the preparation method of semi-aromatic polyamide of a low wastewater discharge is characterized in that may further comprise the steps:
(1) aromatic binary carboxylic acid, the aliphatic diamine that contains 4 to 14 carbon atoms and water are joined carries out prepolymerization reaction in the autoclave pressure;
(2) the above-mentioned prepolymer that obtains is promptly got semiaromatic polyamide composition by solid-phase tack producing reaction or the reaction of fusion tackify;
Described water is the waste water of collecting after pre-polymerization process finishes, and joins in the next prepolymerization reaction; The aliphatic diamine that contains 4 to 14 carbon atoms that contains 0.1～5 weight % in the described waste water.
2. preparation method according to claim 1 is characterized in that aliphatic diamine described in the step (1) is one or more the mixture in straight chain aliphatic diamine, side chain aliphatic diamine or the cycloalphatic diamine.
3. preparation method according to claim 2 is characterized in that described straight chain aliphatic diamine is 1,4-butanediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 carbon diamines or 1,12-12 carbon diamines; Described side chain aliphatic diamine is the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine; Described cycloalphatic diamine is cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
4. preparation method according to claim 1, it is characterized in that aromatic binary carboxylic acid described in the step (1) is terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-naphthalic acid, 1,4-naphthalic acid, 4,4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid.
5. preparation method according to claim 1, it is characterized in that the prepolymerization reaction described in the step (1) is aromatic binary carboxylic acid, the aliphatic diamine, water, end-capping reagent, the catalyzer that contain 4 to 14 carbon atoms to be joined in the autoclave react, temperature of reaction is 200～280 ℃, reaction system pressure 1～5MPa, reaction times is 1～6 hour, the reaction later stage discharge water in the system keep-up pressure stable, after reaction finishes with the prepolymer dried for standby; The water add-on is 15～35 weight % of whole reaction system, and the amount of catalyzer is raw-material 0.01～2 weight %, and the molar weight of end-capping reagent is 0.2～10% of an aromatic binary carboxylic acid; Described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or its salt or its ester; Described end-capping reagent is monocarboxylic acid or monoamine or its mixture.
6. preparation method according to claim 5 is characterized in that described catalyzer is sodium phosphate, sodium phosphite, sodium hypophosphite, potassium phosphite; Described monocarboxylic acid is acetate, propionic acid, butyric acid, lauric acid, stearic acid, phenylformic acid or toluylic acid; Described monoamine is ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, aniline or para-totuidine.
7. preparation method according to claim 1 is characterized in that the solid-phase tack producing reaction described in the step (2) carries out under nitrogen atmosphere or under the vacuum condition, temperature of reaction is 220～280 ℃, and the reaction times is 3～20 hours; The reaction of fusion tackify is to carry out on the extrusion equipment of band venting port, and temperature of reaction is 290～350 ℃, and the reaction times is 1～8 minute.
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| CN102153741B (en) * | 2010-02-11 | 2013-11-06 | 上海杰事杰新材料(集团)股份有限公司 | Homopolymer and copolymer of long-carbon-chain semi-aromatic high-temperature-resistant polyamide and synthesis method thereof |
| CN103827172B (en) * | 2011-09-22 | 2016-06-29 | 尤尼吉可株式会社 | Semiaromatic polyamide composition and the molded body formed by it |
| CN102964590B (en) * | 2012-11-30 | 2014-06-25 | 金发科技股份有限公司 | Polyamide and preparation method and application thereof |
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| CN104530421A (en) * | 2015-01-05 | 2015-04-22 | 无锡殷达尼龙有限公司 | Semi-aromatic polyamide preparation method |
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| CN107189060B (en) * | 2016-03-14 | 2019-09-20 | 浙江新和成特种材料有限公司 | A kind of semiaromatic polyamide composition and preparation method thereof |
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| CN109503828A (en) * | 2018-11-21 | 2019-03-22 | 重庆晟淦新材料科技有限公司 | A kind of semiaromatic Long carbon chain copolymer nylon and its synthetic method |
| CN114058008A (en) * | 2021-12-13 | 2022-02-18 | 山东广垠新材料有限公司 | Process for preparing semi-aromatic polyamides end-capped with monocarboxylic acids, semi-aromatic polyamides and molding compositions |
| CN114058009B (en) * | 2021-12-13 | 2023-11-10 | 山东广垠新材料有限公司 | Process for the preparation of semi-aromatic polyamides with reduced diamine monomer loss, semi-aromatic polyamides and molding compositions |
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| CN1127266A (en) * | 1994-08-17 | 1996-07-24 | 东丽株式会社 | Copolymeric polyamide and preparation of same |
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