CN117986568A - Hyperbranched polyamide resin and preparation method and application thereof - Google Patents
Hyperbranched polyamide resin and preparation method and application thereof Download PDFInfo
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- CN117986568A CN117986568A CN202410164501.7A CN202410164501A CN117986568A CN 117986568 A CN117986568 A CN 117986568A CN 202410164501 A CN202410164501 A CN 202410164501A CN 117986568 A CN117986568 A CN 117986568A
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- polyamide
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 199
- 239000004952 Polyamide Substances 0.000 claims description 124
- 229920002647 polyamide Polymers 0.000 claims description 124
- 150000003839 salts Chemical class 0.000 claims description 86
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 150000004985 diamines Chemical class 0.000 claims description 48
- 238000006116 polymerization reaction Methods 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 34
- -1 benzenediol compound Chemical class 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 239000003063 flame retardant Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 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 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 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 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 239000006224 matting agent Substances 0.000 claims description 4
- 239000002667 nucleating agent Substances 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Chemical class 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 2
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 2
- FLFJVPPJGJSHMF-UHFFFAOYSA-L manganese hypophosphite Chemical compound [Mn+2].[O-]P=O.[O-]P=O FLFJVPPJGJSHMF-UHFFFAOYSA-L 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 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
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 claims description 2
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 36
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 26
- 239000012266 salt solution Substances 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 16
- 239000001361 adipic acid Substances 0.000 description 13
- 235000011037 adipic acid Nutrition 0.000 description 13
- 239000012141 concentrate Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000077 insect repellent Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- LXZIFLXVFHVUKK-UHFFFAOYSA-N pyrene-1,4,5,10-tetracarboxylic acid Chemical compound OC(=O)C1=C2C(C(=O)O)=CC=C(C(C(O)=O)=C3C(O)=O)C2=C2C3=CC=CC2=C1 LXZIFLXVFHVUKK-UHFFFAOYSA-N 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N n-alpha-hexadecene Natural products CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
The invention relates to a hyperbranched polyamide resin and a preparation method and application thereof, wherein the hyperbranched polyamide resin has a structure shown in a formula I.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to hyperbranched polyamide resin and a preparation method and application thereof.
Background
Polyamides commonly known as nylons refer to linear thermoplastic polymers having amide groups (-CO-NH-) on the backbone; the polyamide groups in the polyamide have polarity and can form intermolecular hydrogen bonds, so the polyamide resin has the advantages of toughness, wear resistance, impact resistance, fatigue resistance, corrosion resistance, no toxicity, good spinnability, high fiber strength and good flame retardance, and is widely applied to the fields of automobiles, chemical industry, electronic appliances and the like due to the excellent comprehensive performance. Polyamides have very high molecular weights and thus relatively high relative viscosities and low melt indices; polyamides also have a relatively high crystallinity, and for subsequent injection and extrusion processes, high viscosity, low melt index and high crystallinity are quite difficult to improve filling quality and extrusion speed in the mold, and poor melt flow can greatly increase processing time and cost. This disadvantage has a more pronounced effect on component yields for the production of narrow or thin components or molded articles of complex shape. When the filler or additive is added to the polyamide, the polyamide containing the filler or additive is difficult to fill into the mold in a more uniform and more sufficient manner and at a proper speed due to the high relative viscosity, low melt index and high crystallinity of the polyamide, which also limits the choice of the kind of additive and the amount of filler to be used, making it difficult to improve the dispersibility thereof.
CN105330847a discloses a method for synthesizing high-flow transparent polyamide, after the transparent polyamide is prepared by melt copolymerization of alicyclic diamine, aromatic diacid, aliphatic long carbon chain diacid and polyamine, the transparent polyamide is blended with long carbon chain semi-crystalline polyamide to obtain the high-flow transparent polyamide. It has not been proposed to improve the fluidity of polyamide from the molecular structure design of polyamide resin, and the effect of improving the fluidity of polyamide is not remarkable.
The prior art generally fails to design from the molecular structure of the polyamide resin, and the improvement on the fluidity is not obvious, so that the polyamide resin with a new molecular structure needs to be designed, and the fluidity of the polyamide resin is effectively improved on the basis of ensuring that the polyamide resin has good mechanical properties and a lower yellow index.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide hyperbranched polyamide resin, a preparation method and application thereof, and the hyperbranched polyamide resin has the advantages of low viscosity, high fluidity, easy functionalization, good mechanical property, low yellow index and the like through the design of a molecular structure.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a hyperbranched polyamide resin having a structure according to formula I:
Wherein R 1、R2、R3 is each independently selected from at least one of a C5-C18 linear or branched alkylene.
R 4、R6 is independently selected from at least one of C5-C10 straight-chain or branched alkylene, substituted or unsubstituted C6-C30 arylene.
R 5、R7 is independently selected from at least one of C5-C10 straight-chain or branched alkylene, substituted or unsubstituted C6-C30 arylene.
X is selected from at least one of the following groups:
Wherein, Represents the attachment site of the group; y is selected from single bond,/>O is any one of the following; when Y is a single bond, the two benzene rings are directly connected by a single bond.
A. b are each independently selected from integers from 1 to 5, and may be, for example, 1,2, 3, 4 or 5.
C is selected from 2 or 3.
M is selected from integers from 8 to 23 and may be, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23.
N is an integer selected from 55 to 90, and may be 55、56、57、58、59、60、61、62、63、64、65、66、67、68、69、70、71、72、73、74、75、76、77、78、79、80、81、82、83、84、85、86、87、88、89 or 90, for example.
The substituents in R 4、R6 are each independently selected from at least one of carboxyl, hydroxyl or isocyanate groups.
The substituents of the substituents in R 5、R7 are each independently selected from at least one of amino or hydroxy.
In the present invention, R 1 may be the same group or different groups, R 2 may be the same group or different groups, R 3 may be the same group or different groups, R 4 may be the same group or different groups, R 5 may be the same group or different groups, R 6 may be the same group or different groups, and R 7 may be the same group or different groups.
The hyperbranched polyamide resin provided by the invention has the molecular structure between dendritic macromolecules and linear polymers, has no regular structure like dendritic macromolecules, and no chain entanglement like linear molecules, contains a large number of end groups and three-dimensional spherical structures, and has the advantages of low viscosity, easiness in functionalization and the like; in addition, when the X in the structure shown in the formula I contains an aromatic ring or a cycloalkyl, the heat resistance and the transparency of the hyperbranched polyamide resin can be improved to a certain extent.
The C5-C10 groups in the invention can be C5, C6, C7, C8, C9 or C10 independently.
The C6-C30 in the invention can be C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29 or C30 independently.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
As a preferred embodiment, each R 1、R2、R3 is independently selected from at least one of C5-C18 linear alkylene groups.
Preferably, each R 4、R6 is independently selected from at least one of a C5-C10 linear alkylene, a substituted or unsubstituted C6-C12 arylene.
The substituents in R 4、R6 are each independently selected from at least one of carboxyl, hydroxyl or isocyanate groups.
Preferably, each R 5、R7 is independently selected from at least one of a C5-C10 linear alkylene, a substituted or unsubstituted C6-C20 arylene.
The substituents of the substituents in R 5、R7 are each independently selected from at least one of amino or hydroxy.
Preferably, the number average molecular weight of the hyperbranched polyamide resin is 20000 to 55000, for example 20000, 25000, 30000, 35000, 40000, 45000, 50000 or 55000, and specific point values between the above point values, are limited in space and for the sake of brevity, the invention is not exhaustive of the specific point values comprised in the range.
In the present invention, the C5-C18 may be C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18.
The C6-C12 may be C6, C7, C8, C9, C10, C11 or C12.
The C5-C10 may each independently be C5, C6, C7, C8, C9 or C10.
The C6-C20 may be C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19 or C20.
In a second aspect, the present invention provides a method for preparing a hyperbranched polyamide resin according to the first aspect, the method comprising the steps of:
(1) Mixing diamine containing R 1, tetrabasic acid containing X and a first solvent, and then carrying out a first reaction to obtain a first polyamide salt; mixing diamine containing R 3, dibasic acid containing R 2 and a second solvent, and then carrying out a second reaction to obtain a second polyamide salt; wherein R 1、R2、R3 and X have the same definitions as those of the structure shown in the formula I;
(2) Mixing the first polyamide salt, the second polyamide salt, a third solvent and a blocking agent, and then sequentially performing prepolymerization, final polymerization and granulation to obtain the hyperbranched polyamide resin; the end-capping agent comprises a combination of a diamine and a diacid; the diamine comprises a combination of a diamine containing R 4 and a diamine containing R 6; the dibasic acid comprises a combination of a dibasic acid comprising R 5 and a dibasic acid comprising R 7; wherein, R 4、R5、R6、R7 has the same definition as the structure shown in the formula I.
The preparation method of the hyperbranched polyamide resin provided by the invention can inhibit yellowing of the hyperbranched polyamide resin without adding additional production devices and processes, solves the problems of yellowing and post-processing difficulties in polyamide production for a long time, and has a very large production application prospect.
Illustratively, the R 1 -containing diamine and R 3 -containing diamine each independently include any one or a combination of at least two of pentylene diamine, hexylene diamine, heptylene diamine, octylene diamine, nonylene diamine, decylene diamine, undecylene diamine, dodecylene diamine, tridecylene diamine, tetradecylene diamine, pentadecylene diamine, hexadecylene diamine, heptadecylene diamine, or octadecylene diamine.
Illustratively, the X-containing tetrabasic acid includes any one or a combination of at least two of pyromellitic acid, 1,4,5, 8-naphthalene tetracarboxylic acid, 3,4,9, 10-pyrene tetracarboxylic acid, 1,2,4, 5-cyclohexane tetracarboxylic acid, 4' - (hexafluoroisopropenyl) diphthalic acid, 3', 4' -biphenyl tetracarboxylic acid, 4-oxybisphthalic acid, 1,2,3, 4-cyclopentane tetracarboxylic acid, 1,2,3, 4-butane tetracarboxylic acid, or 1,2,3, 4-cyclobutane tetracarboxylic acid.
Illustratively, the R 2 -containing diacid includes any one or a combination of at least two of glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecandioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanoic acid, hexadecanedioic acid, heptadecanoic acid, or octadecanedioic acid.
Illustratively, the R 4 -containing diamine and the R 6 -containing diamine each independently include any one or a combination of at least two of pentylene diamine, hexylene diamine, heptylene diamine, octylene diamine, nonylene diamine, or decylene diamine.
Illustratively, the R 5 -containing diacid and R 7 -containing diacid each independently include any one or a combination of at least two of glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, or sebacic acid.
Preferably, the first solvent, the second solvent and the third solvent each independently comprise water.
Preferably, the molar ratio of the diamine containing R 1 to the tetrabasic acid containing X is 1:1.
Preferably, the mass ratio of the diamine containing R 1 to the first solvent is (0.2-0.55): 1, for example, it may be 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1 or 0.55:1, etc.
Preferably, the temperature of the first reaction is 80-100deg.C, which may be, for example, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃ or 100 ℃, and specific point values between the above, are for the sake of brevity and for the sake of brevity the present invention is not exhaustive of the specific point values comprised in the range.
Preferably, the time of the first reaction is 30-80min, for example, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min or 80min, and specific point values among the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
Preferably, after the first reaction is finished, the method further comprises the step of performing first concentration on the obtained reaction product to a mass concentration of 100%.
Preferably, the first concentration is performed at a temperature of 100-120 ℃, which may be, for example, 100 ℃,102 ℃,104 ℃,106 ℃,108 ℃,110 ℃,112 ℃,114 ℃,116 ℃,118 ℃ or 120 ℃, and specific values between the above, for the sake of brevity and for the sake of brevity, the present invention is not exhaustive of the specific values included in the range.
Preferably, the first concentration is performed under vacuum.
Preferably, the molar ratio of the diamine containing R 3 to the diacid containing R 2 is 1:1.
Preferably, the mass ratio of the diamine containing R 3 to the second solvent is (0.36-1): 1, for example, it may be 0.36:1, 0.46:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 or 1:1, etc.
Preferably, the temperature of the second reaction is 60-100 ℃, and may be, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃ or 100 ℃, and specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the second reaction time is 30-60min, for example, 30min, 32min, 35min, 38min, 40min, 42min, 45min, 48min, 50min, 52min, 55min, 58min or 60min, and specific point values among the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
Preferably, after the second reaction is finished, the method further comprises the step of performing second concentration on the obtained reaction product to a mass concentration of 100%.
Preferably, the second concentration is performed at 100-120 ℃, which may be, for example, 100 ℃,102 ℃,104 ℃,106 ℃,108 ℃,110 ℃,112 ℃,114 ℃,116 ℃,118 ℃ or 120 ℃, and specific values between the above, for the sake of brevity and for the sake of brevity, the present invention is not exhaustive of the specific values included in the range.
Preferably, the second concentration is performed under vacuum.
Preferably, the molar amount of the first polyamide salt is 10 to 34%, for example, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 31%, 32%, 33% or 34%, and specific point values between the above point values, calculated on the basis of the molar amount of the second polyamide salt as 100%, are limited in space and for the sake of brevity, the present invention is not exhaustive to list the specific point values included in the range.
The molar quantity of the first polyamide salt needs to be controlled within a certain range, so that the mechanical property and the processing property of the hyperbranched polyamide resin are improved while the fluidity of the hyperbranched polyamide resin is ensured.
Preferably, the sum of the masses of the first and second polyamide salts is 50 to 90% (e.g., 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, etc.), more preferably 50 to 80% (e.g., 51%, 53%, 58%, 60%, 62%, 68%, 72%, or 78%, etc.), and still more preferably 60 to 70% (e.g., 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%, etc.), based on 100% of the total mass of the first, second, and third solvents.
Preferably, the molar ratio of the capping agent to the first polyamide salt is 1 (4-22), which may be, for example, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, or 1:22, etc.
Preferably, the molar ratio of diamine to diacid is 1:1.
Preferably, the mixed material of step (2) further comprises an additive.
Preferably, the additive comprises any one or a combination of at least two of a catalyst, a defoamer, a weather-resistant agent, a nucleating agent, an antistatic agent, a flame retardant, an anti-ultraviolet agent, a matting agent or an antioxidant.
Preferably, the catalyst comprises any one or a combination of at least two of phosphoric acid, phosphorous acid, hypophosphorous acid organic matters or hypophosphorous acid salts.
Preferably, the defoamer comprises a silicon-containing compound.
Preferably, the weather-resistant agent comprises any one or a combination of at least two of a benzenediol compound, a salicylate compound, a benzotriazole compound, a benzophenone compound and a hindered amine compound.
Preferably, the nucleating agent comprises any one or a combination of at least two of nano silicon dioxide, nano calcium carbonate, titanate, zincate, montmorillonite, kaolin, talcum powder, siO 2、MgO、ZnO、Al2O3、ZrO2, carbon nano tubes, potassium titanate crystals, polycarbonate or polyarylethersulfone.
Preferably, the antistatic agent comprises any one or a combination of at least two of amine derivatives, quaternary ammonium salts, sulfuric esters, phosphoric esters or polyethylene glycol derivatives.
Preferably, the flame retardant includes any one or a combination of at least two of a halogen flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, or a metal hydroxide flame retardant.
Preferably, the anti-ultraviolet agent comprises any one or a combination of at least two of nano TiO 2, nano ZnO, nano SiO 2, nano Al 2O3 or nano FeO.
Preferably, the matting agent comprises any one or a combination of at least two of titanium dioxide, silicon dioxide, aluminum oxide, sodium carbonate, calcium hydroxide, silicone oil, fatty acid salts or alkylphenols.
Preferably, the antioxidant comprises at least one of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, manganese hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite or zinc hypophosphite, and further preferably sodium hypophosphite.
Preferably, the additive is present in an amount of 0.05 to 0.2% by mass, for example, 0.05%, 0.06%, 0.08%, 0.1%, 0.12%, 0.14%, 0.16%, 0.18% or 0.2% by mass, based on 100% by mass of the total of the first polyamide salt, the second polyamide salt, the third solvent, the capping agent and the additive, and the specific point values between the above point values are limited to a spread and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, after the mixing in step (2) is completed, the pH of the resulting mixture is 7.2-7.8, for example, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, or 7.8.
Preferably, the prepolymerization is divided into three reaction stages, a first reaction stage, a second reaction stage and a third reaction stage.
Preferably, the first reaction stage is carried out under conditions of elevated temperature and elevated pressure.
Preferably, in the first reaction stage, the temperature of the reaction is raised from 80℃to 190-210 ℃ (e.g., 190 ℃, 192 ℃, 194 ℃, 196 ℃, 198 ℃, 200 ℃, 202 ℃, 204 ℃, 206 ℃, 208 ℃, 210 ℃, etc.).
Preferably, the temperature rising rate of the first reaction stage is 1.5-2 ℃/min, for example, 1.5 ℃/min, 1.6 ℃/min, 1.7 ℃/min, 1.8 ℃/min, 1.9 ℃/min or 2 ℃/min, and the specific point values between the above-mentioned point values, are limited in length and for the sake of brevity, the present invention is not exhaustive to list the specific point values included in the range.
Preferably, in the first reaction stage, the pressure of the reaction is raised from 0.1MPa to 1.3-1.9MPa (e.g., 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa, etc.).
Preferably, the pressure rising speed of the first reaction stage is 0.02-0.04MPa/min, for example 0.02MPa/min、0.022MPa/min、0.024MPa/min、0.026MPa/min、0.028MPa/min、0.03MPa/min、0.032MPa/min、0.034MPa/min、0.036MPa/min、0.038MPa/min or 0.04MPa/min, and the specific point values between the above point values are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the second reaction stage is carried out under conditions of elevated temperature and elevated pressure.
Preferably, in the second reaction stage, the temperature of the reaction is raised from 190-210 ℃ (e.g., 190 ℃, 192 ℃, 194 ℃, 196 ℃, 198 ℃, 200 ℃, 202 ℃, 204 ℃, 206 ℃, 208 ℃, or 210 ℃, etc.) to 230-250 ℃ (e.g., 232 ℃, 234 ℃,236 ℃, 238 ℃, 240 ℃, 242 ℃, 244 ℃, 246 ℃, 248 ℃, or 250 ℃, etc.).
Preferably, the temperature rising rate of the second reaction stage is 1 to 1.5 ℃/min, for example, 1 ℃/min, 1.1 ℃/min, 1.2 ℃/min, 1.3 ℃/min, 1.4 ℃/min or 1.5 ℃/min, and the specific point values between the above-mentioned point values, are limited in length and for the sake of brevity, the present invention is not exhaustive to list the specific point values included in the range.
Preferably, in the second reaction stage, the pressure of the reaction is increased from 1.3 to 1.9MPa (e.g., 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, or 1.9MPa, etc.) to 2 to 2.5MPa (e.g., 2MPa, 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa, or 2.5MPa, etc.).
Preferably, the second reaction stage has a pressure-increasing speed of 0.0015-0.09MPa/min, for example 0.0015MPa/min、0.002MPa/min、0.004MPa/min、0.006MPa/min、0.008MPa/min、0.01MPa/min、0.02MPa/min、0.04MPa/min、0.06MPa/min、0.08MPa/min or 0.09MPa/min, and specific values between the above values are limited in space and for brevity, the present invention is not exhaustive of the specific values included in the range.
Preferably, the reaction pressure in the third reaction stage is 2.6 to 4MPa (gauge pressure) (e.g., 2.6MPa, 2.8MPa, 3MPa, 3.2MPa, 3.4MPa, 3.6MPa, 3.8MPa or 4MPa, etc.), more preferably 2.8 to 3.8MPa (gauge pressure) (e.g., 2.8MPa, 2.9MPa, 3MPa, 3.1MPa, 3.2MPa, 3.4MPa, 3.6MPa or 3.8MPa, etc.), still more preferably 3 to 3.5MPa (gauge pressure) (e.g., 3MPa, 3.1MPa, 3.2MPa, 3.3MPa, 3.4MPa or 3.5MPa, etc.).
Preferably, the reaction time of the third reaction stage is 60-90min, for example, 60min, 62min, 65min, 68min, 70min, 2min, 75min, 78min, 80min, 85min, 88min or 90min, and specific point values among the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
Preferably, the reaction temperature in the third reaction stage is 260 to 290℃and may be 260℃to 265℃to 270℃to 275℃to 280℃to 285℃or 290℃or the like.
Preferably, the step of reducing the pressure is further included after the completion of the prepolymerization.
Preferably, the time for the depressurization is 60-90min, for example, 60min, 65min, 70min, 75min, 80min, 85min or 90min, and the specific point values among the above point values are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, by reducing the pressure to 101-200KPa, for example, 101KPa, 110KPa, 120KPa, 130KPa, 140KPa, 150KPa, 160KPa, 170KPa, 180KPa, 190KPa or 200KPa, and specific point values among the above point values, the present invention is not exhaustive to list specific point values included in the range for the sake of brevity and conciseness.
Preferably, the temperature of the final polymerization is 250-270 ℃, which may be 250 ℃, 251 ℃, 252 ℃, 253 ℃, 254 ℃, 255 ℃, 256 ℃, 257 ℃, 258 ℃, 259 ℃, 260 ℃, 261 ℃, 262 ℃, 263 ℃, 264 ℃, 265 ℃, 266 ℃, 267 ℃, 268 ℃, 269 ℃ or 270 ℃, and specific point values between the above point values, for example, are limited in length and for the sake of brevity, the invention is not exhaustive of the specific point values included in the range.
Preferably, the final polymerization time is 10-60min, for example 10min、12min、15min、20min、22min、25min、28min、30min、32min、35min、38min、40min、42min、45min、48min、52min、55min、58min or 60min, and the specific point values between the above point values are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the final polymerization pressure is-0.01 to-0.1 MPa (gauge pressure), for example, -0.01MPa, -0.02MPa, -0.03MPa, -0.04MPa, -0.05MPa, -0.06MPa, -0.07MPa, -0.08MPa, -0.09MPa or-0.1 MPa, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the final polymerization further comprises the steps of sequentially pressurizing and discharging.
Preferably, by said pressurizing to 0.1-0.5MPa (gauge pressure), for example, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5MPa, and specific point values between the above-mentioned point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the preparation method specifically comprises the following steps:
(1) Mixing diamine containing R 1, tetrabasic acid containing X and a first solvent, performing a first reaction, and concentrating the obtained reaction product at 100-120 ℃ until the mass concentration is 100% after the first reaction is completed to obtain a first polyamide salt; mixing diamine containing R 3, diacid containing R 2 and a second solvent, and then carrying out a second reaction, wherein after the second reaction is finished, the obtained reaction product is concentrated to 100% of mass concentration at 100-120 ℃ to obtain a second polyamide salt; the molar ratio of the diamine containing R 1 to the tetrabasic acid containing X is 1:1; the mass ratio of the diamine containing R 1 to the first solvent is (0.2-0.55): 1; the temperature of the first reaction is 80-100 ℃; the time of the first reaction is 30-80min; the molar ratio of the diamine containing R 3 to the diacid containing R 2 is 1:1; the mass ratio of the diamine containing R 3 to the second solvent is (0.36-1): 1; the temperature of the second reaction is 60-100 ℃; the second reaction time is 30-60min;
(2) Mixing the first polyamide salt, the second polyamide salt, a third solvent, a blocking agent and an additive, then carrying out prepolymerization, reducing the pressure to 101-200KPa after the prepolymerization is completed, then carrying out final polymerization, pressurizing to 0.1-0.5MPa (gauge pressure) after the final polymerization is completed, discharging, and granulating to obtain the hyperbranched polyamide resin; after the mixing is completed, the pH value of the obtained mixture is 7.2-7.8; the molar amount of the first polyamide salt is 10-34% based on 100% of the molar amount of the second polyamide salt; the sum of the masses of the first polyamide salt and the second polyamide salt is 50 to 90%, more preferably 50 to 80%, still more preferably 60 to 70%, based on 100% of the total mass of the first polyamide salt, the second polyamide salt and the third solvent; the end-capping agent comprises a combination of a diamine and a diacid; the diamine comprises a combination of a diamine containing R 4 and a diamine containing R 6; the dibasic acid comprises a combination of a dibasic acid comprising R 5 and a dibasic acid comprising R 7; the molar ratio of the diamine to the diacid is 1:1; the mole ratio of the end-capping agent to the first polyamide salt is 1 (4-22); the mass of the additive is 0.05-0.2% based on 100% of the total mass of the first polyamide salt, the second polyamide salt, the third solvent, the end-capping agent and the additive; the prepolymerization is divided into three reaction stages, namely a first reaction stage, a second reaction stage and a third reaction stage; the first reaction stage is carried out under the conditions of temperature rise and pressure rise; in the first reaction stage, the temperature of the reaction is increased from 80 ℃ to 190-210 ℃; the temperature rising speed of the first reaction stage is 1.5-2 ℃/min; in the first reaction stage, the pressure of the reaction is increased from 0.1MPa to 1.3-1.9MPa; the boosting speed of the first reaction stage is 0.02-0.04MPa/min; the second reaction stage is carried out under the conditions of temperature rise and pressure rise; in the second reaction stage, the temperature of the reaction is increased from 190-210 ℃ to 230-250 ℃; the temperature rising speed of the second reaction stage is 1-1.5 ℃/min; in the second reaction stage, the pressure of the reaction is increased from 1.3-1.9MPa to 2-2.5MPa; the step-up speed of the second reaction stage is 0.0015-0.09MPa/min; the reaction pressure in the third reaction stage is 2.6 to 4MPa (gauge pressure), more preferably 2.8 to 3.8MPa (gauge pressure), still more preferably 3 to 3.5MPa (gauge pressure); the reaction time of the third reaction stage is 60-90min; the reaction temperature of the third reaction stage is 260-290 ℃; the time for reducing the pressure is 60-90min; the temperature of the final polymerization is 250-270 ℃; the final polymerization time is 10-60min; the final polymerization pressure is-0.01 to-0.1 MPa (gauge pressure).
In a third aspect, the present invention provides the use of a hyperbranched polyamide resin according to the first aspect in automotive parts, chemical materials or electronic devices.
Compared with the prior art, the invention has the following beneficial effects:
The hyperbranched polyamide resin provided by the invention has the advantages of improved flow property, good mechanical property and low yellow index, and can greatly improve the quality of downstream engineering plastics, film products and fiber products and reduce the processing cost. The hyperbranched polyamide resin provided by the invention has the tensile strength of 55-85MPa, the elongation at break of 10-65%, the bending strength of 65-112MPa, the notched Izod impact strength of 4.3-5.6kj/m 2, the mosquito-repellent incense mould flowability of 1000-3000mm, the YI value of 105 ℃/8h of 6-15 and the melt index of 30-94g/10min under the conditions of 280 ℃/2.16 kg.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
A hyperbranched polyamide resin has the structure that:
the preparation method of the hyperbranched polyamide resin comprises the following steps:
(1) Mixing 10mol of hexamethylenediamine, 10mol of 1,4,5, 8-naphthalene tetracarboxylic acid and 2560g of water in a reaction kettle under the protection of nitrogen to react at 80 ℃ for 30min to obtain a first polyamide salt solution with the mass concentration of 50%, heating to 110 ℃, vacuumizing to concentrate the first polyamide salt solution into a first polyamide salt with the mass concentration of 100%, drying and sealing for later use;
Under the protection of nitrogen, 70mol of hexamethylenediamine, 70mol of adipic acid and 10547g of water are mixed in a reaction kettle for reaction, the reaction temperature is 60 ℃, the reaction time is 30min, a second polyamide salt solution with the mass concentration of 50% is obtained, then the temperature is raised to 110 ℃, the second polyamide salt solution is concentrated into a second polyamide salt with the mass concentration of 100% by vacuumizing, and the second polyamide salt solution is dried and sealed for standby;
(2) The 10L polymerization kettle is vacuumized and filled with nitrogen to replace air for three times, 1060g of pure water is added into the polymerization kettle and protected by the nitrogen, 233g of the first polyamide salt, 1367g of the second polyamide salt, 9.5g of adipic acid, 7.55g of hexamethylenediamine and 3g of sodium hypophosphite are added into the polymerization kettle, the pH value of the obtained mixture is 7.8, stirring is started, the temperature is raised to 80 ℃, and the first reaction stage is started: raising the reaction temperature from 80 ℃ to 210 ℃ at a speed of 2 ℃/min, and raising the reaction pressure from 0.1MPa to 1.7MPa at a speed of 0.026 MPa/min; then enter a second reaction stage: raising the reaction temperature from 210 ℃ to 240 ℃ at a speed of 1 ℃/min, and raising the reaction pressure from 1.7MPa to 2.1MPa at a speed of 0.01 MPa/min; then enter the third reaction stage: the reaction temperature is 265 ℃, the reaction pressure is 2.1MPa (gauge pressure), the reaction time is 90min, the exhaust is reduced to normal pressure after the reaction is completed, the pressure reduction time is 60min, the heating is continued to be raised to 270 ℃, the vacuum pumping is carried out to-0.02 MPa (gauge pressure), the reaction is carried out for 40min, nitrogen is filled into a polymerization kettle until the pressure is 0.3MPa, the melting discharge is started, and the pelletization is carried out by a granulator, so that the hyperbranched polyamide resin is obtained.
Example 2
A hyperbranched polyamide resin has the structure that:
The preparation method of the hyperbranched polyamide resin is different from example 1 in that 325g of the first polyamide salt and 1275g of the second polyamide salt are used in the step (2), and other raw materials, process parameters and steps are the same as those in example 1.
Example 3
A hyperbranched polyamide resin has the structure that:
The process for preparing the hyperbranched polyamide resin was different from example 1 in that 407g of the first polyamide salt and 1193g of the second polyamide salt were used in the step (2), and other raw materials, process parameters and steps were the same as in example 1.
Example 4
A hyperbranched polyamide resin has the structure that:
The process for preparing the hyperbranched polyamide resin was different from example 1 in that 477g of the first polyamide salt and 1123g of the second polyamide salt were used in the step (2), and other raw materials, process parameters and steps were the same as in example 1.
Example 5
A hyperbranched polyamide resin has the structure that:
The preparation method of the hyperbranched polyamide resin is different from example 1 in that 540g of the first polyamide salt and 1060g of the second polyamide salt are used in the step (2), and other raw materials, process parameters and steps are the same as those in example 1.
Example 6
A hyperbranched polyamide resin has the structure that:
the preparation method of the hyperbranched polyamide resin comprises the following steps:
(1) Mixing 1.06mol of hexamethylenediamine, 1.06mol of 3,4,9, 10-pyrene tetracarboxylic acid and 358g of water in a reaction kettle under the protection of nitrogen to react at the temperature of 80 ℃ for 60min to obtain a first polyamide salt solution with the mass concentration of 60%, heating to 120 ℃, vacuumizing to concentrate the first polyamide salt solution into a first polyamide salt with the mass concentration of 100%, drying and sealing for later use;
mixing 5.28mol of hexamethylenediamine, 5.28mol of adipic acid and 795g of water in a reaction kettle under the protection of nitrogen to react at a temperature of 60 ℃ for 30min to obtain a second polyamide salt solution with a mass concentration of 60%, heating to 120 ℃, vacuumizing to concentrate the second polyamide salt solution into a second polyamide salt with a mass concentration of 100%, drying and sealing for later use;
(2) The 10L polymerization kettle was purged three times with nitrogen by evacuating and nitrogen-charging, 1060g of pure water was added thereto, 536g of the first polyamide salt, 1193g of the second polyamide salt, 9.5g of adipic acid, 7.55g of hexamethylenediamine and 3g of sodium hypophosphite were then added thereto, the pH of the resulting mixture was 7.8, stirring was started, and the temperature was raised to 80℃to start the first reaction stage: raising the reaction temperature from 80 ℃ to 210 ℃ at a speed of 2 ℃/min, and raising the reaction pressure from 0.1MPa to 1.7MPa at a speed of 0.026 MPa/min; then enter a second reaction stage: raising the reaction temperature from 210 ℃ to 240 ℃ at a speed of 1 ℃/min, and raising the reaction pressure from 1.7MPa to 2.1MPa at a speed of 0.01 MPa/min; then enter the third reaction stage: the reaction temperature is 265 ℃, the reaction pressure is 3MPa, the reaction time is 90min, the exhaust is reduced to normal pressure after the reaction is completed, the pressure reduction time is 60min, the heating is continued to be raised to 270 ℃, the vacuum pumping is carried out to-0.02 MPa (gauge pressure), the reaction is carried out for 30min, nitrogen is filled into a polymerization kettle to the pressure of 0.3MPa, the melting discharge is started, and the pelletization is carried out by a granulator, so that the hyperbranched polyamide resin is obtained.
Example 7
A hyperbranched polyamide resin has the structure that:
the preparation method of the hyperbranched polyamide resin comprises the following steps:
(1) Under the protection of nitrogen, mixing 1.06mol of hexamethylenediamine, 1.06mol of 1,2,3, 4-cyclobutane tetracarboxylic acid and 240g of water in a reaction kettle for reaction at the temperature of 80 ℃ for 60min to obtain a first polyamide salt solution with the mass concentration of 60%, heating to 120 ℃, vacuumizing to concentrate the first polyamide salt solution into a first polyamide salt with the mass concentration of 100%, drying and sealing for later use;
mixing 5.28mol of hexamethylenediamine, 5.28mol of adipic acid and 795g of water in a reaction kettle under the protection of nitrogen to react at a temperature of 60 ℃ for 30min to obtain a second polyamide salt solution with a mass concentration of 60%, heating to 120 ℃, vacuumizing to concentrate the second polyamide salt solution into a second polyamide salt with a mass concentration of 100%, drying and sealing for later use;
(2) The 10L polymerization kettle was purged three times with nitrogen by evacuating and nitrogen-charging, 1060g of pure water was added thereto, 536g of the first polyamide salt, 1193g of the second polyamide salt, 9.5g of adipic acid, 7.55g of hexamethylenediamine and 3g of sodium hypophosphite were then added thereto, the pH of the resulting mixture was 7.8, stirring was started, and the temperature was raised to 80℃to start the first reaction stage: raising the reaction temperature from 80 ℃ to 210 ℃ at a speed of 2 ℃/min, and raising the reaction pressure from 0.1MPa to 1.7MPa at a speed of 0.026 MPa/min; then enter a second reaction stage: raising the reaction temperature from 210 ℃ to 240 ℃ at a speed of 1 ℃/min, and raising the reaction pressure from 1.7MPa to 2.1MPa at a speed of 0.01 MPa/min; then enter the third reaction stage: the reaction temperature is 265 ℃, the reaction pressure is 2.1MPa, the reaction time is 90min, the exhaust is reduced to normal pressure after the reaction is completed, the pressure reduction time is 60min, the heating is continued to be raised to 270 ℃, the vacuum pumping is carried out to-0.02 MPa (gauge pressure), the reaction is carried out for 30min, nitrogen is filled into a polymerization kettle to the pressure of 0.3MPa, the melting discharge is started, and the pelletization is carried out by a granulator, so that the hyperbranched polyamide resin is obtained.
Example 8
A hyperbranched polyamide resin has the structure that:
the preparation method of the hyperbranched polyamide resin comprises the following steps:
(1) Mixing 1.06mol of hexamethylenediamine, 1.06mol of pyromellitic acid and 240g of water in a reaction kettle under the protection of nitrogen to react at the temperature of 80 ℃ for 60min to obtain a first polyamide salt solution with the mass concentration of 60%, heating to 120 ℃, vacuumizing to concentrate the first polyamide salt solution into a first polyamide salt with the mass concentration of 100%, drying and sealing for later use;
mixing 5.28mol of hexamethylenediamine, 5.28mol of adipic acid and 795g of water in a reaction kettle under the protection of nitrogen to react at a temperature of 60 ℃ for 30min to obtain a second polyamide salt solution with a mass concentration of 60%, heating to 120 ℃, vacuumizing to concentrate the second polyamide salt solution into a second polyamide salt with a mass concentration of 100%, drying and sealing for later use;
(2) The 10L polymerization kettle is vacuumized and filled with nitrogen to replace air for three times, 1060g of pure water is added into the polymerization kettle and protected by the nitrogen, 354g of the first polyamide salt, 1246g of the second polyamide salt, 9.5g of adipic acid, 7.55g of hexamethylenediamine and 3g of sodium hypophosphite are added into the polymerization kettle, the pH value of the obtained mixture is 7.8, stirring is started, the temperature is raised to 80 ℃, and the first reaction stage is started: raising the reaction temperature from 80 ℃ to 210 ℃ at a speed of 2 ℃/min, and raising the reaction pressure from 0.1MPa to 1.7MPa at a speed of 0.026 MPa/min; then enter a second reaction stage: raising the reaction temperature from 210 ℃ to 240 ℃ at a speed of 1 ℃/min, and raising the reaction pressure from 1.7MPa to 2.1MPa at a speed of 0.01 MPa/min; then enter the third reaction stage: the reaction temperature is 265 ℃, the reaction pressure is 2.1MPa, and the reaction time is 90min; and (3) exhausting and reducing the pressure to normal pressure after the reaction is finished, wherein the pressure reduction time is 60min, continuously heating to 270 ℃, vacuumizing to-0.02 MPa (gauge pressure), reacting for 30min, filling nitrogen into a polymerization kettle to the pressure of 0.3MPa, starting to melt and discharge, and granulating by using a granulator to obtain the hyperbranched polyamide resin.
Comparative example 1
A polyamide resin having the structure:
The preparation method of the polyamide resin comprises the following steps:
(1) Mixing 10mol of hexamethylenediamine, 10mol of 1,4,5, 8-naphthalene tetracarboxylic acid and 2560g of water in a reaction kettle under the protection of nitrogen to react at 80 ℃ for 30min to obtain a first polyamide salt solution with the mass concentration of 50%, heating to 110 ℃, vacuumizing to concentrate the first polyamide salt solution into a first polyamide salt with the mass concentration of 100%, drying and sealing for later use;
(2) The 10L polymerization kettle is vacuumized and filled with nitrogen to replace air for three times, and is protected by nitrogen, 1060g of pure water is added into the polymerization kettle, 1600g of first polyamide salt, 9.5g of adipic acid, 7.55g of hexamethylenediamine and 3g of sodium hypophosphite are then added, the pH value of the obtained mixture is 7.8, stirring is started, the temperature is raised to 80 ℃, and the first reaction stage is started: the reaction temperature was increased from 80℃to 210℃at a rate of 2℃per minute, while the reaction pressure was increased from 0.1MPa to 1.7MPa at a rate of 0.026 MPa; then enter a second reaction stage: raising the temperature from 210 ℃ to 240 ℃ at a speed of 1 ℃/min, and raising the reaction pressure from 1.7MPa to 2.1MPa at a speed of 0.01 MPa/min; then enter the third reaction stage: the reaction temperature is 265 ℃, the reaction pressure is 2.1MPa (gauge pressure), the reaction time is 90min, the exhaust is reduced to normal pressure after the reaction is completed, the pressure reduction time is 60min, the heating is continued to be raised to 270 ℃, the vacuum pumping is carried out to-0.02 MPa (gauge pressure), the reaction is carried out for 40min, nitrogen is filled into a polymerization kettle until the pressure is 0.3MPa, the melting discharge is started, and the polyamide resin is obtained through granulation by a granulator.
Comparative example 2
A polyamide resin having the structure:
The preparation method of the polyamide resin comprises the following steps:
(1) Mixing 1.06mol of hexamethylenediamine, 1.06mol of trimesic acid and 240g of water in a reaction kettle under the protection of nitrogen to react at the temperature of 80 ℃ for 60min to obtain a first polyamide salt solution with the mass concentration of 60%, heating to 120 ℃, vacuumizing to concentrate the first polyamide salt solution into a first polyamide salt with the mass concentration of 100%, drying and sealing for later use;
mixing 5.28mol of hexamethylenediamine, 5.28mol of adipic acid and 795g of water in a reaction kettle under the protection of nitrogen to react at a temperature of 60 ℃ for 30min to obtain a second polyamide salt solution with a mass concentration of 60%, heating to 120 ℃, vacuumizing to concentrate the second polyamide salt solution into a second polyamide salt with a mass concentration of 100%, drying and sealing for later use;
(2) The 10L polymerization kettle is vacuumized and filled with nitrogen to replace air for three times, 1060g of pure water is added into the polymerization kettle and protected by the nitrogen, 245g of the first polyamide salt, 1193g of the second polyamide salt, 9.5g of adipic acid, 7.55g of hexamethylenediamine and 3g of sodium hypophosphite are added into the polymerization kettle, the pH value of the obtained mixture is 7.8, stirring is started, the temperature is raised to 80 ℃, and the first reaction stage is started: raising the reaction temperature from 80 ℃ to 210 ℃ at a speed of 2 ℃/min, and raising the reaction pressure from normal pressure to 1.7MPa at a speed of 0.026 MPa/min; then enter a second reaction stage: raising the reaction temperature from 210 ℃ to 240 ℃ at a speed of 1 ℃/min, and raising the reaction pressure from 1.7MPa to 2.1MPa at a speed of 0.01 MPa/min; then enter the third reaction stage: the reaction temperature is 265 ℃, the reaction pressure is 2.1MPa, the reaction time is 90min, the exhaust is reduced to normal pressure after the reaction is completed, the pressure reduction time is 60min, the heating is continued to be raised to 270 ℃, the vacuum pumping is carried out to-0.02 MPa (gauge pressure), the reaction is carried out for 40min, nitrogen is filled into a polymerization kettle to the pressure of 0.3MPa, the melting discharge is started, and the polyamide resin is obtained by granulating by a granulator.
Comparative example 3
A polyamide resin having the structure:
The process for producing the polyamide resin was different from example 1 in that the first polyamide salt in step (2) was 125g and the second polyamide salt was 1475g, and the other raw materials, process parameters and steps were the same as in example 1.
Comparative example 4
A polyamide resin having the structure:
The process for producing the polyamide resin was different from example 1 in that 597g of the first polyamide salt and 1003g of the second polyamide salt were used in the step (2), and the other raw materials, process parameters and steps were the same as those in example 1.
The hyperbranched polyamide resins provided in examples 1-8 and the polyamide resins provided in comparative examples 1-4 were prepared as a spline, the preparation method of which was: the preparation is carried out by using an injection molding machine (manufacturer: sea, model: ZE900 III/160H), the temperature of the production process is 255 ℃ at one stage, 265 ℃ at two stages, 275 ℃ at three stages, 285 ℃ at four stages and 275 ℃ at five stages; the injection pressure during injection molding is 80MPa, and the production period is 18s. The resulting bars were subjected to performance testing as follows.
Performance test:
(1) Tensile strength: the tensile speed at the time of the test was 50mm/min as determined by the method ISO 527-2;
(2) Elongation at break: the tensile speed at the time of the test was 50mm/min as determined by the method ISO 527-2;
(3) Flexural strength: the test conditions were 2mm/min as determined according to ISO 178;
(4) izod notched impact strength: the notch impact strength of the material is tested by adopting a cantilever Liang Baichui impact instrument (manufacturer: universal test, model: PIT-501J); impact strength was measured according to ISO 180-2001, notch depth 2mm, pendulum energy 2.75J;
(5) Fluidity of mosquito-repellent incense mould: adopting a spiral line form of a cavity of an injection molding movable mould panel, performing injection molding under the conditions that the injection molding temperature is 280 ℃, the pressure is 100MPa and the speed is 80%, and measuring the length of a spiral injection molding spline to compare the fluidity of the spiral injection molding spline;
(6) Number average molecular weight Mn: from the elution profile (vertical axis: signal intensity by detector; horizontal axis: elution time) of each sample obtained by using Gel Permeation Chromatography (GPC), the number average molecular weight of the main peak (polymer peak) in the elution profile was calculated from the calibration of the standard sample polymethyl methacrylate (PMMA);
(7) Yellow index YI: according to HG/T3862 test;
(8) Melt index MI: the test conditions were 280℃and 2.16kg, determined according to ISO 1133.
TABLE 1
From comparison of example 1, comparative example 3 and comparative example 4, it is known that in the preparation of hyperbranched polyamide resins, the molar amounts of the first polyamide salt and the second polyamide salt need to be controlled within a proper range, the molar amount of the first polyamide salt is too low, and the fluidity of the hyperbranched polyamide resin is deteriorated due to the reduced number of branches; the molar amount of the first polyamide salt is too high, the difficulty of reaction with the second polyamide salt increases due to its steric hindrance, resulting in a decrease in the number average molecular weight of the hyperbranched polyamide resin, while its fluidity increases, the tensile strength, elongation at break, flexural strength and izod notched impact strength are markedly deteriorated, and the yellow index increases.
As can be seen from the comparison of the example 1 and the comparative example 1 and the comparison of the example 8 and the comparative example 2, the hyperbranched polyamide resin provided by the invention has better processing flow property, obviously improves the tensile strength, the elongation at break, the bending strength and the izod notch impact strength, and has lower yellow index.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A hyperbranched polyamide resin characterized in that the hyperbranched polyamide resin has a structure shown in formula I:
Wherein each R 1、R2、R3 is independently selected from at least one of a C5-C18 linear or branched alkylene group;
R 4、R6 is independently selected from at least one of C5-C10 straight-chain or branched alkylene, substituted or unsubstituted C6-C30 arylene;
R 5、R7 is independently selected from at least one of C5-C10 straight-chain or branched alkylene, substituted or unsubstituted C6-C30 arylene;
X is selected from at least one of the following groups:
Wherein, Represents the attachment site of the group;
Y is selected from single bond, O is any one of the following;
a. b are each independently selected from integers from 1 to 5;
c is selected from 2 or 3;
m is selected from integers from 8 to 23;
n is an integer from 55 to 90;
Each of the substituted substituents in R 4、R6 is independently selected from at least one of carboxyl, hydroxyl, or isocyanate groups;
The substituents of the substituents in R 5、R7 are each independently selected from at least one of amino or hydroxy.
2. The hyperbranched polyamide resin according to claim 1 wherein each R 1、R2、R3 is independently selected from at least one of C5-C18 linear alkylene groups;
Preferably, each R 4、R6 is independently selected from at least one of a C5-C10 linear alkylene, a substituted or unsubstituted C6-C12 arylene;
Each of the substituted substituents in R 4、R6 is independently selected from at least one of carboxyl, hydroxyl, or isocyanate groups;
Preferably, each R 5、R7 is independently selected from at least one of a C5-C10 linear alkylene, a substituted or unsubstituted C6-C20 arylene;
each of the substituted substituents in R 5、R7 is independently selected from at least one of amino or hydroxy;
preferably, the number average molecular weight of the hyperbranched polyamide resin is 20000 to 55000.
3. The method of preparing the hyperbranched polyamide resin according to claim 1 or 2, characterized in that the method comprises the steps of:
(1) Mixing diamine containing R 1, tetrabasic acid containing X and a first solvent, and then carrying out a first reaction to obtain a first polyamide salt; mixing diamine containing R 3, dibasic acid containing R 2 and a second solvent, and then carrying out a second reaction to obtain a second polyamide salt;
Wherein R 1、R2、R3 and X have the same definitions as those of the structure shown in the formula I;
(2) Mixing the first polyamide salt, the second polyamide salt, a third solvent and a blocking agent, and then sequentially performing prepolymerization, final polymerization and granulation to obtain the hyperbranched polyamide resin;
the end-capping agent comprises a combination of a diamine and a diacid;
The diamine comprises a combination of a diamine containing R 4 and a diamine containing R 6;
the dibasic acid comprises a combination of a dibasic acid comprising R 5 and a dibasic acid comprising R 7;
Wherein, R 4、R5、R6、R7 has the same definition as the structure shown in the formula I.
4. The method of preparing according to claim 3, wherein the first solvent, the second solvent, and the third solvent each independently comprise water;
Preferably, the molar ratio of the diamine containing R 1 to the tetrabasic acid containing X is 1:1;
preferably, the mass ratio of the diamine containing R 1 to the first solvent is (0.2-0.55): 1;
preferably, the temperature of the first reaction is 80-100 ℃;
preferably, the time of the first reaction is 30-80min;
Preferably, after the first reaction is finished, the method further comprises the step of carrying out first concentration on the obtained reaction product to 100% of mass concentration;
Preferably, the first concentration is carried out at a temperature of 100-120 ℃.
5. The method of claim 3 or 4, wherein the molar ratio of diamine containing R 3 to diacid containing R 2 is 1:1;
Preferably, the mass ratio of the diamine containing R 3 to the second solvent is (0.36-1): 1;
preferably, the temperature of the second reaction is 60-100 ℃;
preferably, the second reaction time is 30-60min;
preferably, after the second reaction is finished, the method further comprises the step of performing second concentration on the obtained reaction product to reach a mass concentration of 100%;
preferably, the second concentration is carried out at a temperature of 100-120 ℃.
6. The production method according to any one of claims 3 to 5, wherein the molar amount of the first polyamide salt is 10 to 34% based on 100% of the molar amount of the second polyamide salt;
Preferably, the sum of the masses of the first and second polyamide salts is 50 to 90%, further preferably 50 to 80%, more preferably 60 to 70%, based on 100% of the total mass of the first, second and third solvent;
Preferably, the molar ratio of the end-capping agent to the first polyamide salt is 1 (4-22);
preferably, the molar ratio of diamine to diacid is 1:1;
Preferably, the mixed material of step (2) further comprises additives;
preferably, the additive comprises any one or a combination of at least two of a catalyst, a defoamer, a weather-resistant agent, a nucleating agent, an antistatic agent, a flame retardant, an anti-ultraviolet agent, a matting agent or an antioxidant;
preferably, the catalyst comprises any one or a combination of at least two of phosphoric acid, phosphorous acid, hypophosphorous acid organic matters or hypophosphorous acid salts;
Preferably, the defoamer comprises a silicon-containing compound;
Preferably, the weather-resistant agent comprises any one or a combination of at least two of a benzenediol compound, a salicylate compound, a benzotriazole compound, a benzophenone compound and a hindered amine compound;
Preferably, the nucleating agent comprises any one or a combination of at least two of nano silicon dioxide, nano calcium carbonate, titanate, zincate, montmorillonite, kaolin, talcum powder, siO 2、MgO、ZnO、Al2O3、ZrO2, carbon nano tubes, potassium titanate crystals, polycarbonate or polyarylethersulfone;
preferably, the antistatic agent comprises any one or a combination of at least two of amine derivatives, quaternary ammonium salts, sulfuric esters, phosphoric esters or polyethylene glycol derivatives;
Preferably, the flame retardant comprises any one or a combination of at least two of halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants or metal hydroxide flame retardants;
preferably, the anti-ultraviolet agent comprises any one or a combination of at least two of nano TiO 2, nano ZnO, nano SiO 2, nano Al 2O3 or nano FeO;
preferably, the matting agent comprises any one or a combination of at least two of titanium dioxide, silicon dioxide, aluminum oxide, sodium carbonate, calcium hydroxide, silicone oil, fatty acid salts or alkylphenols;
Preferably, the antioxidant comprises at least one of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, manganese hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite or zinc hypophosphite, and further preferably sodium hypophosphite;
Preferably, the additive is present in an amount of 0.05 to 0.2% by mass based on 100% by mass of the total of the first polyamide salt, the second polyamide salt, the third solvent, the capping agent and the additive.
7. The process according to any one of claims 3 to 6, wherein the pH of the resulting mixture after the completion of the mixing in step (2) is 7.2 to 7.8;
Preferably, the prepolymerization is divided into three reaction stages, namely a first reaction stage, a second reaction stage and a third reaction stage;
preferably, the first reaction stage is carried out under conditions of elevated temperature and elevated pressure;
Preferably, in the first reaction stage, the temperature of the reaction is increased from 80 ℃ to 190-210 ℃;
Preferably, the temperature rising speed of the first reaction stage is 1.5-2 ℃/min;
Preferably, in the first reaction stage, the pressure of the reaction is increased from 0.1MPa to 1.3-1.9MPa;
Preferably, the pressure rising speed of the first reaction stage is 0.02-0.04MPa/min;
preferably, the second reaction stage is carried out under conditions of elevated temperature and elevated pressure;
preferably, in the second reaction stage, the temperature of the reaction is increased from 190-210 ℃ to 230-250 ℃;
preferably, the temperature rising speed of the second reaction stage is 1-1.5 ℃/min;
Preferably, in the second reaction stage, the pressure of the reaction is increased from 1.3-1.9MPa to 2-2.5MPa;
preferably, the step-up speed of the second reaction stage is 0.0015-0.09MPa/min;
preferably, the reaction pressure in the third reaction stage is 2.6 to 4MPa (gauge pressure), more preferably 2.8 to 3.8MPa (gauge pressure), still more preferably 3 to 3.5MPa (gauge pressure);
Preferably, the reaction time of the third reaction stage is 60-90min;
Preferably, the reaction temperature of the third reaction stage is 260-290 ℃.
8. The method according to any one of claims 3 to 7, wherein the step of reducing the pressure is further included after the completion of the prepolymerization;
Preferably, the depressurization time is 60-90min;
Preferably, by said depressurization to 101-200KPa;
preferably, the temperature of the final polymerization is 250-270 ℃;
preferably, the final polymerization time is 10-60min;
preferably, the final polymerization pressure is-0.01 to-0.1 MPa (gauge pressure);
Preferably, the final polymerization further comprises the step of sequentially pressurizing and discharging;
preferably, the pressurization is carried out to 0.1 to 0.5MPa (gauge pressure).
9. The preparation method according to any one of claims 3 to 8, characterized in that it comprises the following steps:
(1) Mixing diamine containing R 1, tetrabasic acid containing X and a first solvent, performing a first reaction, and concentrating the obtained reaction product at 100-120 ℃ until the mass concentration is 100% after the first reaction is completed to obtain a first polyamide salt; mixing diamine containing R 3, diacid containing R 2 and a second solvent, and then carrying out a second reaction, wherein after the second reaction is finished, the obtained reaction product is concentrated to 100% of mass concentration at 100-120 ℃ to obtain a second polyamide salt;
The molar ratio of the diamine containing R 1 to the tetrabasic acid containing X is 1:1;
the mass ratio of the diamine containing R 1 to the first solvent is (0.2-0.55): 1;
the temperature of the first reaction is 80-100 ℃;
The time of the first reaction is 30-80min;
the molar ratio of the diamine containing R 3 to the diacid containing R 2 is 1:1;
The mass ratio of the diamine containing R 3 to the second solvent is (0.36-1): 1;
the temperature of the second reaction is 60-100 ℃;
The second reaction time is 30-60min;
(2) Mixing the first polyamide salt, the second polyamide salt, a third solvent, a blocking agent and an additive, then carrying out prepolymerization, reducing the pressure to 101-200KPa after the prepolymerization is completed, then carrying out final polymerization, pressurizing to 0.1-0.5MPa (gauge pressure) after the final polymerization is completed, discharging, and granulating to obtain the hyperbranched polyamide resin;
After the mixing is completed, the pH value of the obtained mixture is 7.2-7.8;
the molar amount of the first polyamide salt is 10-34% based on 100% of the molar amount of the second polyamide salt;
The sum of the masses of the first polyamide salt and the second polyamide salt is 50 to 90%, more preferably 50 to 80%, still more preferably 60 to 70%, based on 100% of the total mass of the first polyamide salt, the second polyamide salt and the third solvent;
the end-capping agent comprises a combination of a diamine and a diacid;
The diamine comprises a combination of a diamine containing R 4 and a diamine containing R 6;
the dibasic acid comprises a combination of a dibasic acid comprising R 5 and a dibasic acid comprising R 7;
the molar ratio of the diamine to the diacid is 1:1;
The mole ratio of the end-capping agent to the first polyamide salt is 1 (4-22);
the mass of the additive is 0.05-0.2% based on 100% of the total mass of the first polyamide salt, the second polyamide salt, the third solvent, the end-capping agent and the additive;
The prepolymerization is divided into three reaction stages, namely a first reaction stage, a second reaction stage and a third reaction stage;
the first reaction stage is carried out under the conditions of temperature rise and pressure rise;
In the first reaction stage, the temperature of the reaction is increased from 80 ℃ to 190-210 ℃;
the temperature rising speed of the first reaction stage is 1.5-2 ℃/min;
in the first reaction stage, the pressure of the reaction is increased from 0.1MPa to 1.3-1.9MPa;
the boosting speed of the first reaction stage is 0.02-0.04MPa/min;
The second reaction stage is carried out under the conditions of temperature rise and pressure rise;
In the second reaction stage, the temperature of the reaction is increased from 190-210 ℃ to 230-250 ℃;
The temperature rising speed of the second reaction stage is 1-1.5 ℃/min;
In the second reaction stage, the pressure of the reaction is increased from 1.3-1.9MPa to 2-2.5MPa;
The step-up speed of the second reaction stage is 0.0015-0.09MPa/min;
the reaction pressure in the third reaction stage is 2.6 to 4MPa (gauge pressure), more preferably 2.8 to 3.8MPa (gauge pressure), still more preferably 3 to 3.5MPa (gauge pressure);
The reaction time of the third reaction stage is 60-90min;
the reaction temperature of the third reaction stage is 260-290 ℃;
the time for reducing the pressure is 60-90min;
The temperature of the final polymerization is 250-270 ℃;
the final polymerization time is 10-60min;
the final polymerization pressure is-0.01 to-0.1 MPa (gauge pressure).
10. Use of the hyperbranched polyamide resin according to claim 1 or 2, characterized in that the hyperbranched polyamide resin is used in automotive parts, chemical materials or electronic devices.
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