CN110511375A - A kind of static resistant polyamide composite material and preparation method - Google Patents
A kind of static resistant polyamide composite material and preparation method Download PDFInfo
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- CN110511375A CN110511375A CN201810494151.5A CN201810494151A CN110511375A CN 110511375 A CN110511375 A CN 110511375A CN 201810494151 A CN201810494151 A CN 201810494151A CN 110511375 A CN110511375 A CN 110511375A
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 67
- 229920002647 polyamide Polymers 0.000 title claims abstract description 67
- 230000003068 static effect Effects 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 73
- 239000002253 acid Substances 0.000 claims abstract description 40
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 29
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 148
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 46
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 40
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 35
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 26
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 235000011037 adipic acid Nutrition 0.000 claims description 17
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 15
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 14
- 239000001361 adipic acid Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052790 beryllium Inorganic materials 0.000 claims description 6
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052730 francium Inorganic materials 0.000 claims description 6
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052705 radium Inorganic materials 0.000 claims description 6
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- PWLXTFFHCFWCGG-UHFFFAOYSA-N Heneicosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC(O)=O PWLXTFFHCFWCGG-UHFFFAOYSA-N 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical group CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 4
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- PXGXIMYFYPBSIL-UHFFFAOYSA-N [Mg].OP(O)O Chemical compound [Mg].OP(O)O PXGXIMYFYPBSIL-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 244000052616 bacterial pathogen Species 0.000 claims description 3
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 3
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 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 3
- 239000004137 magnesium phosphate Substances 0.000 claims description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 3
- 229960002261 magnesium phosphate Drugs 0.000 claims description 3
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 3
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 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 3
- FRXCPDXZCDMUGX-UHFFFAOYSA-N tridecane-1,1-diamine Chemical compound CCCCCCCCCCCCC(N)N FRXCPDXZCDMUGX-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000002216 antistatic agent Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 150000001279 adipic acids Chemical class 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N N-undecane Natural products CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 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 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention provides a kind of static resistant polyamide composite materials, its raw materials for production includes: 20-80 parts of aliphatic/aromatic binary acid, 0.2-10 parts of binary acid containing sulfonate groups, 20-80 parts of aliphatic diamine, 2-30 parts of graphene aqueous solution, 0.1-0.4 parts of end-capping reagent, 0.01-0.06 parts of catalyst, 30-160 parts of deionized water.The present invention also provides the preparation methods of the composite material.Static resistant polyamide composite material prepared by the present invention has good antistatic property, preferable mechanical property, excellent compatibility, preferable heat resistance and higher heat distortion temperature, expands its application range, also reduces production cost.
Description
Technical field
The invention belongs to synthesis of polymer material technical field, it is related to a kind of static resistant polyamide composite material and its preparation
Method.
Background technique
Polyamide is commonly called as nylon, refers in macromolecular main chain containing there are many a major class of recurring amide radical group (- CONH-)
Polymer.Since nineteen thirty-nine comes out, just it has been more and more widely used.PA6,PA66,PA11,PA12,PA610,
The various nylon such as PA612, MXD6 are come out one after another, and now annual yield is more than 270 × 104T occupies important in engineering plastics
Status.Polyamide is excellent electrical-insulation polymeric material, and surface resistivity is usually 1014~1016Ω, volume resistance
Rate is 1013~1014Ω ˙ cm, but only when the surface resistivity of polyamide reaches 108~1010Ω, volume resistivity reach
1011When Ω ˙ cm, it is just able to satisfy antistatic requirement.Static resistant polyamide is highly important functional polymer material, main to apply
In fields such as mining machinery, mine electrical equipment, electronic equipment part, textile machinery parts.
Material can be made to discharge rapidly by the surface conductivity or volume conductance that improve polyamide material prevents electrostatic
Aggregation, most common method are the various antistatic agents of addition.Ideal antistatic agent should have antistatic efficiency good and hold
Long, heat-resist and polyamide has moderate compatibility.Small organic molecule antistatic agent used now, due to being steamed by surface
Hair is influenced to factors such as friction, the washings on moulded products internal migration and surface, and antistatic effect can reduce or even disappear completely
It loses, is unable to satisfy the long-term antistatic requirement of product.Permanent antistatic agent is mostly the hydrophily high polymer of a kind of high molecular weight,
With lasting antistatic effect, but its additive amount needed it is higher, with the compatibility of polyamide substrate is poor, cost of material compared with
Height equally limits such static resistant polyamide composite material so that the mechanical property of product is poor, poor fluidity, price are high
Be widely used.
There is the polymerization process for being reported in polyamide that graphene is added, by graphene interconnected, so that material has
Preferable conductivity reduces the surface resistivity and volume resistivity of material, reaches the requirement of static resistant polyamide, but nanoscale
Graphene surface can be very high, easily reunite, do not propose how rationally to solve graphene in these reports in polyamide preparation
Agglomeration traits in the process, so that conductive effect of graphene is had a greatly reduced quality, the additive amount of only increase graphene be can be only achieved
Required electric conductivity and antistatic property.However, the graphene production cost of good dispersion is very under existing processing conditions
Height, increasing graphene additive amount will definitely increase the production cost of static resistant polyamide composite material, can equally hinder its application
It promotes.
Summary of the invention
In view of the deficiencies of the prior art, primary and foremost purpose is to provide a kind of static resistant polyamide composite material to the present invention.
Second object of the present invention is to provide a kind of preparation method of static resistant polyamide composite material.
In order to achieve the above objectives, solution of the invention is:
20-80 parts of aliphatic/aromatic binary acid,
0.2-10 parts of binary acid containing sulfonate groups,
20-80 parts of aliphatic diamine,
2-30 parts of graphene aqueous solution,
0.1-0.4 parts of end-capping reagent,
0.01-0.06 parts of catalyst,
30-160 parts of deionized water.
Preferably, the aliphatic/aromatic binary acid is 30-60 parts；
Preferably, the binary acid containing sulfonate groups is 0.5-5 parts；
Preferably, the aliphatic diamine is 30-60 parts；
Preferably, the graphene aqueous solution is 5-20 parts；
Preferably, the end-capping reagent is 0.2-0.3 parts；
Preferably, the catalyst is 0.02-0.05 parts；
Preferably, the deionized water is 40-150 parts.
The weight fraction ratio of the aliphatic dibasic acid and the aromatic acid is 0:100-100:0.
The aliphatic dibasic acid be selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid,
One of heneicosanedioic acid, dodecanedioic acid and tridecandioic acid or more than one；
The aromatic acid in terephthalic acid (TPA), M-phthalic acid, phthalic acid and naphthalenedicarboxylic acid one
Kind or more than one；
The aliphatic diamine be selected from butanediamine, pentanediamine, 2 methyl pentamethylenediamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine,
One of hendecane diamines, dodecamethylene diamine and tridecane diamine or more than one；
The end-capping reagent be selected from one of benzoic acid, acetic acid, propionic acid, adipic acid or more than one；
The catalyst is selected from sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, phosphorous acid
One of zinc, sodium hypophosphite, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc or more than one.
The binary acid containing sulfonate groups be selected from terephthalic acid (TPA) -5- Sulfonic Lithium, terephthalic acid (TPA) -5- sodium sulfonate,
Terephthalic acid (TPA) -5- potassium sulfonate, terephthalic acid (TPA) -5- sulfonic acid rubidium, terephthalic acid (TPA) -5- sulfonic acid caesium, terephthalic acid (TPA) -5- sulfonic acid
Francium, M-phthalic acid -5- Sulfonic Lithium, 5-sodium sulfo isophthalate, M-phthalic acid -5- potassium sulfonate, M-phthalic acid -5-
Sulfonic acid rubidium, M-phthalic acid -5- sulfonic acid caesium, M-phthalic acid -5- sulfonic acid francium, terephthalic acid (TPA) -5- sulfonic acid beryllium, terephthaldehyde
Acid -5- sulfonic acid magnesium, terephthalic acid (TPA) -5- sulfoacid calcium, terephthalic acid (TPA) -5- sulfonic acid strontium, terephthalic acid (TPA) -5- barium sulfonate, to benzene
Dioctyl phthalate -5- sulfonic acid radium, M-phthalic acid -5- sulfonic acid beryllium, M-phthalic acid -5- sulfonic acid magnesium, M-phthalic acid -5- sulfoacid calcium,
M-phthalic acid -5- sulfonic acid strontium, M-phthalic acid -5- barium sulfonate, M-phthalic acid -5- sulfonic acid radium, succinic acid sodium sulfonate, oneself two
Acid -2- sodium sulfonate, adipic acid -3- sodium sulfonate, decanedioic acid -2- sodium sulfonate, decanedioic acid -3- sodium sulfonate and decanedioic acid -4- sodium sulfonate
One of or more than one；
Mass fraction shared by graphene is 1-10% in the graphene aqueous solution；
The partial size of the graphene is 0.1-500nm.
A kind of preparation method of static resistant polyamide composite material comprising following steps:
(1) binary acid by 20-80 parts of aliphatic/aromatic binary acid, 0.2-10 parts containing sulfonate groups, 20-80 parts
Aliphatic diamine, 2-30 part graphene aqueous solution, 0.1-0.4 parts of end-capping reagents, 0.01-0.06 parts of catalyst, 30-160 parts go
Ionized water is added sequentially in autoclave；
(2) by autoclave vacuum nitrogen gas to replace the air in autoclave, nitrogen is then passed to pressure
Power reaches 30-50kPa,
(3) autoclave is heated, is warming up to the first temperature, isothermal reaction 1-3 hours；
(4) it is continuously heating to second temperature, pressure is increased to 1-3MPa, and is steamed by water in release autoclave
Gas makes pressure maintain 1-3MPa；
(5) slowly reach third temperature to temperature within heating 1-3 hours, heat up pressure release after finishing, while keeping temperature not
Become, by reacting kettle inner pressure pressure release to normal pressure, is escaped up to without tail gas within 0.5-2 hours.
(6) after the reaction was completed, inflated with nitrogen to pressure reaches 0.5-1.0MPa in reaction kettle, finally cuts material extrusion tie rod
Grain, obtains the static resistant polyamide composite material；
Further, the second temperature is higher than the first temperature, and the third temperature is higher than second temperature；
Further, first temperature is 80-150 DEG C, and the second temperature is 180-240 DEG C, and the third temperature is
220-340℃。
By adopting the above scheme, the beneficial effects of the present invention are:
First, the present invention by the polymerization process of polyamide simultaneously graphene aqueous solution and sulfonate groups is added,
And the ion of sulfonate and the polar group of graphene surface form stronger attraction such as hydroxyl, carboxyl, so as to effective
Improve graphene characteristic easy to reunite, so that nanoscale graphene can be evenly dispersed in polyamide molecule interchain, improves graphite
The electrical efficiency of alkene, improves the antistatic property of product, while reducing the additional amount of graphene in process of producing product, reduces life
Produce cost；
Second, the present invention by the polymerization process of polyamide simultaneously graphene aqueous solution and sulfonate groups is added,
And the conductive energy of sulfonate ion itself, it acts synergistically with the electric conductivity of graphene, it is quiet further to improve resisting for product
Electrical property, and sulfonate is compounded with graphene, it, can be into one while significantly improving the antistatic property of product
Step reduces the additional amount of graphene, reduces production cost；
Third, the present invention by the polymerization process of polyamide simultaneously graphene aqueous solution and sulfonate groups is added,
Sulfonate ion can make nanoscale graphene polyamide molecule interchain is evenly dispersed, compatibility is splendid, therefore will not influence
The mechanical property of polyamide compoiste material, mechanical property is substantially suitable with the pure polyamide for being not added with graphene, avoids
There are the inorganic fillers such as addition antistatic agent, especially carbon black, so that polyamide compoiste material mechanical property was substantially reduced
Problem；
4th, the present invention by the polymerization process of polyamide simultaneously graphene aqueous solution and sulfonate groups is added,
Sulfonate ion can make nanoscale graphene evenly dispersed in polyamide molecule interchain, and during product crystallisation by cooling from
To the effect of nucleating agent, nucleus, promotion product crystallization are provided for the crystallization of polyamide molecule chain, improves the thermal deformation temperature of product
Degree；
5th, the present invention by the polymerization process of polyamide simultaneously graphene aqueous solution and sulfonate groups is added,
Sulfonate ion may also function as the effect of lubricant, so as to improve the mobility of polyamide compoiste material, is blended and changes in the later period
Property during can greatly increase the contents of the third components such as glass, so as to improve product mechanical property, reduce production cost.
6th, the present invention by the polymerization process of polyamide simultaneously graphene aqueous solution and sulfonate groups is added,
Sulfonate ion can make nanoscale graphene evenly dispersed in polyamide molecule interchain, and graphene and sulfonate groups have very
Good thermal stability, in the blending and modifying and use process in later period, processing and use environment temperature can also be increased, and improve
The flexibility of blending and modifying technique, the application range for expanding product；
7th, the present invention by the polymerization process of polyamide simultaneously graphene aqueous solution and sulfonate groups is added,
Sulfonate ion can make nanoscale graphene evenly dispersed in polyamide molecule interchain, can be according to antistatic in practical application
It is required that graphene and sulfonate content in flexible modulation product, to meet the requirement of practical application.
Specific embodiment
The present invention provides a kind of static resistant polyamide composite material and preparation methods.
<static resistant polyamide composite material>
A kind of static resistant polyamide composite material, raw materials for production comprise the following components in parts by weight:
20-80 parts of aliphatic/aromatic binary acid,
0.2-10 parts of binary acid containing sulfonate groups,
20-80 parts of aliphatic diamine,
2-30 parts of graphene aqueous solution,
0.1-0.4 parts of end-capping reagent,
0.01-0.06 parts of catalyst,
30-160 parts of deionized water.
Wherein, the aliphatic/aromatic binary acid is preferably 30-60 parts
Aliphatic diamine can be preferably 30-60 parts.
Binary acid containing sulfonate groups can be preferably 0.5-5 parts.
End-capping reagent can be preferably 0.2-0.3 parts.
Catalyst can be preferably 0.02-0.05 parts.
Deionized water can be preferably 40-150 parts.
The weight fraction ratio of aliphatic dibasic acid and the aromatic acid can be between 0:100-100:0.
Graphene aqueous solution can be the aqueous solution that mass fraction shared by graphene is 1-10%.
Aliphatic dibasic acid can be succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, ten
One or more of one docosandioic acid, dodecanedioic acid and tridecandioic acid.
Aromatic acid can be one of terephthalic acid (TPA), M-phthalic acid, phthalic acid and naphthalenedicarboxylic acid
Or more than one.
Aliphatic diamine can be butanediamine, pentanediamine, 2 methyl pentamethylenediamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, ten
One or more of one alkane diamines, dodecamethylene diamine and tridecane diamine.
End-capping reagent can for one of benzoic acid, acetic acid, propionic acid, adipic acid or more than one.
Catalyst can be sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, zinc phosphite,
One of sodium hypophosphite, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc or more than one.
Binary acid containing sulfonate groups can be terephthalic acid (TPA) -5- Sulfonic Lithium, terephthalic acid (TPA) -5- sodium sulfonate, right
Phthalic acid -5- potassium sulfonate, terephthalic acid (TPA) -5- sulfonic acid rubidium, terephthalic acid (TPA) -5- sulfonic acid caesium, terephthalic acid (TPA) -5- sulfonic acid
Francium, M-phthalic acid -5- Sulfonic Lithium, 5-sodium sulfo isophthalate, M-phthalic acid -5- potassium sulfonate, M-phthalic acid -5-
Sulfonic acid rubidium, M-phthalic acid -5- sulfonic acid caesium, M-phthalic acid -5- sulfonic acid francium, terephthalic acid (TPA) -5- sulfonic acid beryllium, terephthaldehyde
Acid -5- sulfonic acid magnesium, terephthalic acid (TPA) -5- sulfoacid calcium, terephthalic acid (TPA) -5- sulfonic acid strontium, terephthalic acid (TPA) -5- barium sulfonate, to benzene
Dioctyl phthalate -5- sulfonic acid radium, M-phthalic acid -5- sulfonic acid beryllium, M-phthalic acid -5- sulfonic acid magnesium, M-phthalic acid -5- sulfoacid calcium,
M-phthalic acid -5- sulfonic acid strontium, M-phthalic acid -5- barium sulfonate, M-phthalic acid -5- sulfonic acid radium, succinic acid sodium sulfonate, oneself two
Acid -2- sodium sulfonate, adipic acid -3- sodium sulfonate, decanedioic acid -2- sodium sulfonate, decanedioic acid -3- sodium sulfonate and decanedioic acid -4- sodium sulfonate
One of or more than one.
<preparation method of static resistant polyamide composite material>
A kind of preparation method of static resistant polyamide composite material comprising following steps:
(1) binary acid by 20-80 parts of aliphatic/aromatic binary acid, 0.2-10 parts containing sulfonate groups, 20-80 parts
Aliphatic diamine, 2-30 part graphene aqueous solution, 0.1-0.4 parts of end-capping reagents, 0.01-0.06 parts of catalyst, 30-160 parts go
Ionized water is added sequentially in autoclave；
(2) by autoclave vacuum nitrogen gas to replace the air in autoclave, nitrogen is then passed to pressure
Power reaches 30-50kPa,
(3) autoclave is heated, is warming up to the first temperature, isothermal reaction 1-3 hours；
(4) it is continuously heating to second temperature, pressure is increased to 1-3MPa, and is steamed by water in release autoclave
Gas makes pressure maintain 1-3MPa；
(5) slowly reach third temperature DEG C to temperature within heating 1-3 hours, heat up pressure release after finishing, while keeping temperature
It is constant, it by reacting kettle inner pressure pressure release to normal pressure, is escaped up to without tail gas within 0.5-2 hours.
(6) after the reaction was completed, inflated with nitrogen to pressure reaches 0.5-1.0MPa in reaction kettle, finally cuts material extrusion tie rod
Grain, obtains the static resistant polyamide composite material；
Wherein, first temperature is 80-150 DEG C, and the second temperature is 180-240 DEG C, and the third temperature is
220-340 DEG C, and the second temperature is higher than the first temperature, and the third temperature is higher than second temperature；
In step (2), pressure can be preferably 40kPa.
In step (3), the first temperature is preferably to 110 DEG C.
In step (3), the time of isothermal reaction can be preferably 1.5 hours.
In step (4), second temperature can be preferably to 200-220 DEG C.
In step (4), pressure can be preferably 2MPa.
In step (5), third temperature is preferably 220-290 DEG C.
In step (5), venting duration can be preferably 1 hour.
In step (6), the pressure being filled with after nitrogen can be preferably 0.7MPa.
Below in conjunction with illustrated embodiment and comparative example, the present invention is further illustrated.
Comparative example 1
The preparation method of the static resistant polyamide composite material of this comparative example comprising following steps:
(1), the graphene that parts by weight are 56 parts of adipic acids, 44 parts of hexamethylene diamines, 20 parts of graphene mass fractions are 5% is weighed
Aqueous solution, 0.25 part of end-capping reagent acetic acid, 0.03 part of catalyst sodium hypophosphite, 100 parts of deionized waters, and the above component is added
Into autoclave；
(2), vacuumize, inflated with nitrogen three times, replace autoclave in air, then pass to nitrogen to pressure and reach
40kPa, so that reaction carries out under inert gas protection always, heating autoclave is warming up to 100 DEG C, isothermal reaction 1.5
Hour；It is continuously heating to 220 DEG C later, pressure is increased to 2MPa, passes through the method for vapor in release reaction kettle at this time
It keeps pressure in 2MPa, slowly pressure release after 1.5 hours to 275 DEG C of heating, while keeping temperature-resistant, through 1 hour by reaction kettle
Interior pressure pressure release is to normal pressure, until escaping without tail gas.
(3), after the reaction was completed, inflated with nitrogen to pressure reaches 0.7MPa in reaction kettle, and material is finally extruded tie rod pelletizing,
Product is obtained, the thermodynamic property and electrical performance testing of products therefrom the results are shown in Table 1.
Comparative example 2
The preparation method of the static resistant polyamide composite material of this comparative example comprising following steps:
(1), weighing parts by weight is 54 parts of adipic acids, 44 parts of hexamethylene diamines, 2 parts of succinic acid sodium sulfonates, 0.25 part of end-capping reagent second
Acid, 0.03 part of catalyst sodium hypophosphite, 100 parts of deionized waters, and the above component is added in autoclave；
(2), vacuumize, inflated with nitrogen three times, replace autoclave in air, then pass to nitrogen to pressure and reach
40kPa, so that reaction carries out under inert gas protection always, heating autoclave is warming up to 100 DEG C, isothermal reaction 1.5
Hour；It is continuously heating to 220 DEG C later, pressure is increased to 2MPa, passes through the method for vapor in release reaction kettle at this time
It keeps pressure in 2MPa, slowly pressure release after 1.5 hours to 275 DEG C of heating, while keeping temperature-resistant, through 1 hour by reaction kettle
Interior pressure pressure release is to normal pressure, until escaping without tail gas.
(3), after the reaction was completed, inflated with nitrogen to pressure reaches 0.7MPa in reaction kettle, and material is finally extruded tie rod pelletizing,
Product is obtained, the thermodynamic property and electrical performance testing of products therefrom the results are shown in Table 1.
Embodiment 1
The preparation method of the static resistant polyamide composite material of the present embodiment comprising following steps:
(1), weighing parts by weight is 54 parts of adipic acids, 44 parts of hexamethylene diamines, 2 parts of succinic acid sodium sulfonates, 20 parts of graphene quality
Score be 5% graphene aqueous solution, 0.25 part of end-capping reagent acetic acid, 0.03 part of catalyst sodium hypophosphite, 100 parts of deionizations
Water, and the above component is added in autoclave；
(2), vacuumize, inflated with nitrogen three times, replace autoclave in air, then pass to nitrogen to pressure and reach
40kPa, so that reaction carries out under inert gas protection always, heating autoclave is warming up to 100 DEG C, isothermal reaction 1.5
Hour；It is continuously heating to 220 DEG C later, pressure is increased to 2MPa, passes through the method for vapor in release reaction kettle at this time
It keeps pressure in 2MPa, slowly pressure release after 1.5 hours to 275 DEG C of heating, while keeping temperature-resistant, through 1 hour by reaction kettle
Interior pressure pressure release is to normal pressure, until escaping without tail gas.
(3), after the reaction was completed, inflated with nitrogen to pressure reaches 0.7MPa in reaction kettle, and material is finally extruded tie rod pelletizing,
Product is obtained, the thermodynamic property and electrical performance testing of products therefrom the results are shown in Table 1.
Embodiment 2
The preparation method of the static resistant polyamide composite material of the present embodiment comprising following steps:
(1), weighing parts by weight is 54 parts of adipic acids, 36 parts of butanediamine, 10 parts of 5-sodium sulfo isophthalates, 30 parts of stones
Black alkene content be 10% graphene aqueous solution, 0.4 part of end-capping reagent benzoic acid, 0.06 part of catalyst sodium phosphate, 40 parts of deionizations
Water, and the above component is added in autoclave；
(2), vacuumize, inflated with nitrogen three times, replace autoclave in air, then pass to nitrogen to pressure and reach
50kPa, so that reaction carries out under inert gas protection always, heating autoclave is warming up to 80 DEG C, and isothermal reaction 3 is small
When；It is continuously heating to 180 DEG C later, pressure is increased to 1MPa, is protected at this time by the method for vapor in release reaction kettle
Pressure is held in 1MPa, slowly pressure release after 3 hours to 320 DEG C of heating, while keeping temperature-resistant, it will be in reaction kettle through 0.5 hour
Pressure pressure release is to normal pressure, until escaping without tail gas.
(3), after the reaction was completed, inflated with nitrogen to pressure reaches 1.0MPa in reaction kettle, and material is finally extruded tie rod pelletizing,
Product is obtained, the thermodynamic property and electrical performance testing of products therefrom the results are shown in Table 1.
Embodiment 3
The preparation method of the static resistant polyamide composite material of the present embodiment comprising following steps:
(1), weighing parts by weight is 45 parts of terephthalic acid (TPA)s, 55 parts of decamethylene diamines, 0.2 part of terephthalic acid (TPA) -5- sulfoacid calcium, 2
Graphene aqueous solution that part graphene content is 1%, 0.1 part of end-capping reagent adipic acid, 0.01 part of catalyst zinc phosphite, 150 parts
Deionized water, and the above component is added in autoclave；
(2), vacuumize, inflated with nitrogen three times, replace autoclave in air, then pass to nitrogen to pressure and reach
30kPa, so that reaction carries out under inert gas protection always, heating autoclave is warming up to 150 DEG C, and isothermal reaction 1 is small
When；It is continuously heating to 240 DEG C later, pressure is increased to 3MPa, is protected at this time by the method for vapor in release reaction kettle
Pressure is held in 3MPa, slowly pressure release after 2 hours to 330 DEG C of heating, while keeping temperature-resistant, through 2 hours by reaction kettle internal pressure
Power pressure release is to normal pressure, until escaping without tail gas.
(3), after the reaction was completed, inflated with nitrogen to pressure reaches 0.5MPa in reaction kettle, and material is finally extruded tie rod pelletizing,
Product is obtained, the thermodynamic property and electrical performance testing of products therefrom the results are shown in Table 1.
Embodiment 4
The preparation method of the static resistant polyamide composite material of the present embodiment comprising following steps:
(1), weighing parts by weight is 31 parts of terephthalic acid (TPA)s, 20 parts of M-phthalic acids, 43 parts of hexamethylene diamines, 6 parts of adipic acid -2-
Sodium sulfonate, the graphene aqueous solution that 10 parts of graphene mass fractions are 10%, 0.3 part of end-capping reagent propionic acid, 0.04 part of catalyst
Sodium phosphite, 120 parts of deionized waters, and the above component is added in autoclave；
(2), vacuumize, inflated with nitrogen three times, replace autoclave in air, then pass to nitrogen to pressure and reach
45kPa, so that reaction carries out under inert gas protection always, heating autoclave is warming up to 120 DEG C, isothermal reaction 2.5
Hour；It is continuously heating to 225 DEG C later, pressure is increased to 2MPa, passes through the method for vapor in release reaction kettle at this time
It keeps pressure in 2MPa, slowly pressure release after 1 hour to 300 DEG C of heating, while keeping temperature-resistant, through 0.8 hour by reaction kettle
Interior pressure pressure release is to normal pressure, until escaping without tail gas.
(3), after the reaction was completed, inflated with nitrogen to pressure reaches 0.7MPa in reaction kettle, and material is finally extruded tie rod pelletizing,
Product is obtained, the thermodynamic property and electrical performance testing of products therefrom the results are shown in Table 1.
Table 1
By comparing comparative example 1, the polymerization process of comparative example 2 and embodiment 1 and test data it can be concluded that,
Comparative example 1 joined 1% graphene, comparative example 2 joined 2% dicarboxylic acid monomer containing sulfonate groups, implement
1% graphene and 2% is added simultaneously and contains sulfonate groups for example 1, remaining component, dosage, polymerization technique are identical, products obtained therefrom
Structure is also essentially identical, and comparative example 2 chains molecule due to joined 2% dicarboxylic acid monomer containing sulfonate groups
Structure is irregular, and crystallinity is caused to be lower, and fusing point, tensile strength, modulus and heat distortion temperature are substantially reduced, and embodiment 1 exists
1% graphene is added on the basis of comparative example 2, fusing point, tensile strength, modulus and heat distortion temperature are all obviously improved, say
Bright addition graphene can improve the crystallization of product really, play the role of nucleating agent, increase crystallinity, so that product fusing point liter
Height, tensile strength is got higher, modulus increases, heat distortion temperature increases；Compare comparative example 1, comparative example 2 and embodiment 1
Surface resistivity and volume resistivity, the conductivity of embodiment 1 illustrate to be added significantly more than the sum of the conductivity of both fronts
Dicarboxylic acid monomer containing sulfonate groups, the ion of sulfonate can with the polar group of graphene surface, such as hydroxyl, carboxyl, shape
At stronger attraction, so that the reunion of graphene is effectively improved, so that nanoscale graphene is equal in polyamide molecule interchain
Even dispersion, the electric conductivity of the ion of sulfonate and the electric conductivity of graphene act synergistically, and can greatly improve leading for graphene
Electrical efficiency improves the antistatic property of product.
It is also known by comparing the polymerization process and test result of each embodiment, the mechanical property of product, thermal property, table
The content of graphene, the content of the dicarboxylic acid monomer containing sulfonate groups have close pass in surface resistivity and volume resistivity and raw material
System, the content of graphene is higher, and the content of the dicarboxylic acid monomer containing sulfonate groups is higher, and graphene dispersion is more uniform, polyamide
The thermal properties such as the mechanical property of resin is better, fusing point, heat distortion temperature are higher, surface resistivity and volume resistivity are lower,
Antistatic property is better, and vice versa, the unit that furthermore mechanical property of product, thermal property and electric property polymerize with participation
Component is also closely related, thus, the present invention is by being added graphene aqueous solution and sulfonate groups simultaneously in the course of the polymerization process, sulphur
The ion of hydrochlorate can form stronger attraction such as hydroxyl, carboxyl with the polar group of graphene surface, can be effectively improved stone
The reunion of black alkene promotes polyamide crystallization, improves so that nanoscale graphene is evenly dispersed in polyamide molecule interchain
The thermodynamic properties such as crystallinity, fusing point, heat distortion temperature, tensile strength, the bending modulus of product, while nanoscale graphene
In the more uniform dispersion of polyamide molecule interchain, graphene nano particle is connected with each other, the electric conductivity of the ion of sulfonate
It acts synergistically with the electric conductivity of graphene, so that material has preferable conductivity, reduces the surface resistivity and body of material
Product resistivity, reaches the requirement of static resistant polyamide, so as to improve the antistatic property of its final products, changes to later product
Property production and application all have active influence.
The above-mentioned description to embodiment is that this hair can be understood and used for the ease of those skilled in the art
It is bright.Those skilled in the art obviously readily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiments, without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments.
Those skilled in the art's principle according to the present invention, not departing from improvement that scope of the invention is made and modification all should be at this
Within the protection scope of invention.
Claims (10)
1. a kind of static resistant polyamide composite material, it is characterised in that: its raw materials for production comprises the following components in parts by weight:
20-80 parts of aliphatic/aromatic binary acid,
0.2-10 parts of binary acid containing sulfonate groups,
20-80 parts of aliphatic diamine,
2-30 parts of graphene aqueous solution,
0.1-0.4 parts of end-capping reagent,
0.01-0.06 parts of catalyst,
30-160 parts of deionized water.
2. static resistant polyamide composite material according to claim 1, it is characterised in that: the aliphatic/aromatic two
First acid is 30-60 parts；And/or
The binary acid containing sulfonate groups is 0.5-5 parts；And/or
The aliphatic diamine is 30-60 parts；And/or
The graphene aqueous solution is 5-20 parts；And/or
The end-capping reagent is 0.2-0.3 parts；And/or
The catalyst is 0.02-0.05 parts；And/or
The deionized water is 40-150 parts.
3. static resistant polyamide composite material according to claim 1 or 2, it is characterised in that: the aliphatic dibasic acid
Weight fraction ratio with the aromatic acid is 0:100-100:0.
4. static resistant polyamide composite material according to claim 1 or 2, it is characterised in that: the aliphatic dibasic acid
Selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid and
One of tridecandioic acid or more than one；And/or
The aromatic acid be selected from one of terephthalic acid (TPA), M-phthalic acid, phthalic acid and naphthalenedicarboxylic acid or
More than one；And/or
The aliphatic diamine is selected from butanediamine, pentanediamine, 2 methyl pentamethylenediamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 11
One of alkane diamines, dodecamethylene diamine and tridecane diamine or more than one；And/or
The end-capping reagent be selected from one of benzoic acid, acetic acid, propionic acid, adipic acid or more than one；And/or
The catalyst is selected from sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, zinc phosphite, secondary
One of sodium phosphite, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc or more than one.
5. static resistant polyamide composite material according to claim 4, it is characterised in that: the aliphatic dibasic acid is for oneself
One or more of diacid and decanedioic acid；And/or
The aromatic acid is one or more of terephthalic acid (TPA) and M-phthalic acid；And/or
The aliphatic diamine is one or more of hexamethylene diamine and decamethylene diamine；And/or
The end-capping reagent is one or more of acetic acid and adipic acid；And/or
The catalyst is sodium hypophosphite.
6. static resistant polyamide composite material according to claim 1 or 2, it is characterised in that: described to contain sulfonate groups
Binary acid be selected from terephthalic acid (TPA) -5- Sulfonic Lithium, terephthalic acid (TPA) -5- sodium sulfonate, terephthalic acid (TPA) -5- potassium sulfonate, to benzene
Dioctyl phthalate -5- sulfonic acid rubidium, terephthalic acid (TPA) -5- sulfonic acid caesium, terephthalic acid (TPA) -5- sulfonic acid francium, M-phthalic acid -5- Sulfonic Lithium,
5-sodium sulfo isophthalate, M-phthalic acid -5- potassium sulfonate, M-phthalic acid -5- sulfonic acid rubidium, M-phthalic acid -5- sulfonic acid
Caesium, M-phthalic acid -5- sulfonic acid francium, terephthalic acid (TPA) -5- sulfonic acid beryllium, terephthalic acid (TPA) -5- sulfonic acid magnesium, terephthalic acid (TPA) -5-
Sulfoacid calcium, terephthalic acid (TPA) -5- sulfonic acid strontium, terephthalic acid (TPA) -5- barium sulfonate, terephthalic acid (TPA) -5- sulfonic acid radium, isophthalic diformazan
Acid -5- sulfonic acid beryllium, M-phthalic acid -5- sulfonic acid magnesium, M-phthalic acid -5- sulfoacid calcium, M-phthalic acid -5- sulfonic acid strontium, isophthalic
Dioctyl phthalate -5- barium sulfonate, M-phthalic acid -5- sulfonic acid radium, succinic acid sodium sulfonate, adipic acid -2- sodium sulfonate, adipic acid -3- sulphur
One of sour sodium, decanedioic acid -2- sodium sulfonate, decanedioic acid -3- sodium sulfonate and decanedioic acid -4- sodium sulfonate or more than one；
Preferably, the binary acid containing sulfonate groups is in 5-sodium sulfo isophthalate and succinic acid sodium sulfonate
More than one.
7. static resistant polyamide composite material according to claim 1 or 2, it is characterised in that: the graphene aqueous solution
Mass fraction shared by middle graphene is the aqueous solution of 1-10%；And/or
The partial size of the graphene is 0.1-500nm.
8. a kind of preparation method of the static resistant polyamide composite material as described in claim 1 to 7 is any, it is characterised in that:
The following steps are included:
(1) binary acid by 20-80 parts of aliphatic/aromatic binary acid, 0.2-10 parts containing sulfonate groups, 20-80 parts of fat
Race's diamine, 2-30 part graphene aqueous solution, 0.1-0.4 parts of end-capping reagents, 0.01-0.06 parts of catalyst, 30-160 parts of deionizations
Water is added sequentially in autoclave；
(2) it by autoclave vacuum nitrogen gas to replace the air in autoclave, then passes to nitrogen to pressure and reaches
30-50kPa,
(3) autoclave is heated, is warming up to the first temperature, isothermal reaction 1-3 hours；
(4) it is continuously heating to second temperature, pressure is increased to 1-3MPa, and is made by vapor in release autoclave
Pressure maintains 1-3MPa；
(5) slowly reach third temperature to temperature within heating 1-3 hours, heat up pressure release after finishing, while keeping temperature-resistant,
It by reacting kettle inner pressure pressure release to normal pressure, is escaped up to without tail gas within 0.5-2 hours.
(6) after the reaction was completed, inflated with nitrogen to pressure reaches 0.5-1.0MPa in reaction kettle, and material is finally extruded tie rod pelletizing,
Obtain the static resistant polyamide composite material.
9. a kind of preparation method of static resistant polyamide composite material as claimed in claim 8, it is characterised in that: described first
Temperature is 80-150 DEG C, and the second temperature is 180-240 DEG C, and the third temperature is 220-340 DEG C.
10. a kind of preparation method of static resistant polyamide composite material as claimed in claim 8, it is characterised in that: described
Two temperature are higher than the first temperature, and the third temperature is higher than second temperature.
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| CN113429570A (en) * | 2021-05-12 | 2021-09-24 | 浙江中科玖源新材料有限公司 | Sulfonated polyamide binder for lithium-sulfur battery and positive plate |
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