CN116804094A - Para aminobenzoic acid intercalation hydrotalcite-like fire retardant, preparation method and application thereof - Google Patents
Para aminobenzoic acid intercalation hydrotalcite-like fire retardant, preparation method and application thereof Download PDFInfo
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- CN116804094A CN116804094A CN202310847499.9A CN202310847499A CN116804094A CN 116804094 A CN116804094 A CN 116804094A CN 202310847499 A CN202310847499 A CN 202310847499A CN 116804094 A CN116804094 A CN 116804094A
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- aminobenzoic acid
- flame retardant
- aluminum
- solution
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000003063 flame retardant Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000009830 intercalation Methods 0.000 title claims abstract description 28
- 230000002687 intercalation Effects 0.000 title claims abstract description 28
- 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 abstract description 67
- 239000003822 epoxy resin Substances 0.000 claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 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 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 abstract description 6
- 229920000620 organic polymer Polymers 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 14
- 229960001545 hydrotalcite Drugs 0.000 description 14
- 229910001701 hydrotalcite Inorganic materials 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- -1 compounds Chemical compound 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 7
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 7
- 229960004050 aminobenzoic acid Drugs 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 7
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000002572 peristaltic effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000004224 protection Effects 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 229940091250 magnesium supplement Drugs 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229960002337 magnesium chloride Drugs 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229940063656 aluminum chloride Drugs 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000002431 foraging effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction 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
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a para aminobenzoic acid intercalation hydrotalcite-like fire retardant, a preparation method and application thereof. The preparation method comprises the following steps: and (3) reacting a mixed system containing para-aminobenzoic acid and/or para-aminobenzoate, divalent metal chloride, an aluminum source and alkali to obtain the para-aminobenzoic acid intercalated hydrotalcite-like flame retardant. The invention designs and utilizes a low-cost and simple-operation coprecipitation method to synthesize the magnesium-based hydrotalcite-like compound intercalated with the para-aminobenzoic acid, and uses 4NP-LDH as an additive flame retardant in epoxy resin to improve the flame retardant property of the composite material, and the mechanical property of the composite material is maintained to the greatest extent while the flame retardant property of the organic polymer is improved.
Description
Technical Field
The invention relates to a para aminobenzoic acid intercalation hydrotalcite-like flame retardant and a preparation method and application thereof, belonging to the technical field of hydrotalcite preparation.
Background
LDHs (layered double hydroxides ) are typical anionic intercalation layered compounds, collectively known as Hydrotalcite (HT) and hydrotalcite-like compounds (hydrotalcite like compounds, HTLCs), whose laminates are composed of binary or multi-metal hydroxides, and are interlaminar filled with the corresponding anions to balance the charge in the laminate. The general structural formula of the common LDHs isTypical representatives thereof are natural hydrotalcite (Mg 6 Al 2 (OH) 16 ·4H 2 O), other divalent (e.g. Mn 2+ 、Ni 2+ 、Zn 2+ Etc.) and trivalent (e.g. Fe 3+ 、Co 3 + 、Cr 3+ Etc.) metal ions may also form similar layered compounds, which may be collectively referred to as hydrotalcite-like compounds, the interlayer anions of which may be incorporated into the metal hydroxide layers by ion exchange, co-precipitation and memory effect processes.
LDHs can be regarded as supermolecular structures with host-guest interactions, where metal ions in the LDHs host layer interact with hydroxyl groups in strong chemical bonds, and anions between the host layer and the guest layer interact mainly through coulombic static electricity, hydrogen bonds or van der waals forces, and form a composite material with a supermolecular structure in an orderly manner. In the materials, the interaction of a host and a guest and the nano property of the two-dimensional lamellar material lead the two-dimensional lamellar material to have unique physical and chemical properties such as light, electricity, magnetism, catalysis, adsorption and the like. Therefore, LDHs are widely used in the fields of catalysis and adsorption, optics, electrochemistry, magnetism, corrosion protection, and the like.
Because of the adjustability of the types and the proportion of cations in the LDHs laminate, and the interchangeability and intercalation of anions between layers, the LDHs has great adjustability in nature, materials can be designed by selecting anions and cations involved in the LDHs according to different requirements, and the functionalization of the materials or the modification of the functions of the materials can be realized by adjusting and controlling laminate ions in the LDHs according to diversified requirements on the properties of the materials, so that the LDHs has great development and application potential.
When natural hydrotalcite or artificial synthetic hydrotalcite is directly added into high polymer flame retardant, the performance of the flame retardant is similar to magnesium hydroxide, aluminum hydroxide and the like, and the flame retardant mode mainly adopts decomposition reaction to absorb heat and release H 2 O and CO 2 And the generated oxide layer isolates the combustible gas from diffusing and retarding, and meanwhile, the generated oxide can catalyze the combustible gas to carbon to a certain extent and can realize effective smoke suppression on smoke adsorption. However, a large amount of the flame retardant must be added to achieve a good flame retardant effect, and the mechanical properties are obviously reduced.
The magnesium aluminum LDHs and other flame retardants such as magnesium hydroxide, organic phosphoric acid, borate and the like have synergistic flame retardant effect, so that the flame retardant property of the magnesium aluminum LDHs can be improved to a certain extent, and the addition amount of the magnesium aluminum LDHs is reduced. But as a main inorganic powder flame-retardant filler, the mechanical property is still obvious, and when the flame-retardant filler is compounded with a large amount of organic phosphoric acid and the like, the flame retardant can generate certain toxicity, and the cost of the flame-retardant can be increased to a certain extent.
The LDHs with the metal element of the artificially synthesized hydroxide laminate as the transition metal and the composite material thereof have better flame-retardant effect. LDHs such as Xin added with Ni-Fe as laminate metal ion to ring2wt% of the oxygen resin can reduce the peak value of the maximum heat release rate in cone calorimeter from 1730 to 1070kW/m 2 The synthesis raw material is nitrate, urea is used as an alkali source and a carbon source, and the synthesis is carried out for 24 hours under the hydrothermal condition at 150 ℃, so that the synthesis cost is high, and the large-scale continuous production is difficult under the high-temperature and high-pressure condition. The flame-retardant effect of the hydrotalcite can be improved by intercalation modification of magnesium aluminum hydrotalcite by organic acid radical anions, so as to reduce the addition amount, for example Ehsan Naderi Kalali and the like, introducing a LDHs with the mixed ions of cyclodextrin, chalcone and dodecylsulfonic acid intercalated together, the LDHs has better flame-retardant effect, the UL-94 vertical combustion can reach V-0 level by adding 7 percent by weight of the epoxy resin, and the peak value of the heat release rate in conical heat is reduced from 938 in pure epoxy resin to 318Wm -2 However, the nitrate is adopted as the raw material, and the preparation process of the intercalation anions is more complex, thereby greatly increasing the production complexity and cost.
From the viewpoint of production cost, many flame retardants based on LDHs are difficult to put into practical use due to problems such as high raw material price and complicated production process.
In addition, because of the problem of compatibility with the polymer, the flame retardant effect of the green and environment-friendly inorganic powder flame retardant such as magnesium hydroxide and aluminum hydroxide is difficult to be fully exerted in the polymer. On the one hand, when the addition amount is small, the mechanism of solid phase flame retardance determines that the flame retardance is limited, and the UL-94 cannot reach any flame retardance grade, and the peak value of the maximum heat release rate in the cone-shaped calorimetric test is less reduced compared with that of a pure polymer. On the other hand, when the addition amount is large, because the compatibility leads to serious agglomeration of the flame retardant filler, the flame retardant filler is difficult to uniformly mix, so that the polymer composite material cannot be used, and even though the high-addition-amount composite material prepared by a special addition way (such as ball milling premixing) has better flame retardant property, the mechanical property of the high-addition-amount composite material is obviously reduced. These problems can be solved by surface modification to increase compatibility, introducing transition metals or preparing special morphologies to improve flame retardant properties. Surface modification in many cases has limited ability to change the decrease in mechanical properties, and the additional modification process greatly increases its cost of preparation. Similar to the surface modification effect, although changing the special morphology or introducing transition metal can also greatly improve the flame retardant property, however, it is often difficult to achieve the UL-94 test V-0 level even at low addition levels, and the special preparation method often results in a significant increase in cost. Although the transition metal nano powder with the catalytic effect can achieve better flame retardant effect under the condition of small addition amount, the preparation process is complex and the preparation cost is high. In the comprehensive view, the practical low-cost inorganic powder flame retardant can not be produced at present easily, and simultaneously, the large addition amount and the high flame retardant property can be realized, and the mechanical property can be reduced; the powder with the special shape and the powder with the catalytic flame retardant property have the advantages of complex synthesis method, high cost and almost no practical value in production.
In summary, when natural hydrotalcite is used for flame retardance, the addition amount is large, the mechanical property is obviously reduced, the large addition amount cannot be achieved without special adding equipment (when the addition amount is large, inorganic powder is settled in the polymer and even separated out from the surface, so that the mechanical property is seriously affected), and the flame retardance cannot be effectively achieved. The preparation process of the inorganic acid radical intercalation hydrotalcite-like compound with special morphology generally needs high temperature and high pressure, consumes larger energy, has the problem that the flame retardant property is improved because a large amount of inorganic acid radical intercalation hydrotalcite-like compound cannot be added, and has larger mechanical property. When the transition metal is adopted to prepare the LDHs with high catalytic activity, the preparation process is complex, the cost is high, and mass production cannot be realized.
In addition, the existing reported synthesis method of zinc-aluminum hydrotalcite intercalated by p-benzoate is a roasting reduction method, which needs to prepare nitrate radical or other ion intercalated LDHs (usually adopting a hydrothermal method of more than 1 ℃ to realize regular morphology) firstly, then roasting at high temperature (500 ℃) and then carrying out structure restoration, the preparation process is complex, the time consumption is long, the energy consumption is high, the nitrate is often utilized for preparation, the production cost is high,
disclosure of Invention
The invention aims to provide a para aminobenzoic acid intercalation hydrotalcite-like fire retardant and a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of a para aminobenzoic acid intercalation hydrotalcite-like fire retardant, which comprises the following steps:
and (3) reacting a mixed system containing para-aminobenzoic acid and/or para-aminobenzoate, divalent metal chloride, an aluminum source and alkali to obtain the para-aminobenzoic acid intercalated hydrotalcite-like compound.
The invention also provides the para aminobenzoic acid intercalation hydrotalcite-like fire retardant prepared by the preparation method.
The invention also provides a flame-retardant epoxy resin composite material, which comprises the paraaminobenzoic acid intercalation hydrotalcite-like flame retardant, epoxy resin, an auxiliary agent and a curing agent.
The invention also provides a preparation method of the flame-retardant epoxy resin composite material, which comprises the following steps:
uniformly stirring the para-aminobenzoic acid intercalated hydrotalcite-like flame retardant, epoxy resin and auxiliary agent, adding a curing agent for curing, and curing to obtain the flame-retardant epoxy resin composite material.
Compared with the prior art, the invention has the beneficial effects that:
1) The preparation method of the para aminobenzoic acid intercalated hydrotalcite-like flame retardant provided by the invention utilizes a simple coprecipitation method, utilizes magnesium chloride with abundant and low cost resources as a magnesium source, takes para aminobenzoic acid as an anion source, takes sodium hydroxide as an alkali source, takes aluminum chloride or metaaluminate as an aluminum source for preparation, has low cost and is convenient for mass production.
2) According to the invention, the para aminobenzoic acid intercalated hydrotalcite-like compound is added with epoxy resin according to a certain proportion to prepare the composite material, so that inorganic powder does not settle in the composite material, the flame retardant property and the ultraviolet resistance of the composite material are improved, and the mechanical property is better maintained to the greatest extent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is an XRD spectrum of 4NP-LDH obtained in example 1 of the present invention.
FIG. 2 is an XRD spectrum of 4NP-LDH obtained in example 2 of the present invention.
FIG. 3 is a schematic view of the water droplet angle of 4NP-LDH obtained in example 2 of the present invention.
FIG. 4 is a graph showing the TG pattern of 4NP-LDH obtained in example 2 of the present invention.
FIG. 5 is a DTG trace of 4NP-LDH obtained in example 2 of the present invention.
Fig. 6 is an XRD spectrum of 4NP-LDH of LDHs prepared in example 3 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has provided the technical scheme of the present invention through long-term research and a great deal of practice, and the technical scheme of the present invention will be clearly and completely described below, which is mainly a para aminobenzoic acid intercalation hydrotalcite-like fire retardant, and a preparation method and application thereof.
The embodiment of the invention provides a preparation method of a para aminobenzoic acid intercalation hydrotalcite-like fire retardant, which comprises the following steps:
and (3) reacting a mixed system containing para-aminobenzoic acid and/or para-aminobenzoate, divalent metal chloride, an aluminum source and alkali to obtain the para-aminobenzoic acid intercalated hydrotalcite-like flame retardant.
Para aminobenzoic acid is an important organic synthesis intermediate, is widely applied to the fields of medicines and dyes, and has certain ultraviolet absorptivity.
In some specific embodiments, the divalent metal element in the divalent metal chloride comprises any one or a combination of two or more of magnesium, copper, calcium, zinc, manganese, and iron.
Further, the aluminum source comprises any one or more than two of aluminum salt, aluminum hydroxide, sodium aluminate and sodium metaaluminate;
further, the alkali comprises any one or a combination of sodium hydroxide and potassium hydroxide.
In some specific embodiments, the ratio of aluminum element to the amount of para-aminobenzoic acid and/or para-aminobenzoate material in the mixed system is from 1:1 to 1:6.
Further, the ratio of the amounts of the substances of the divalent metal element and the aluminum element in the mixed system is 1:1-4:1.
Further, the concentration of aluminum element in the mixed system is 0-0.8mol/L.
In some specific embodiments, the preparation method of the para-aminobenzoic acid intercalation hydrotalcite-like flame retardant specifically comprises the following steps:
preparing a divalent metal chloride into a first solution;
preparing a second solution from para-aminobenzoic acid and/or para-aminobenzoate, an aluminum source and a base;
and mixing the first solution and the second solution for reaction to obtain the para aminobenzoic acid intercalation hydrotalcite-like fire retardant.
In some specific embodiments, when the aluminum source is aluminum chloride, the amount n of the base material in the mixed system B1 Is 0.9× (2 (n) M +n A )+n O )～1.1×(2(n M +n A )+n O ) Wherein n is M The amount of the substance being a divalent metal element, n A The amount of the substance being a trivalent metal element, n O Is the amount of substance of para aminobenzoic acid.
Preferably, when the aluminum source is aluminum hydroxide, the amount of the base material is n B1 -3n A 。
Preferably, when the aluminum source is sodium metaaluminate or sodium aluminate, the amount of the base material is n B1 -4n A 。
In some specific embodiments, the preparation method of the para-aminobenzoic acid intercalation hydrotalcite-like flame retardant further comprises aging, washing and drying after the reaction of the mixed system is finished, so as to obtain the para-aminobenzoic acid intercalation hydrotalcite-like flame retardant.
Further, the reaction time is 0.5-3h.
Further, the aging temperature is 20 to 160 ℃, preferably 60 to 90 ℃.
Further, the aging time is 3-72 hours, preferably 6-48 hours;
further, the drying temperature is 20-120 ℃.
In some more specific embodiments, the preparation method of the para-aminobenzoic acid intercalated hydrotalcite-like flame retardant comprises the following steps:
(1) Weighing bivalent metal chloride with a certain mass, and assuming the mass of the bivalent metal chloride is n M A solution A having a constant concentration (0.1 to 4.0 mol/L) is prepared.
(2) According to the different aluminum sources, the solution B is prepared according to different proportions, and the concentration of aluminum element in the solution is required to be ensured to be (0-0.8 mol/L). When the aluminum source is aluminum chloride, weighing a proper amount of the aluminum source, ensuring that the ratio of the total mass of the divalent metal element to the trivalent metal element is a specified value (1.0-4.0), and assuming that the mass is n A Weighing p-benzoic acid according to a certain multiple (1-6) of the amount of the substance of the trivalent metal element, and assuming that the amount of the substance is n O Weighing a certain amount of alkali to make the amount of the alkali n B1 Is in accordance with (2 (n) M +n A )+n O ) Mixing the three materials, adding appropriate amount of water to obtain solution B 1 . When the aluminum source is aluminum hydroxide, the amount of the aluminum element and the organic acid is unchanged, and only the amount n of the alkali substance is required B2 Satisfy n B1 -3n A Then formulated as solution B2. When the aluminum source is sodium metaaluminate or sodium aluminate, the amount of the substances of aluminum element and organic acid is unchanged, and only the amount nB3 of the substances of alkali is required to satisfy n B1 -4 nA Then is prepared into solution B 3 。
(4) The entire reaction may be stirred or sonicated with or without nitrogen protection (without nitrogen protection, some of the LDHs are converted to carbonate intercalation).
(5) The reaction feeding mode can be added according to any one of the following three modes: (a) A is placed in a reaction vessel, the reaction temperature is controlled to a specified temperature (20-90 ℃ C.), and then B (optionally, B is specified) 1 ，B 2 Or B is a 3 ) Adding the solution A at a constant speed; (b) B is placed in a reaction container, the reaction temperature is controlled to be a specified temperature (20-90 ℃), and then A is added into the solution B at a constant speed; (c) The reaction vessel was preheated and held at the indicated temperature (20-90 ℃) and then both A, B solutions were added simultaneously to the reaction vessel at a proportional rate uniformly, ensuring that the addition was started simultaneously and completed simultaneously.
(6) After the materials are added, the materials are continuously stirred for a certain time (0.5 to 3 hours) in a reactor under the condition that the materials are kept at a constant temperature, and then are transferred into an aging container (when the aging temperature is higher than the boiling point of water, a pressure-resistant and temperature-resistant container is needed), and are aged for a certain time (3 to 72 hours) at a certain temperature (20 to 160 ℃).
(7) Filtering, adding water to wash until the filtrate is neutral, and washing the solid for a plurality of times by using a certain amount of water (0.1-2 times of the volume of the reaction liquid), and further washing out soluble impurities.
(8) The filter cake is dried to constant weight under vacuum or nitrogen atmosphere at a certain temperature (normal temperature-160 ℃), and air drying can be selected, which has the disadvantage that a small part of LDHs can be converted into hydrotalcite with carbonate intercalation or partial oxidation of acid radicals can occur at a higher temperature.
The embodiment of the invention also provides the para aminobenzoic acid intercalation hydrotalcite-like flame retardant prepared by the preparation method.
The embodiment of the invention also provides a flame-retardant epoxy resin composite material, which comprises the paraaminobenzoic acid intercalation hydrotalcite-like flame retardant, epoxy resin and a curing agent.
The embodiment of the invention also provides a preparation method of the flame-retardant epoxy resin composite material, which comprises the following steps:
uniformly stirring the para-aminobenzoic acid intercalated hydrotalcite-like flame retardant, epoxy resin and auxiliary agent, adding a curing agent for curing, and curing to obtain the flame-retardant epoxy resin composite material.
In some specific embodiments, the temperature of the agitation is 60-90 ℃ and the time of the agitation is 0.5-24 hours.
Further, the curing time is 0.5-5 hours.
Further, the curing temperature is 120-160 ℃, and the curing time is 0.5-5h.
In some more specific embodiments, the method of preparing a flame retardant epoxy resin composite includes:
the epoxy resin (the domestic bisphenol A type epoxy resin E44 is adopted as a model polymer, the epoxy equivalent is 210-215 g, the viscosity is 20-40 Pa.s) is preheated to a certain temperature (60-90 ℃, the process is used for reducing the viscosity of the epoxy resin and ensuring a certain fluidity), the LDHs intercalated by the para-aminobenzoic acid radical is slowly added according to the mass percentage (0-50 wt%) of the specified epoxy resin composite material, the temperature is kept for a certain time (0.5-24 h) to uniformly mix, then the curing agent is added for rapid stirring and casting to a mould, and the epoxy resin composite material is prepared after curing for a certain time (0.5-5 h) at a certain temperature (120-160 ℃).
The mechanism of the invention is as follows: the structure of the para-aminobenzoic acid contains benzene rings, when the para-aminobenzoic acid is heated and decomposed, carbon can be formed in the presence of oxides formed by thermal decomposition of hydroxide laminates, if the para-aminobenzoic acid is filled with organic polymers by fillers, the organic polymers can be more easily formed into carbon during thermal decomposition or combustion, meanwhile, amino contained in the 4NP-LDH can interact with polymers such as epoxy resin and the like, the influence of the addition of the fillers of the organic polymers on the mechanical properties of the para-aminobenzoic acid is reduced to a certain extent, and a certain amount of gas can be released during the thermal decomposition of amino compounds, so that the structure of the combustion products is loose, and a certain expansion flame retardant effect is achieved. In addition, the 4NP-LDH has certain ultraviolet absorptivity, and can enhance the ultraviolet aging resistance of the organic polymer. Therefore, the 4NP-LDH flame-retardant filler is synthesized by taking a low-cost coprecipitation method and cheap magnesium chloride as raw materials, and has great scientific and economic values for the utilization of magnesium chloride resources and the flame-retardant application of the 4NP-LDH in epoxy resin.
In summary, the invention designs and utilizes a low-cost and simple-operation coprecipitation method to synthesize the magnesium-based hydrotalcite-like compound (4 NP-LDH) intercalated with the para-aminobenzoic acid, takes magnesium chloride as a main raw material to synthesize the magnesium-based hydrotalcite-like compound 4NP-LDH and uses the magnesium-based hydrotalcite-like compound as a polymer flame retardant filler to be applied to polymer flame retardance, can be added into a polymer to realize flame retardance, and can also realize mechanical property retention characteristics, and the 4NP-LDH flame retardant filler with structural characteristics such as morphology and the like is not needed to be considered excessively in application.
In addition, 4NP-LDH is used as an additive flame retardant to be applied to epoxy resin, and the flame retardant property of the composite material is improved. The invention can provide theoretical basis for synthesizing other amino acid radical intercalation magnesium-based hydrotalcite, and as the amino acid radical plays a role of crosslinking and solidifying in the epoxy resin, the co-precipitation method for synthesizing the amino acid radical intercalation hydrotalcite can also improve the flame retardant property of the organic polymer and simultaneously maintain the mechanical property to the maximum extent.
The technical solution of the present invention will be described in further detail below with reference to a number of preferred embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. It should be noted that the examples described below are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
Synthesis of 4NP-LDH
Firstly preparing 50mL of solution A and 30mL of solution B with a certain composition, wherein the solution A contains 2.03g of magnesium chloride hexahydrate, the solution B contains 1.21g of aluminum chloride hexahydrate, 1.8g of sodium hydroxide and 2.06g of p-aminobenzoic acid, adding the solution B into the solution A at the rate of 2mL/min by using a peristaltic pump, simultaneously introducing nitrogen into a reaction system for protection, stirring for 1 hour, transferring the solution A into a conical flask, sealing the conical flask, and then placing the conical flask into a constant-temperature oven at 60 ℃ for ageing for 24 hours. The aged suspension was suction filtered, washed until the funnel outlet liquid ph=7. Then 50mL of absolute ethyl alcohol is used for washing for multiple times, then the filter cake is dried in vacuum for 10 hours at 60 ℃, and the dried filter cake is ground and then is screened by a 200-mesh sieve for standby. The secondary water adopts a boiling method to remove carbon dioxide and oxygen. The XRD spectrum of the synthesized 4NP-LDH is shown in FIG. 1.
Example 2
Synthesis of 4NP-LDH
Firstly preparing 500mL of solution A and 300mL of solution B with a certain composition, wherein the solution A contains 20.3g of magnesium chloride hexahydrate, the solution B contains 12.1g of aluminum chloride hexahydrate, 18g of sodium hydroxide and 20.6g of p-aminobenzoic acid, adding the solution B into the solution A at a rate of 20mL/min by using a peristaltic pump, simultaneously introducing nitrogen into a reaction system for protection, stirring for 1 hour, transferring the solution A into a conical flask, sealing the solution A, and then placing the solution B into a constant-temperature oven at 60 ℃ for ageing for 24 hours. The aged suspension was suction filtered, washed until the funnel outlet liquid ph=7. Then 50mL of absolute ethyl alcohol is used for washing for multiple times, then the filter cake is dried in vacuum for 10 hours at 60 ℃, and the dried filter cake is ground and then is screened by a 200-mesh sieve for standby. The secondary water adopts a boiling method to remove carbon dioxide and oxygen. The XRD spectrum of the synthesized 4NP-LDH is shown in FIG. 2.
In addition to XRD, the water drop angle of the 4NP-LDH synthesized by amplification was tested, and from the results, it can be seen that the 4NP-LDH had greater lipophilicity than the ordinary LDHs (water drop angle of 20-30 degrees), and the 4NP-LDH water drop angle is shown in FIG. 3.
Thermogravimetric analysis of 4NP-LDH showed better thermal desorption properties, and the TG and DTG curves are shown in fig. 4 and 5.
Example 3
Synthesis of 4NP-LDH
Firstly preparing 50mL of solution A and 30mL of solution B with a certain composition, wherein the solution A contains 2.03g of magnesium chloride hexahydrate, the solution B contains 1.21g of aluminum chloride hexahydrate, 1.8g of sodium hydroxide and 2.06g of p-aminobenzoic acid, adding the solution B into the solution A at a rate of 2mL/min by using a peristaltic pump, at the moment, protecting the solution A from nitrogen, stirring for 1 hour, transferring the solution A into a conical flask, sealing the solution A, and then placing the solution B into a constant-temperature oven at 60 ℃ for ageing for 24 hours. The aged suspension was suction filtered, washed until the funnel outlet liquid ph=7. Then 50mL of absolute ethyl alcohol is used for washing for multiple times, then the filter cake is dried in vacuum for 10 hours at 60 ℃, and the dried filter cake is ground and then is screened by a 200-mesh sieve for standby. The secondary water adopts a boiling method to remove carbon dioxide and oxygen. The XRD spectrum of the synthesized 4NP-LDH is shown in FIG. 6.
Example 4
Synthesis of 4NP-LDH
Firstly preparing 50mL of solution A and 30mL of solution B with a certain composition, wherein the solution A contains 2.03g of magnesium chloride hexahydrate, the solution B contains 1.21g of aluminum chloride hexahydrate, 1.8g of sodium hydroxide and 2.06g of p-aminobenzoic acid, adding the solution B into the solution A at a rate of 2mL/min by using a peristaltic pump, at the moment, no nitrogen is used for protection, stirring for 0.5 hour at 90 ℃, transferring the solution A into a conical flask, sealing the conical flask, and then placing the conical flask into a constant-temperature oven at 20 ℃ for aging for 72 hours. The aged suspension was suction filtered, washed until the funnel outlet liquid ph=7. Then 50mL of absolute ethyl alcohol is used for washing for multiple times, then the filter cake is dried in vacuum for 16 hours at 20 ℃, and the dried filter cake is ground and then is screened by a 200-mesh sieve for standby. The secondary water adopts a boiling method to remove carbon dioxide and oxygen.
Example 5
Synthesis of 4NP-LDH
Firstly preparing 50mL of solution A and 30mL of solution B with a certain composition, wherein the solution A contains 2.03g of magnesium chloride hexahydrate, the solution B contains 1.21g of aluminum chloride hexahydrate, 1.8g of sodium hydroxide and 2.06g of p-aminobenzoic acid, adding the solution B into the solution A at a rate of 2mL/min by using a peristaltic pump, at the moment, stirring for 3 hours at normal temperature without nitrogen protection, transferring the solution A into a conical flask, sealing the conical flask, and then placing the conical flask into a constant-temperature oven at 160 ℃ for ageing for 3 hours. The aged suspension was suction filtered, washed until the funnel outlet liquid ph=7. Then 50mL of absolute ethyl alcohol is used for washing for multiple times, then the filter cake is dried in vacuum for 6 hours at 120 ℃, and the dried filter cake is ground and then is screened by a 200-mesh sieve for standby. The secondary water adopts a boiling method to remove carbon dioxide and oxygen.
Example 6
Synthesis of 4NP-LDH
Firstly preparing 50mL of solution A and 30mL of solution B with a certain composition, wherein the solution A contains 2.03g of magnesium chloride hexahydrate, the solution B contains 1.21g of aluminum chloride hexahydrate, 1.8g of sodium hydroxide and 2.06g of p-aminobenzoic acid, adding the solution B into the solution A at a rate of 2mL/min by using a peristaltic pump, at the moment, protecting the solution A from nitrogen, stirring for 1 hour, transferring the solution A into a conical flask, sealing the solution A, and then placing the solution B into a constant-temperature oven at 90 ℃ for aging for 48 hours. The aged suspension was suction filtered, washed until the funnel outlet liquid ph=7. Then 50mL of absolute ethyl alcohol is used for washing for multiple times, then the filter cake is dried in vacuum for 10 hours at 60 ℃, and the dried filter cake is ground and then is screened by a 200-mesh sieve for standby. The secondary water adopts a boiling method to remove carbon dioxide and oxygen.
Example 7
Synthesis of 4NP-LDH
Firstly preparing 50mL of solution A and 30mL of solution B with a certain composition, wherein the solution A contains 2.03g of magnesium chloride hexahydrate, the solution B contains 1.21g of aluminum chloride hexahydrate, 1.8g of sodium hydroxide and 2.06g of p-aminobenzoic acid, adding the solution B into the solution A at a rate of 2mL/min by using a peristaltic pump, at the moment, protecting the solution A from nitrogen, stirring for 1 hour, transferring the solution A into a conical flask, sealing the solution A, and then placing the solution B into a constant-temperature oven at 150 ℃ for aging for 6 hours. The aged suspension was suction filtered, washed until the funnel outlet liquid ph=7. Then 50mL of absolute ethyl alcohol is used for washing for multiple times, then the filter cake is dried in vacuum for 10 hours at 60 ℃, and the dried filter cake is ground and then is screened by a 200-mesh sieve for standby. The secondary water adopts a boiling method to remove carbon dioxide and oxygen.
Example 8
Preparation of epoxy resin flame-retardant material
Placing epoxy resin into a constant temperature oven at 60 ℃ to be preheated for 1 hour, taking out and weighing the epoxy resin, adding a 200mL beaker, placing the beaker into an oil pan at 90 ℃ to be preheated for 30 minutes in a constant temperature oil bath, adding NLDHs into the beaker at a constant speed according to a required proportion, and magnetically stirring the mixture for 2 hours to uniformly disperse the NLDHs. Weighing a certain proportion of curing agent 4,4' -diaminodiphenyl methane, adding the curing agent into a beaker, increasing the stirring speed, and mixing for 10min. The beaker is placed in a vacuum drying oven for vacuumizing to remove bubbles. Injecting the standby composite epoxy resin after bubble removal into a preheated mold, naturally cooling at 100 ℃ for 2 hours and 150 ℃ for 2 hours to obtain a sample strip, and waiting for subsequent testing. The results of the epoxy cone calorimetric test with varying proportions of 4NP-LDH are shown in Table 1. From the data presented above, it is evident that 4NP-LDH can significantly improve the flame retardancy of epoxy resins.
TABLE 1 4NP-LDH cone calorimetric data sheet
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (10)
1. The preparation method of the para aminobenzoic acid intercalation hydrotalcite-like fire retardant is characterized by comprising the following steps:
and (3) reacting a mixed system containing para-aminobenzoic acid and/or para-aminobenzoate, divalent metal chloride, an aluminum source and alkali to obtain the para-aminobenzoic acid intercalated hydrotalcite-like flame retardant.
2. The method according to claim 1, characterized in that: the divalent metal element in the divalent metal chloride comprises any one or more than two of magnesium, copper, calcium, zinc, manganese and iron;
and/or the aluminum source comprises any one or more than two of aluminum salt, aluminum hydroxide, sodium aluminate and sodium metaaluminate;
and/or the alkali comprises any one or a combination of two of sodium hydroxide and potassium hydroxide.
3. The method of manufacturing according to claim 1, characterized in that: the ratio of the aluminum element to the substances of the para-aminobenzoic acid and/or para-aminobenzoate in the mixed system is 1:1-1:6;
and/or the ratio of the amount of the divalent metal element to the amount of the aluminum element in the mixed system is 1:1-4:1;
and/or the concentration of aluminum element in the mixed system is 0-0.8mol/L.
4. The method of manufacturing according to claim 1, comprising:
preparing a divalent metal chloride into a first solution;
preparing a second solution from para-aminobenzoic acid and/or para-aminobenzoate, an aluminum source and a base;
and mixing the first solution and the second solution for reaction to obtain the para aminobenzoic acid intercalation hydrotalcite-like compound.
5. The method of manufacturing according to claim 1, characterized in that: when the aluminum source is aluminum chloride, the amount n of the alkali substance in the mixed system B1 Is 0.9× (2 (n) M +n A )+n O )～1.1×(2(n M +n A )+n O ) Wherein n is M The amount of the substance being a divalent metal element, n A The amount of the substance being a trivalent metal element, n O An amount of a substance that is para-aminobenzoic acid;
preferably, when the aluminum source is aluminum hydroxide, the amount of the base material is n B1 -3n A ；
Preferably, when the aluminum source is sodium metaaluminate or sodium aluminate, the amount of the base material is n B1 -4n A 。
6. The method of manufacturing according to claim 1, further comprising: and after the reaction of the mixed system is finished, aging, washing and drying to obtain the para aminobenzoic acid intercalated hydrotalcite-like flame retardant.
7. The method of manufacturing according to claim 6, wherein: the temperature of the reaction is 20-90 ℃, and the reaction time is 0.5-3h;
and/or the aging temperature is 20-160 ℃, preferably 60-90 ℃;
and/or the aging time is 3-72 hours, preferably 6-48 hours;
and/or the drying temperature is 20-120 ℃.
8. Para-aminobenzoic acid intercalated hydrotalcite-like flame retardant prepared by the preparation method according to any one of claims 1 to 7.
9. A flame retardant epoxy resin composite material comprising the para-aminobenzoic acid intercalated hydrotalcite-like flame retardant according to claim 8, an epoxy resin and a curing agent.
10. The method for preparing the flame retardant epoxy resin composite material of claim 9, comprising: uniformly stirring the para-aminobenzoic acid intercalated hydrotalcite-like flame retardant, epoxy resin and auxiliary agent, adding a curing agent for curing, and curing to obtain a flame-retardant epoxy resin composite material;
preferably, the stirring temperature is 60-90 ℃, and the stirring time is 0.5-24 hours;
preferably, the curing time is 0.5-5 hours;
preferably, the curing temperature is 120-160 ℃, and the curing time is 0.5-5h.
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