CN112920400A - Bio-based semi-aromatic polyamide copolymer and preparation method, composition and application thereof - Google Patents
Bio-based semi-aromatic polyamide copolymer and preparation method, composition and application thereof Download PDFInfo
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- CN112920400A CN112920400A CN202011596479.1A CN202011596479A CN112920400A CN 112920400 A CN112920400 A CN 112920400A CN 202011596479 A CN202011596479 A CN 202011596479A CN 112920400 A CN112920400 A CN 112920400A
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- Prior art keywords
- bio
- semi
- aromatic polyamide
- copolymer
- salt
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- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 115
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 150000004985 diamines Chemical class 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 229920006021 bio-based polyamide Polymers 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 23
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 16
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 12
- DVPHDWQFZRBFND-DMHDVGBCSA-N 1-o-[2-[(3ar,5r,6s,6ar)-2,2-dimethyl-6-prop-2-enoyloxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-[4-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chlorophenyl)-4-oxoazetidin-3-yl]oxy-4-oxobutanoyl]oxyethyl] 4-o-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chloropheny Chemical group C1([C@H]2[C@H](C(N2SC(C)CC)=O)OC(=O)CCC(=O)OC(COC(=O)CCC(=O)O[C@@H]2[C@@H](N(C2=O)SC(C)CC)C=2C(=CC=CC=2)Cl)[C@@H]2[C@@H]([C@H]3OC(C)(C)O[C@H]3O2)OC(=O)C=C)=CC=CC=C1Cl DVPHDWQFZRBFND-DMHDVGBCSA-N 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000006082 mold release agent Substances 0.000 claims description 7
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 235000019438 castor oil Nutrition 0.000 abstract description 8
- 239000004359 castor oil Substances 0.000 abstract description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract description 8
- 235000019484 Rapeseed oil Nutrition 0.000 abstract description 6
- 239000003549 soybean oil Substances 0.000 abstract description 6
- 235000012424 soybean oil Nutrition 0.000 abstract description 6
- -1 amide salts Chemical class 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- VVZJLMKXPZPTPO-UHFFFAOYSA-N benzene-1,4-dicarboxamide nonane Chemical compound C(C1=CC=C(C(=O)N)C=C1)(=O)N.CCCCCCCCC VVZJLMKXPZPTPO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 150000003951 lactams Chemical class 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000155 melt Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- 239000010773 plant oil Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QXOYPGTWWXJFDI-UHFFFAOYSA-N nonanedinitrile Chemical compound N#CCCCCCCCC#N QXOYPGTWWXJFDI-UHFFFAOYSA-N 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 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 1
- BRSICLJIUFXBCB-UHFFFAOYSA-N 2-methyloctane-1,1-diol Chemical compound CCCCCCC(C)C(O)O BRSICLJIUFXBCB-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002028 Biomass Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- HOKKHZGPKSLGJE-GSVOUGTGSA-N N-Methyl-D-aspartic acid Chemical compound CN[C@@H](C(O)=O)CC(O)=O HOKKHZGPKSLGJE-GSVOUGTGSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000005819 Potassium phosphonate Substances 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
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- 238000005576 amination reaction Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 1
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- LEMKWEBKVMWZDU-UHFFFAOYSA-N nonanedial Chemical compound O=CCCCCCCCC=O LEMKWEBKVMWZDU-UHFFFAOYSA-N 0.000 description 1
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- 239000003279 phenylacetic acid Substances 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 235000011009 potassium phosphates Nutrition 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 description 1
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- 238000007086 side reaction Methods 0.000 description 1
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- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a preparation method of a bio-based semi-aromatic polyamide copolymer. The invention takes reproducible castor oil or rapeseed oil or soybean oil as raw materials to prepare a bio-based diamine monomer, then the bio-based diamine monomer reacts with terephthalic acid to form a salt, and then the bio-based diamine monomer reacts with other amide salts or lactam by melt polymerization to synthesize the bio-based poly (nonane terephthalamide) copolymer. The bio-based semi-aromatic polyamide copolymer prepared by the invention has a bio-based content of more than 50 percent, is different from other petroleum-based sources, reduces the dependence and consumption on petroleum resources, reduces the emission of carbon dioxide, reduces carbon footprint, and is low-carbon and environment-friendly; the preparation method has good controllability, does not contain organic solvent and is environment-friendly; the semi-aromatic polyamide copolymer-containing composition prepared by the copolymer has good heat resistance, can still keep good rigidity and strength at high temperature, and can be widely applied to the fields of electronic appliances and automobiles, in particular to electronic connector parts.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a bio-based semi-aromatic polyamide copolymer, and a preparation method, a composition and application thereof.
Background
Semi-aromatic nylon PA9T is a polyamide material obtained by polycondensation of nonane diamine and terephthalic acid, has the characteristics of high temperature resistance of aromatic nylon and easy processing of aliphatic nylon, and has the advantages of balanced rigidity and toughness, good chemical resistance, extremely low water absorption rate of only 0.17 percent, good dimensional stability, better comprehensive performance of traditional nylon, and important application in the electronic and electrical industry, the automobile industry and the fiber industry.
The industrial production method of nonanediamine (a monomer of PA 9T) was first identified by the company of Coly, Japan, and PA9T resin was first developed. The method is characterized in that butadiene is used as a raw material, 2, 7-diene-1-octanol is obtained through catalytic reaction (patent US4417079), alcohol is catalyzed and oxidized by a copper chromite catalyst to generate 7-ene-1-octanal (patent US4510331), aldehyde is carbonylated by carbon monoxide under high pressure catalysis to generate a mixture of nonane dialdehyde and 2-methyl octanediol (patent EP1489087), and dialdehyde is reduced and aminated under high pressure catalysis to generate a mixture of nonane diamine and 2-methyl octanediol diamine (patent JP58167547), and the reaction formula is as follows:
the process technology is advanced, but petroleum raw materials are used as a starting point, the petroleum raw materials are non-renewable resources, the finally synthesized product is not pure nonanediamine, the current products produced in an industrialized mode are all mixtures of two isomers of Nonanediamine (NMDA) and 2-methyl-1, 8-octanediamine (MODA), the content of nonanediamine is low, and the application of the product in the fields of medicines and foods is limited by using the petroleum-based products as the raw materials. The petroleum resource is non-renewable resource, the energy crisis is a future worldwide problem, renewable natural resources are utilized to replace the traditional industrial mode, and the method is one of the directions of solving the energy shortage and sustainable development. Compared with the traditional petroleum-based plastic, the bio-based plastic produced by using the biomass can consume less petrochemical raw material resources, and reduces the consumption and dependence on energy sources such as petroleum and natural gas. The bio-based 1,9 nonane diamine monomer is obtained by extracting castor oil or other natural vegetable oil from castor seeds, obtaining oleic acid from other natural vegetable oil such as rapeseed oil or soybean oil through saponification and acidification, and then carrying out oxidative cracking on the oleic acid to break double bonds of the oleic acid to obtain azelaic acid, wherein the azelaic acid can be obtained through potassium permanganate oxidation, hydrogen peroxide oxidation, ozone oxidation or other oxidant oxidation, the product yield and the influence on the environment are comprehensively considered, and the hydrogen peroxide oxidation effect is the best. Azelaic acid is subject to ammoniation and dehydration to obtain azelaic acid nitrile, and then is subject to hydrogenation reaction under the action of a certain catalyst to obtain nonane diamine, wherein the reaction scheme is shown in figure 1.
Chinese patent CN 106220513B discloses a method for preparing nonane diamine, which takes bio-based nonane diacid as a raw material, and prepares nonane dinitrile through neutralization reaction, dehydration reaction and decompression reaction in sequence, and the nonane dinitrile is subjected to hydrogenation reaction to prepare the nonane diamine, thereby realizing the aim of preparing a pure product of the nonane diamine from crude crystals of the nonane diacid, wherein the final molar conversion rate of the nonane diamine is 95-99%, and the product purity is more than 99%.
Therefore, in view of the problems of non-renewable petroleum-based nonanediamine source and low product purity, there is a need to develop a bio-based semi-aromatic polyamide copolymer to solve the above problems.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a semi-aromatic polyamide copolymer whose repeating structural unit satisfies any one of the following three conditions:
(a)
(b)
(c)
wherein, the synthetic monomers of the repeating structural units shown in the formulas 1-1, 2-1 and 3-1 all contain nonane diamine, the nonane diamine is bio-based 1,9 nonane diamine and is derived from natural plant castor oil or other natural plant oils, the other natural plant oils can be, but are not limited to, rapeseed oil or soybean oil,
in the formula 2-2, x represents at least one of 5, 6, 9, 10 and 12; y represents at least one of 6, 9, 10, 11, 12, 13, 14, 16 and 18;
in the formula 3-2, z represents one of 6, 11 and 12.
The present application also provides a method for preparing the above semi-aromatic polyamide copolymer, synthesis of the semi-aromatic polyamide copolymer (a), i.e., a method for preparing a copolymer composed of the repeating structural unit represented by formula 1-1, comprising the steps of:
reacting the first bio-based polyamide salt (9T) with the second bio-based polyamide salt (9I) to obtain a semi-aromatic polyamide copolymer (a),
wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid; the synthetic monomers of the second bio-based polyamide salt include nonanediamine and isophthalic acid.
Specifically, terephthalic acid and nonane diamine are respectively dissolved in water, and then the mixture is injected into a reaction kettle according to the molar ratio of 1: 1-1.05, and salifying reaction is carried out at a certain temperature to obtain a first bio-based polyamide salt (9T); respectively dissolving isophthalic acid and nonane diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain a second bio-based polyamide salt (9I);
adding a first bio-based polyamide salt (9T), a second bio-based polyamide salt (9I) and water into a polymerization reaction kettle, vacuumizing, heating, and carrying out melt polymerization reaction to obtain the semi-aromatic polyamide copolymer (a), wherein the intrinsic viscosity is controlled to be 1.2-2.5 dl/g.
The present application also provides a process for preparing the above-mentioned semi-aromatic polyamide copolymer, synthesis of the semi-aromatic polyamide copolymer (b), i.e., a process for preparing a copolymer composed of repeating structural units represented by the formulae 2-1 and 2-2, comprising the steps of:
reacting the third polyamidate (XY) with the first biobased polyamidate (9T) to obtain a semi-aromatic polyamide copolymer (b),
wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid; the synthetic monomers of the third polyesteramide include monomeric diacids and monomeric diamines.
Specifically, monomer diacid and monomer diamine are respectively dissolved in water, then the mixture is injected into a reaction kettle according to the molar ratio of 1: 1-1.05, and salifying reaction is carried out at a certain temperature to obtain third polyesteramide (XY);
respectively dissolving terephthalic acid and nonane diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain a first bio-based polyamide salt (9T);
and adding the third polyesteramide (XY), the first bio-based polyesteramide (9T) and water into a polymerization reaction kettle, vacuumizing, heating, and carrying out melt polymerization reaction to obtain the semi-aromatic polyamide copolymer (b). Wherein the intrinsic viscosity is controlled to be 1.2 to 2.5 dl/g.
The present application also provides a process for preparing the above-mentioned semi-aromatic polyamide copolymer, synthesis of the semi-aromatic polyamide copolymer (c), i.e., a process for preparing a copolymer composed of repeating structural units represented by the formulae 3-1 and 3-2, comprising the steps of:
reacting the first biobased polyamide salt (9T) with a lactam monomer to obtain the semi-aromatic polyamide copolymer (c). Wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid.
Specifically, terephthalic acid and nonane diamine are respectively dissolved in water, and then the mixture is injected into a reaction kettle according to the molar ratio of 1: 1-1.05, and salifying reaction is carried out at a certain temperature to obtain a first bio-based polyamide salt (9T);
adding the first bio-based polyamide salt (9T), the lactam monomer and water into a polymerization reaction kettle, vacuumizing, heating, and carrying out melt polymerization reaction to obtain the semi-aromatic polyamide copolymer (c). Wherein the intrinsic viscosity is controlled to be 1.2 to 2.5 dl/g.
The present application also provides a composition comprising a semi-aromatic polyamide copolymer as defined above, and at least one additive selected from the group consisting of: inorganic filler, dye, flame retardant, antioxidant, mold release agent, stabilizer and mixture thereof.
The application also provides the application of the semi-aromatic polyamide copolymer-containing composition in the aspects of electronic appliances and automobiles.
Compared with the prior art, the invention has the beneficial effects that:
1. the nonane diamine monomer adopted by the synthetic polyamide material is from natural plant castor oil, is a renewable resource, and reduces the dependence and consumption on petroleum resources;
2. the polyamide is synthesized by preparing the monomer into nylon salt and then carrying out melt polymerization, so that the controllability of the reaction is greatly improved, the degradation and the quality loss of the synthesized monomer in the reaction process are reduced, the occurrence of side reactions is reduced, and the synthesis of a high-quality and high-molecular-weight product is facilitated;
3. most of the preparation schemes of the invention adopt non-organic solvents, so that the preparation method has small burden on the environment and has environmental protection significance.
4. The semi-aromatic polyamide copolymer composition prepared by the invention has good heat resistance, can still keep good rigidity and strength at high temperature, and can be widely applied to the fields of electronic and electric appliances and automobiles, in particular to electronic connector parts.
Drawings
FIG. 1 is a reaction scheme of nonanediamine.
Detailed Description
The technical solutions of the present invention are further illustrated by the following specific embodiments, but the present invention is not limited thereto.
The invention provides a semi-aromatic polyamide copolymer, the repeating structural unit of which satisfies any one of the following three conditions:
(a)
(b)
(c)
wherein, the synthetic monomers of the repeating structural units shown in the formulas 1-1, 2-1 and 3-1 all contain nonane diamine, the nonane diamine is bio-based 1,9 nonane diamine and is derived from natural plant castor oil or other natural plant oil, and the other natural plant oil can be, but is not limited to, rapeseed oil or soybean oil.
In the formula 2-2, x represents at least one of 5, 6, 9, 10 and 12; y represents at least one of 6, 9, 10, 11, 12, 13, 14, 16 and 18;
in the formula 3-2, z represents one of 6, 11 and 12.
Wherein, nonane diamine is a bio-based 1,9 nonane diamine monomer, castor oil or other natural vegetable oil is extracted from the seeds of castor oil, the other natural vegetable oil can be, but is not limited to, rapeseed oil or soybean oil, oleic acid is obtained through saponification and acidification reactions, and then the oleic acid is subjected to oxidative cracking to break the double bonds of the oleic acid, so that azelaic acid is obtained. Azelaic acid is subjected to cyanation and amination under certain conditions to obtain nonanediamine.
Compared with the prior art, the invention takes reproducible castor oil or rapeseed oil or soybean oil as raw materials to prepare the bio-based diamine monomer, then the bio-based diamine monomer reacts with terephthalic acid to form salt, and then the bio-based diamine monomer reacts with other amide salt or lactam by melt polymerization to synthesize the bio-based poly (nonane terephthalamide) copolymer. The semi-aromatic polyamide copolymer prepared by the invention has the bio-based content of more than 50 percent, is different from other petroleum-based sources, reduces the dependence and consumption on petroleum resources, reduces the emission of carbon dioxide, reduces carbon footprint, and is low-carbon and environment-friendly; the preparation method has good controllability, does not contain organic solvent and is environment-friendly; the semi-aromatic polyamide copolymer-containing composition prepared by the copolymer has good heat resistance, can still keep good rigidity and strength at high temperature, and can be widely applied to the fields of electronic appliances and automobiles, in particular to electronic connector parts.
Accordingly, the synthesis of a semi-aromatic polyamide copolymer (a) comprises the steps of:
reacting the first bio-based polyamide salt (9T) with the second bio-based polyamide salt (9I) to obtain a semi-aromatic polyamide copolymer (a),
wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid; the synthetic monomers of the second bio-based polyamide salt include nonanediamine and isophthalic acid.
Specifically, terephthalic acid and nonane diamine are respectively dissolved in water, and then the mixture is injected into a reaction kettle according to the molar ratio of 1: 1-1.05, and salifying reaction is carried out at a certain temperature to obtain a first bio-based polyamide salt (9T);
respectively dissolving isophthalic acid and nonane diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain a second bio-based polyamide salt (9I);
adding the first bio-based polyamide salt (9T), the second bio-based polyamide salt (9I) and water into a polymerization reaction kettle, vacuumizing, heating, and carrying out melt polymerization reaction to obtain the semi-aromatic polyamide copolymer (a), wherein the intrinsic viscosity is controlled to be 1.2-2.5 dl/g.
Preferably, terephthalic acid or isophthalic acid is dispersed in water 2 to 6 times the weight of the dispersion, nonanediamine is dispersed in water 1 to 3 times the weight of the dispersion, the reaction temperature is 60 to 120 ℃, and the pH value after the reaction is 7.2 to 7.6.
Preferably, in the melt polymerization reaction, the mass of the added water is 25-40 wt% of the sum of the mass of the first bio-based polyamide salt (9T) and the mass of the second bio-based polyamide salt (9I); the melt polymerization reaction specifically comprises:
adding the dried first bio-based polyamide salt (9T), the dried second bio-based polyamide salt (9I), a catalyst, a molecular weight regulator and a certain amount of water into a high-pressure polymerization kettle, introducing nitrogen for 3 times for replacement, stirring, gradually heating to 180 ℃, keeping for 1-2 hours, heating to 220 ℃ within 30min, keeping the pressure at 1.7-2.5 MPa, reacting at a constant temperature for 4-6 hours, releasing steam in the kettle, reducing the pressure to normal pressure within 1 hour, continuing to heat until the water is volatilized, slowly heating to 280-300 ℃, and reacting for 2-3 hours to obtain the semi-aromatic polyamide copolymer (a).
Preferably, the first bio-based polyamide salt (9T) and the second bio-based polyamide salt (9I) are concentrated, filtered and dried, respectively, before being subjected to the melt polymerization reaction. Specifically, ionic water and ethanol are used as detergents for water washing and alcohol washing, and drying treatment is carried out for 3-8 hours at the temperature of 80-120 ℃ under normal pressure or vacuum.
Wherein, for the semi-aromatic polyamide copolymer (b), the method comprises the following steps:
reacting the third polyamidate (XY) with the first biobased polyamidate (9T) to obtain a semi-aromatic polyamide copolymer (b),
wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid; the synthetic monomers of the third polyesteramide include monomeric diacids and monomeric diamines.
Preferably, the diamine monomer is at least one selected from the group consisting of hexamethylenediamine, nonanediamine, decanediamine and dodecanediamine; the diacid monomer is at least one of adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid and octadecanedioic acid.
Accordingly, the synthesis of a semi-aromatic polyamide copolymer (b) comprises the steps of:
respectively dissolving monomer diacid and monomer diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain third polyesteramide (XY);
respectively dissolving terephthalic acid and nonane diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain a first bio-based polyamide salt (9T);
adding the third polyesteramide (XY), the first bio-based polyesteramide (9T) and water into a polymerization reaction kettle, vacuumizing, heating, and carrying out melt polymerization reaction to obtain a semi-aromatic polyamide copolymer (b); wherein the intrinsic viscosity is controlled to be 1.2 to 2.5 dl/g.
Preferably, terephthalic acid, monomer diacid and monomer diamine are dispersed in water with the weight of 2-6 times of that of the terephthalic acid, the monomer diacid and the monomer diamine, and nonane diamine is dispersed in water with the weight of 1-3 times of that of the nonane diamine, wherein the reaction temperature is 60-120 ℃, and the pH value after the reaction is 7.2-7.6.
Preferably, in the melt polymerization reaction, the mass of the added water is 25-40 wt% of the sum of the mass of the first bio-based polyamide salt (9T) and the mass of the third polyamide salt (XY); the melt polymerization reaction specifically comprises:
adding the dried first bio-based polyamide salt (9T), the dried third polyamide salt (XY), a catalyst, a molecular weight regulator and a certain amount of water into a high-pressure polymerization kettle, introducing nitrogen for replacing for 3 times, stirring, gradually heating to 180 ℃, keeping for 1-2 hours, heating to 220 ℃ within 30min, keeping the pressure at 1.7-2.5 MPa, reacting for 4-6 hours at constant temperature, releasing steam in the kettle, reducing the pressure to normal pressure within 1 hour, continuing heating until water volatilizes, slowly heating to 280-300 ℃, and reacting for 2-3 hours to obtain the semi-aromatic polyamide copolymer (b).
Preferably, the first bio-based polyamidate (9T) and the third polyamidate (XY) are concentrated, filtered and dried, respectively, before the melt polymerization reaction is performed. Specifically, ionic water and ethanol are used as detergents for water washing and alcohol washing, and drying treatment is carried out for 3-8 hours at the temperature of 80-120 ℃ under normal pressure or vacuum.
Wherein, for the semi-aromatic polyamide copolymer (c), the method comprises the following steps:
reacting the first bio-based polyamide salt (9T) with a lactam monomer to obtain the semi-aromatic polyamide copolymer (c), wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid.
Specifically, the synthesis of the semi-aromatic polyamide copolymer (c) comprises the steps of:
respectively dissolving terephthalic acid and nonane diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain a first bio-based polyamide salt (9T);
adding a first bio-based polyamide salt (9T), a lactam monomer and water into a polymerization reaction kettle, vacuumizing, heating, and carrying out melt polymerization reaction to obtain a semi-aromatic polyamide copolymer (c); wherein the intrinsic viscosity is controlled to be 1.2 to 2.5 dl/g.
Preferably, terephthalic acid is dispersed in water 2 to 6 times of the weight of the terephthalic acid, nonane diamine is dispersed in water 1 to 3 times of the weight of the nonane diamine, the reaction temperature is 60 to 120 ℃, and the pH value after the reaction is 7.2 to 7.6.
Preferably, in the melt polymerization reaction, the mass of the added water is 25-40 wt% of the sum of the mass of the first bio-based polyamide salt (9T) and the mass of the lactam monomer; the melt polymerization reaction specifically comprises:
adding the dried first bio-based polyamide salt (9T), the lactam monomer, the catalyst, the molecular weight regulator and a certain amount of water into a high-pressure polymerization kettle, introducing nitrogen for replacing for 3 times, stirring, gradually heating to 180 ℃ for 1-2 hours, heating to 220 ℃ within 30min, keeping the pressure at 1.7-2.5 MPa, reacting for 4-6 hours at constant temperature, releasing steam in the kettle, reducing the pressure to normal pressure within 1 hour, continuing heating until the water is volatilized, slowly heating to 280-300 ℃, and reacting for 2-3 hours to obtain the semi-aromatic polyamide copolymer (c).
Preferably, the first bio-based polyamide salt (9T) is concentrated, filtered and dried before being subjected to the melt polymerization reaction. Specifically, ionic water and ethanol are used as detergents for water washing and alcohol washing, and drying treatment is carried out for 3-8 hours at the temperature of 80-120 ℃ under normal pressure or vacuum.
Preferably, the lactam monomer is selected from at least one of caprolactam, undecanolactam and dodecanolactam.
Preferably, in the synthesis process of the semi-aromatic polyamide copolymer (a), the semi-aromatic polyamide copolymer (b) and the semi-aromatic polyamide copolymer (c), the catalyst can be a phosphorus-based compound, and can be one or more of but not limited to sodium phosphate, potassium phosphate, sodium phosphite, potassium phosphite, sodium hypophosphite and potassium hypophosphite, the invention adopts sodium phosphite, and the mass of the catalyst is 0.01-2.5%, preferably 0.05-1% relative to the total mass of dibasic acid in the initial feeding.
In the synthesis process of the semi-aromatic polyamide copolymer (a), the semi-aromatic polyamide copolymer (b) and the semi-aromatic polyamide copolymer (c), the molecular weight regulator can be selected from monobasic acid, and can be specifically but not limited to 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 or phenylacetic acid. The invention adopts one of benzoic acid or acetic acid, and the molar weight of the added molecular weight regulator is 0.1-5%, preferably 0.5-3% of the total molar weight of the raw material dicarboxylic acid.
Accordingly, there is provided a composition comprising the semi-aromatic polyamide copolymer described above, and further comprising at least one additive selected from the group consisting of: inorganic filler, dye, flame retardant, antioxidant, mold release agent, stabilizer and mixture thereof.
Preferably, the flame retardant comprises, by mass, 30-70 parts of a semi-aromatic polyamide copolymer, 0-15 parts of a flame retardant, 0.2-2 parts of a mixture of an antioxidant and a mold release agent, and 30-60 parts of glass fibers.
The technical solution of the present invention is further illustrated by the following preferred examples, but is not to be construed as limiting the present invention in any way.
The various properties in the examples were determined as follows:
1. intrinsic viscosity [ eta ]
The nylon sample to be tested is dissolved in concentrated sulfuric acid by adopting an Ubbelohde viscometer to obtain solutions with the concentrations of 0.1, 0.5 and 1.0g/dL, and the inherent viscosity number eta ln of the sample solution is measured by the Ubbelohde viscometer in a constant temperature water bath environment at the temperature of 30 ℃.
ηln＝[ln(t/t0)]/C(dL/g)
Where t0 is the flow-through time of the solvent (sec), t is the flow-through time of the solution (sec), and C is the concentration of the sample solution (g/dL).
Extrapolating the data of eta ln to the concentration of 0 to obtain the intrinsic viscosity eta of the sample.
2. Melting Point
Melting points were measured using a DSC differential scanning calorimeter. And calibrating with pure indium and pure zinc, wherein all DSC experiments are carried out in the same nitrogen flow, and the weight of the sample is 5-6 mg. The sample is firstly heated to a set temperature at a heating rate of 10 ℃/min, and then is cooled to the normal temperature at the same rate after the heat history is eliminated at a constant temperature of 5 min.
3. Number average molecular weight
By Gel Permeation Chromatography (GPC) with hexafluoroisopropanol as solvent.
4. Other properties
Tensile strength is measured according to ASTM D-638, flexural strength and flexural modulus are measured according to ASTM D-790, notched Izod impact strength is measured according to ASTM D-256, heat distortion temperature is measured according to ASTM D-648, and flame retardancy is measured according to UL 94.
Example 1
A method for preparing a semi-aromatic polyamide copolymer (a), comprising the steps of:
step 1: dispersing terephthalic acid in 4 times of water by weight, dispersing biobased 1,9 nonanediamine in 2 times of water by weight, injecting the terephthalic acid and the biobased 1,9 nonanediamine into a reaction kettle by a metering pump at a molar ratio of 1:1.05, and introducing nitrogen to replace air in the reaction kettle. Heating to 60 ℃, starting a stirring device, setting the rotating speed to be 60r/min, carrying out salt forming reaction, monitoring and supplementing amine and acid by measuring pH value on line, reacting for 3 hours, carrying out suction filtration and separation on reactants when the pH value reaches 7.2-7.6, washing with absolute ethyl alcohol, and drying the products at 80 ℃ for 12 hours under a vacuum condition to obtain a first bio-based polyamide salt (9T); the second biobased polyamide salt (9I) was prepared by replacing terephthalic acid with isophthalic acid according to the above method and was used.
Step 2: adding 0.2 wt% of sodium phosphite catalyst, 1.5 wt% of benzoic acid serving as a molecular weight regulator and 30 wt% of deionized water into a stainless steel high-pressure reaction kettle according to the proportion (the proportion of the sum of the two salts) in Table 1 after drying, sealing the reaction kettle, vacuumizing, introducing nitrogen, vacuumizing again, introducing nitrogen to replace air in the reaction kettle for three times, setting the rotating speed at 100r/min, gradually heating to 190 ℃ for 1-2 h, heating to 220 ℃ within 30min, keeping the pressure at 2.4MPa, reacting for 4-6 h at constant temperature, releasing steam in the kettle, reducing to normal pressure within 1h, continuing to heat until water is volatilized, slowly heating to 290-310 ℃, reacting for 2-3 h, and then performing reaction extrusion through a double-screw extruder to obtain a semi-aromatic polyamide copolymer (a), namely a bio-based polyamide (9T/9I) copolymer, the molecular formula of which is shown below, the melting point of the obtained product is 305 ℃, the intrinsic viscosity is 2.1dl/g, the number average molecular weight is 35200, and the results are shown in Table 1.
Wherein n is0Is an integer, n0Is 60.
Example 2
A method for preparing a semi-aromatic polyamide copolymer (b), comprising the steps of:
step 1: dodecanedioic acid is dispersed in water which is 5 times of the weight of dodecanedioic acid, nonanediamine is dispersed in water which is 2 times of the weight of the dodecanedioic acid, dodecanedioic acid and the nonanediamine are injected into a reaction kettle by a metering pump, a stirring device is started, the rotating speed is set to be 60r/min, and nitrogen is introduced to replace air in the reaction kettle. Heating to 80 ℃ for salt forming reaction, monitoring and supplementing amine and acid by measuring pH value on line, reacting for 3 hours, performing suction filtration and separation on the reactant when the pH value reaches 7.2-7.6, washing with absolute ethyl alcohol and deionized water, and drying the product at 80 ℃ for 12 hours under a vacuum condition to obtain a third bio-based polyamide salt (912); a first biobased polyamide salt (9T) was prepared for use according to the method of example 1.
Step 2: adding 0.2 wt% of sodium phosphite catalyst and 1.5 wt% of benzoic acid serving as a molecular weight regulator into a stainless steel autoclave according to the proportion (the proportion of the sum of the two salts) in Table 1 after drying, sealing the autoclave, vacuumizing, introducing nitrogen to replace air in the autoclave for three times, setting the rotating speed at 100r/min, gradually heating to 190 ℃ for 1-2 h, heating to 220 ℃ within 30min, keeping the pressure at 1.7MPa, carrying out constant-temperature reaction for 4-6 h, releasing steam in the autoclave, reducing the pressure to normal pressure within 1h, continuously heating to water volatilization, slowly heating to 280-300 ℃, reacting for 2-3 h, and then carrying out reaction and extrusion through a double-screw extruder to obtain a semi-aromatic polyamide copolymer (b), and a bio-based polyamide (9T/912) copolymer, the molecular formula is shown below, and the melting point of the obtained product is 290 ℃, the intrinsic viscosity is 2.05dl/g, the number average molecular weight is 38300, and the results are shown in Table 1.
Wherein m is1And n1Is an integer, m1+n1＝130。
Example 3
A method for preparing a semi-aromatic polyamide copolymer (b), comprising the steps of:
step 1: dispersing sebacic acid in water of which the weight is 4 times that of the sebacic acid, dispersing hexamethylenediamine in water of which the weight is 2 times that of the hexamethylenediamine, injecting the sebacic acid and the hexamethylenediamine with the molar ratio of 1:1 into a reaction kettle by using a metering pump, starting a stirring device, setting the rotating speed to be 60r/min, and introducing nitrogen to replace air in the reaction kettle. Heating to 80 ℃ for salt forming reaction, monitoring and supplementing amine and acid by measuring pH value on line, reacting for 3 hours, performing suction filtration and separation on the reactant when the pH value reaches 7.2-7.6, washing with absolute ethyl alcohol and deionized water, and drying the product at 80 ℃ for 12 hours under a vacuum condition to obtain a third bio-based polyamide salt (610); a first biobased polyamide salt (9T) was prepared for use according to the method of example 1.
Step 2: adding 0.2 wt% of sodium phosphite catalyst, 1.5 wt% of benzoic acid serving as a molecular weight regulator and 30 wt% of deionized water into a stainless steel reaction kettle according to the proportion (the proportion of the sum of the two salts) in Table 1 after drying, sealing the reaction kettle, vacuumizing, introducing nitrogen to replace air in the reaction kettle for three times, setting the rotating speed to be 200r/min, gradually heating to 180 ℃, keeping the temperature for 1-2 hours, heating to 220 ℃ within 30 minutes, keeping the pressure at 1.7MPa, carrying out constant-temperature reaction for 4-6 hours, releasing steam in the kettle, reducing the pressure to normal pressure within 1 hour, continuing to heat until water is volatilized, slowly heating to 280-300 ℃, reacting for 2-3 hours, and then carrying out reaction extrusion through a double-screw extruder to obtain a semi-aromatic polyamide copolymer (b), namely, the bio-based polyamide (9T/610) copolymer, the molecular formula of which is shown below, the melting point of the obtained product is 295 ℃, the intrinsic viscosity is 2.1dl/g, and the number average molecular weight is 40300, which is shown in Table 1.
Wherein m is2And n2Is an integer, m2+n2＝140。
Example 4
A method for preparing a semi-aromatic polyamide copolymer (c), comprising the steps of:
step 1: a first biobased polyamide salt (9T) was prepared for use according to the method of example 1.
Step 2: adding 0.2 wt% of sodium phosphite catalyst, 1.5 wt% of benzoic acid serving as a molecular weight regulator and 30 wt% of deionized water into a stainless steel high-pressure reaction kettle according to the proportion (the proportion of the sum of the two materials) in Table 1 after drying, sealing the reaction kettle, vacuumizing, introducing nitrogen to replace air in the reaction kettle for three times, setting the rotating speed at 100r/min, gradually heating to 180 ℃, keeping the temperature for 1-2 hours, heating to 220 ℃ within 30 minutes, keeping the pressure at 1.7MPa, carrying out constant-temperature reaction for 4-6 hours, releasing steam in the kettle, reducing the temperature to normal pressure within 1 hour, continuing to heat until water is volatilized, slowly heating to 280-300 ℃, reacting for 2-3 hours, and carrying out reaction and extrusion through a double-screw extruder to obtain a semi-aromatic polyamide copolymer (c), namely a bio-based polyamide (9T/6) copolymer, the molecular formula of which is shown below, the melting point of the obtained product is 290 ℃, the intrinsic viscosity is 2.2dl/g, and the number average molecular weight is 40600, as shown in Table 1.
Wherein p is1And q is1Is an integer, p1+q1＝150。
TABLE 1 Synthesis ratio of semi-aromatic Polyamide copolymer and its intrinsic viscosity and melting Point
| Example 1 | Example 2 | Example 3 | Example 4 | |
| (9T) Polyamide salt (mol) | 90 | 90 | 90 | 90 |
| (9I) Polyamic salts (mol) | 10 | —— | —— | —— |
| (912) Polyamic salts (mol) | —— | 10 | —— | —— |
| (610) Polyamic salts (mol) | —— | —— | 10 | —— |
| Caprolactam (mol) | —— | —— | —— | 10 |
| Intrinsic viscosity (dl/g) | 2.1 | 2.05 | 2.1 | 2.2 |
| Melting Point (. degree.C.) | 305 | 290 | 295 | 290 |
Compositions containing bio-based semi-aromatic polyamide copolymers, weighed in weight percent as shown in table 2.
The semi-aromatic polyamide copolymer, the flame retardant synergist, the heat stabilizer, the antioxidant and the mold release agent are mixed and stirred uniformly, the mixed materials are added into a hopper of a double-screw extruder, glass staple fibers are fed from the side, and the semi-aromatic polyamide copolymer-containing composition is prepared through melt blending, extrusion and granulation, wherein the performances of the semi-aromatic polyamide copolymer-containing composition are shown in Table 2.
TABLE 2 mechanical Properties of compositions containing semi-aromatic Polyamide copolymers
| Properties of the Polyamide composition | Example 1 | Example 2 | Example 3 | Example 4 |
| Semi-aromatic Polyamide copolymer (a) (%) | 52 | |||
| Semi-aromatic Polyamide copolymer (b) (%) | 52 | |||
| Semi-aromatic polyamide copolymer (c) ((c))％) | 52 | |||
| Semi-aromatic Polyamide copolymer (d) (%) | 52 | |||
| Glass short fiber (%) | 30 | 30 | 30 | 30 |
| Diethyl phosphinate flame retardant (%) | 12 | 12 | 12 | 12 |
| Phosphate flame retardant synergist (%) | 2 | 2 | 2 | 2 |
| Metal salt Heat stabilizer (%) | 3 | 3 | 3 | 3 |
| Low molecular weight polyethylene mold release agent (%) | 0.6 | 0.6 | 0.6 | 0.6 |
| Phenol + phosphite complex antioxidant (%) | 0.4 | 0.4 | 0.4 | 0.4 |
| Tensile Strength (MPa) | 150 | 140 | 145 | 150 |
| Flexural Strength (MPa) | 200 | 180 | 190 | 1800 |
| Flexural modulus (MPa) | 10000 | 9000 | 9500 | 9000 |
| Notched impact Strength (KJ/m)2) | 12 | 14 | 13 | 15 |
| Heat distortion temperature (. degree. C.) of 1.82MPa | 270 | 260 | 265 | 255 |
| UL94(class)(0.8mm) | V0 | V0 | V0 | V0 |
As can be seen from Table 2, the semi-aromatic polyamide copolymer composition has good heat resistance and maintains good rigidity and strength at high temperatures.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the best embodiments, the present invention is not limited to the above disclosed embodiments, but should cover various modifications, equivalent combinations, made according to the essence of the present invention.
Claims (10)
1. A bio-based semi-aromatic polyamide copolymer characterized in that its repeating structural unit satisfies any one of the following three conditions:
(a)
(b)
(c)
wherein, the synthetic monomers of the repeating structural units shown in the formulas 1-1, 2-1 and 3-1 all contain nonane diamine which is bio-based 1,9 nonane diamine,
in the formula 2-2, x represents at least one of 5, 6, 9, 10 and 12; y represents at least one of 6, 9, 10, 11, 12, 13, 14, 16 and 18;
in the formula 3-2, z represents one of 6, 11 and 12.
2. A method for preparing a copolymer of the repeating structural unit represented by the formula 1-1 as claimed in claim 1, comprising the steps of:
reacting the first bio-based polyamide salt with the second bio-based polyamide salt to obtain a semi-aromatic polyamide copolymer,
wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid; the synthetic monomers of the second bio-based polyamide salt include nonanediamine and isophthalic acid.
3. The method of claim 2,
respectively dissolving terephthalic acid and nonane diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain a first bio-based polyamide salt;
respectively dissolving isophthalic acid and nonane diamine in water, injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain a second bio-based polyamide salt;
adding the first bio-based polyamide salt, the second bio-based polyamide salt and water into a polymerization reaction kettle, vacuumizing, heating, and carrying out melt polymerization reaction to obtain the semi-aromatic polyamide copolymer.
4. A method for producing a copolymer of the repeating structural units represented by the formulae 2-1 and 2-2 according to claim 1, comprising the steps of:
reacting the third polyamide salt with the first biobased polyamide salt to obtain a semi-aromatic polyamide copolymer,
wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid; the synthetic monomers of the third polyesteramide include monomeric diacids and monomeric diamines.
5. The method of claim 4,
respectively dissolving monomer diacid and monomer diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain third polyesteramide;
respectively dissolving terephthalic acid and nonane diamine in water, then injecting the mixture into a reaction kettle according to the molar ratio of 1: 1-1.05, and carrying out salt forming reaction at a certain temperature to obtain a first bio-based polyamide salt;
and adding the third polyesteramide, the first bio-based polyesteramide and water into a polymerization reaction kettle, vacuumizing, heating, and carrying out melt polymerization reaction to obtain the semi-aromatic polyamide copolymer.
6. A process for producing the copolymer of claim 1, which is composed of the repeating structural units represented by the formulae 3-1 and 3-2,
reacting a first bio-based polyamide salt with a lactam monomer to obtain a semi-aromatic polyamide copolymer, wherein the synthetic monomers of the first bio-based polyamide salt comprise nonanediamine and terephthalic acid.
7. The semi-aromatic polyamide copolymer of claim 6 wherein the lactam monomer is selected from at least one of caprolactam, undecanolactam, and dodecanolactam.
8. A semi-aromatic polyamide copolymer-containing composition comprising the semi-aromatic polyamide copolymer of claim 1, and further comprising at least one additive selected from the group consisting of: inorganic filler, dye, flame retardant, antioxidant, mold release agent, stabilizer and mixture thereof.
9. The semi-aromatic polyamide copolymer-containing composition according to claim 8, comprising the semi-aromatic polyamide copolymer, a flame retardant, an antioxidant, a mold release agent, and glass fibers in parts by mass.
10. Use of a semi-aromatic polyamide copolymer-containing composition according to any one of claims 8 to 9 in electronic appliances and automobiles.
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