CN108485058A - A kind of preparation method for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable - Google Patents
A kind of preparation method for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable Download PDFInfo
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- CN108485058A CN108485058A CN201810173375.6A CN201810173375A CN108485058A CN 108485058 A CN108485058 A CN 108485058A CN 201810173375 A CN201810173375 A CN 201810173375A CN 108485058 A CN108485058 A CN 108485058A
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- Prior art keywords
- zirconium phosphate
- basic zirconium
- size
- controllable
- preparation
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- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 title claims abstract description 129
- 229910000166 zirconium phosphate Inorganic materials 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 239000000138 intercalating agent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000013019 agitation Methods 0.000 claims abstract description 14
- 229910001463 metal phosphate Inorganic materials 0.000 claims abstract description 14
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 230000008021 deposition Effects 0.000 claims abstract description 3
- -1 polyene amine Chemical class 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 150000003754 zirconium Chemical class 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007836 KH2PO4 Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- 239000011259 mixed solution Substances 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 5
- 239000012429 reaction media Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 44
- 229920001155 polypropylene Polymers 0.000 description 25
- 239000003063 flame retardant Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 23
- 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 description 21
- 239000012265 solid product Substances 0.000 description 20
- 241000446313 Lamella Species 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000002411 thermogravimetry Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000007731 hot pressing Methods 0.000 description 12
- 239000000155 melt Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- 238000003825 pressing Methods 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 150000002171 ethylene diamines Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 101100284769 Drosophila melanogaster hemo gene Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 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 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- UXZGUPGQSWTOHR-UHFFFAOYSA-M benzyl-dodecyl-dimethylphosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[P+](C)(C)CC1=CC=CC=C1 UXZGUPGQSWTOHR-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of preparation methods for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable.Phosphoric acid or metal phosphate are add to deionized water the solution for being made into a concentration of 3~12mol/L by this method, add water-soluble inorganic zirconates, surfactant and intercalator, and 20~30min of mechanical agitation, fully dispersed under 200~500r/min rotating speeds；Mixed liquor is transferred in hydrothermal reaction kettle, 3~72h is reacted at 150~250 DEG C；After reaction, by mixed solution cooled to room temperature；White depositions centrifugation, washing, it is dry, obtain the controllable easy-stripping type laminar nano basic zirconium phosphate of size.Compared with prior art, the present invention does not use fluorochemical using water as reaction medium, and preparation process is simple, prepared basic zirconium phosphate size is controllable within the scope of 100~3000nm, crystallinity is high, compound with regular structure, easily peelable, good with polymer compatibility in process.
Description
Technical field
The present invention relates to nanometer two-dimensional layer metallic compound and preparation method thereof, in more detail a kind of size is controllable
The preparation method of easy-stripping type laminar nano basic zirconium phosphate.
Background technology
Laminar nano basic zirconium phosphate is a kind of New Two Dimensional nano material, has excellent ion exchange, absorption and solid acid
Catalysis etc. characteristics, can be applied to atomic energy industry (collecting of radioactive element), chemical materials (catalyst or catalyst carrier),
The fields such as medical and health (pharmaceutical intermediate, antiseptic, hemo system raw material).Further, since possessing between laminar nano zirconium phosphate layer
LargelySour point (H+) and Lewis acid points (Zr4+), in the high temperature process can catalytic polymer be cross-linked into charcoal, formed and caused
The transmission of close protective layer, blocking oxygen and heat makes it have unique advantage in flame retardance of polymer field.
Laminar nano basic zirconium phosphate lamella size size and dispersity have decisive impact the performance of its performance.So
And the bedded zirconium phosphate size synthesized by existing method is inhomogenous in polydispersity, lamella size, a large amount of hydroxyl is also contained on surface
Base, interlaminar action power are larger, lamella is complicated in stacked state, stripping process, seriously limit its further genralrlization application.
Currently, the preparation method of laminar nano basic zirconium phosphate mainly has circumfluence method, the precipitation method and hydro-thermal method.Clearfield etc.
People has synthesized the alpha zirconium phosphate (α-ZrP) of layer structure using circumfluence method for the first time.The method is simple for process, but the reaction time is long, closes
At crystal form size it is smaller, about 100~400nm (Clearfield A, Stynes J A.The preparation of
crystalline zirconium phosphate and some observations on its ion exchange
behavior[J].J.Inorg.Nucl.Chem.,1964,26(1):117‐129.).Alberti et al. is with hydrofluoric acid and oxygen chlorine
It is that raw material has synthesized that crystal particle diameter is larger by the precipitation method to change zirconium, the high α-ZrP of crystallinity, but the method it is high to equipment requirement and
With corrosivity (Alberti G, Torracca E.Crystalline insoluble salts of polybasic
metals‐II.Synthesis of crystalline zirconium or titanium phosphate by direct
precipitation[J].J.Inorg.Nucl.Chem.,1968,30(1):317‐318.).Chinese invention applies for a patent CN
1640817A is acted on by the complex catalysis of a small amount of hydrofluoric acid, at lower temperature (60~90 DEG C), using minimum phosphoric acid/
Zirconium oxychloride raw material proportioning prepares the Zirconium phosphate crystal with layered nano-structure.This method be used only a small amount of hydrofluoric acid and
Concentrated phosphoric acid reduces the pollution to environment, but the nanometer basic zirconium phosphate lamella size range prepared is smaller (1300~1700nm),
It still needs to use hydrofluoric acid in preparation process, there is certain corrosivity to equipment.
In order to overcome that circumfluence method and hydrogen fluorine method are long there are the reaction time, crystallinity is low and to equipment requirement it is high, corrosivity is strong
The defects of, while intercalation or stripping are carried out to basic zirconium phosphate.Chen etc. is existed using zirconium oxychloride and phosphoric acid as raw material by hydro-thermal method
It is reacted at 200 DEG C for 24 hours, has obtained the good α-ZrP of crystal form, then carrying out pre- intercalation enlargement layer to it using diglycolamine
Away from, then by it and maleic anhydride stem grafting polyolefin melt blending, the stripping of ZrP is realized by the esterification of acid anhydrides and hydroxyl
From polymer/zirconium phosphate nano composite material (Chen L, Sun D, Li J, et of the acquisition with good dispersion
al.Exfoliation of layered zirconium phosphate nanoplatelets by melt
compounding[J].Materials&Design,2017,122:247‐254.).But this method is first to synthesize common phosphorus
Sour zirconium, this basic zirconium phosphate are in stacked state, and surface contains a large amount of hydroxyl, and interlaminar action power is larger, then use intercalator into
The pre- intercalation of row, then remove, the process is more complicated, and ineffective, and the α-ZrP of synthesis have higher crystallinity, crystal grain
Diameter is larger, and lamella size is uncontrollable.
Invention content
The purpose of the present invention is being directed to defect existing for existing nanometer basic zirconium phosphate preparation method, it is controllable to provide a kind of size
The preparation method of easy-stripping type laminar nano basic zirconium phosphate.
For prior art problem, the present invention is by regulating and controlling phosphoric acid (or metal phosphate) concentration, the use of surfactant
Amount and reaction time obtain the nanometer basic zirconium phosphate with different lamella sizes, realize the controlledly synthesis of basic zirconium phosphate；In basic zirconium phosphate shape
The easily peelable nanometer basic zirconium phosphate of acquisition is modified at intercalator is passed through in the process.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable, includes the following steps：
1) phosphoric acid or metal phosphate are add to deionized water to the solution for being made into a concentration of 3~12mol/L, added
Water-soluble inorganic zirconates, surfactant and intercalator, 20~30min of mechanical agitation under 200~500r/min rotating speeds, fully
Dispersion；The surfactant is dodecyl sodium sulfate, neopelex, dodecyl dimethyl Benzylphosphonium Bromide
It is one or more in ammonium and Cetyltrimethylammonium bromide；The intercalator is methylamine, ethamine, ethylenediamine, the tetrabutyl
One or more of ammonium hydroxide, polyene amine and polyetheramine；
2) mixed liquor is transferred in hydrothermal reaction kettle, 3~72h is reacted at 150~250 DEG C；After reaction, it will mix
Close solution cooled to room temperature；
3) supernatant liquor is outwelled, white depositions centrifugation, washing control pH >=5.0 of final cleaning solution, dry, obtain
The controllable easy-stripping type laminar nano basic zirconium phosphate of size.
To further realize the object of the invention, it is preferable that the metal phosphate is Na3PO4、Na2HPO4、K3PO4、
K2HPO4And KH2PO4One or more of.
Preferably, the inorganic zirconium salts be one or both of zirconium oxychloride, zirconium carbonate, zirconium sulfate and zirconium nitrate with
On.
Preferably, the zirconates addition is 0.02~0.2 times of phosphoric acid or metal phosphate mole.
Preferably, the dosage of the surfactant is the 5%~20% of zirconates mole.
Preferably, the molar ratio of the intercalator and zirconates is 1:1~4:1.
Preferably, mixed liquor charge in hydrothermal reaction kettle is that kettle serves as a contrast the 3/5~3/4 of volume.
Preferably, the centrifugation is that lower layer's milky white precipitate object is centrifuged 10 under the rotating speed of 9000~12000r/min
~15min；The washing is to be washed with deionized, and centrifuges and wash repetition 3~5 times.
Preferably, the drying is vacuum drying, and temperature is at 80~100 DEG C, and the time is 8~12h.
Preferably, a diameter of 100~3000nm of the easy-stripping type laminar nano basic zirconium phosphate, interlamellar spacing are
Application of the nanometer basic zirconium phosphate in Halogenless fire retarded polymer：Before processing, by the nanometer basic zirconium phosphate and gather
Propylene is dried in vacuo 6~8 hours at 80~100 DEG C, is added on the open warm-up mill that double roller temperature is 170~190 DEG C
Polypropylene divides 2~3 times and layered nanometer basic zirconium phosphate is added, be kneaded uniform slice after 12~15min after it melts packet roller,
10~12min of hot pressing, room temperature are cold-pressed 8~12min, slice at 170~190 DEG C on vulcanizing press, obtain having good
The anti-flaming polypropylene material of flame retardant property and thermal stability.
The present invention provides a kind of easy-stripping type layer that size is controllable for defect existing for existing basic zirconium phosphate preparation method
The preparation method of shape nanometer basic zirconium phosphate：With soluble zirconates and phosphoric acid (or metal phosphate) for primary raw material, while table is added
Face activating agent obtains different by regulating and controlling phosphoric acid (or metal phosphate) concentration, dosage of surfactant and reaction time
The nanometer basic zirconium phosphate of layer size, realizes size controlledly synthesis；It is obtained during the reaction by the modification of intercalator easily peelable
Nanometer basic zirconium phosphate.The method enormously simplifies the preparation process of easy-stripping type nanometer basic zirconium phosphate, simple and practicable, while can also prepare
The nanometer basic zirconium phosphate that crystallinity is high, size is uniform and size is controllable is established for the further genralrlization application of laminar nano basic zirconium phosphate
Basis.
The present invention has the following advantages：
1) using surfactant, there has been no prior art reports in the preparation process of basic zirconium phosphate.It is a discovery of the invention that should
Class surfactant can promote the crystallization of basic zirconium phosphate, be obtained by the type and dosage that regulate and control surfactant various sizes of
Basic zirconium phosphate, to realize that size is controllable.
2) intercalator, the basic zirconium phosphate of this method synthesis is added by one-step method in the present invention in basic zirconium phosphate forming process
Interlamellar spacing is larger, and interlaminar action power is smaller, easily peelable.The present invention is modified by intercalator in basic zirconium phosphate forming process and obtains layer
Spacing larger and easily peelable nanometer basic zirconium phosphate can overcome the stripping of laminar nano basic zirconium phosphate difficulty, easily reunite in the polymer
Disadvantage.
3) nanometer basic zirconium phosphate of the present invention can pass through concentration, the dosage of surfactant of regulation and control phosphoric acid (or metal phosphate)
Different lamella size (100~3000nm) is obtained with the reaction time, realizes the size controlledly synthesis of laminar nano basic zirconium phosphate.
4) preparation process of the present invention does not introduce fluorochemical using water as reaction medium, and preparation process is simple, and process is easy to
Control.
5) basic zirconium phosphate prepared by is cheap, can be used as nano-meter flame retardants, catalyst and catalyst carrier.Prepared
Basic zirconium phosphate can be used as catalyst and catalyst carrier, nano-meter flame retardants, is suitable for polymer halogen-free flameproof and is modified field.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the nanometer basic zirconium phosphate that comparative example 1 is prepared.
Fig. 2 is the easy-stripping type nanometer basic zirconium phosphate infrared spectrum that embodiment 1,2,5,9 obtains.
Specific implementation mode
To more fully understand the present invention, below by embodiment, the invention will be further described, but the reality of the present invention
It is without being limited thereto to apply mode.
Embodiment 1
The concentrated phosphoric acid of a concentration of 3mol/L of 60mL is prepared, 6.00g zirconium oxychlorides and 6.00g methylamines, 0.20g dodecanes is added
Base benzene sulfonic acid sodium salt, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 300r/min, and mixed solution is then poured into hydro-thermal
In reaction kettle (100mL), 3h is reacted under the conditions of 200 DEG C.After reaction, by mixed solution cooled to room temperature.It outwells
Supernatant liquor, lower layer's milky white precipitate object, which is carried out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid, and what is obtained consolidates
Body product is washed with appropriate amount of deionized water, then carries out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionized water purge step
Rapid 4 times, make pH >=5 of centrifugal clear liquid.Solid product after washing dries 12h in 80 DEG C of baking ovens, is then scanned Electronic Speculum
Observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization, result are that average grain diameter is about 100nm, and interlamellar spacing is aboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:
mPP=2:98), uniform slice after mixing 15min, on vulcanizing press at 180 DEG C after hot pressing 10min, room temperature cold pressing 8min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 2
The concentrated phosphoric acid of a concentration of 6mol/L of 60mL is prepared, 6.00g zirconium sulfates and 6.00g ethylenediamines, 0.20g dodecanes is added
Base benzene sulfonic acid sodium salt, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 500r/min, and mixed solution is then poured into hydro-thermal
In reaction kettle (100mL), 12h is reacted under the conditions of 150 DEG C.After reaction, by mixed solution cooled to room temperature.It outwells
Supernatant liquor, lower layer's milky white precipitate object, which is carried out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid, and what is obtained consolidates
Body product is washed with appropriate amount of deionized water, then carries out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionized water purge step
Rapid 3 times, make pH >=5 of centrifugal clear liquid.Solid product after washing dries 12h in 80 DEG C of baking ovens, is then scanned Electronic Speculum
Observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization, result are that average grain diameter is about 450nm, and interlamellar spacing is aboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 80 DEG C, it is 170 DEG C open in double roller temperature
The polypropylene after drying is first added on warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:mPP
=2:98), uniform slice after mixing 15min, on vulcanizing press at 180 DEG C after hot pressing 10min, room temperature cold pressing 12min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 3
The concentrated phosphoric acid of a concentration of 3mol/L of 75mL is prepared, 10.00g zirconium carbonates and 7.50g ethylenediamines, 0.75g 18 is added
Alkyl trimethyl ammonium bromide, mechanical agitation 30min keeps its fully dispersed under the rotating speed of 300r/min, then falls mixed solution
Enter in hydrothermal reaction kettle (100mL), reacts 36h under the conditions of 250 DEG C.After reaction, mixed solution is naturally cooled into room
Temperature.Supernatant liquor is outwelled, lower layer's milky white precipitate object, which is carried out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid, obtains
To solid product washed with appropriate amount of deionized water, then carry out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionized water
Washing step 4 times, makes pH >=5 of centrifugal clear liquid.Solid product after washing dries 12h in 80 DEG C of baking ovens, is then swept
Electronic Speculum observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization are retouched, result is that average grain diameter is about 810nm, interlayer
Away from aboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 8 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:
mPP=2:98), uniform slice after mixing 15min, on vulcanizing press at 180 DEG C after hot pressing 12min, room temperature cold pressing 8min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 4
The potassium dihydrogen phosphate of a concentration of 6mol/L of 60mL is prepared, 6.00g zirconium oxychlorides and 8.00g ethylenediamines, 0.60g is added
Cetyltrimethylammonium bromide, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 300r/min, then will mix molten
Liquid pours into hydrothermal reaction kettle (100mL), reacts 72h under the conditions of 200 DEG C.After reaction, by mixed solution natural cooling
To room temperature.Supernatant liquor is outwelled, lower layer's milky white precipitate object, which is carried out centrifugal treating (12000r/min, 10min), makes solid-liquid point
From obtained solid product is washed with appropriate amount of deionized water, then carries out centrifugal treating again.Repeat above-mentioned centrifugal treating and go from
Sub- water wash step 4 times, makes pH >=5 of centrifugal clear liquid.Solid product after the washing dry 12h in 80 DEG C of baking ovens, then into
Row scanning electron microscopic observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization, result are about for average grain diameter
1050nm, interlamellar spacing are aboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 100 DEG C, the opening for being 190 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:
mPP=2:98), uniform slice after mixing 15min, on vulcanizing press at 180 DEG C after hot pressing 10min, room temperature cold pressing 8min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 5
The concentrated phosphoric acid of a concentration of 12mol/L of 60mL is prepared, 6.00g zirconium oxychlorides and 10.00g ethylenediamines, 0.20g ten is added
Dialkyl benzene sulfonic acids sodium, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 200r/min, then pours into mixed solution
In hydrothermal reaction kettle (100mL), 12h is reacted under the conditions of 200 DEG C.After reaction, by mixed solution cooled to room temperature.
Supernatant liquor is outwelled, lower layer's milky white precipitate object, which is carried out centrifugal treating (9000r/min, 15min), makes separation of solid and liquid, obtains
Solid product is washed with appropriate amount of deionized water, then carries out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionized water washing
Step 5 time makes pH >=5 of centrifugal clear liquid.Solid product after washing dries 12h in 100 DEG C of baking ovens, is then scanned electricity
Sem observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization, result are that average grain diameter is about 1500nm, interlamellar spacing
AboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:
mPP=2:98), uniform slice after mixing 12min, on vulcanizing press at 180 DEG C after hot pressing 12min, room temperature cold pressing 8min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 6
The concentrated phosphoric acid of a concentration of 12mol/L of 60mL is prepared, 6.00g zirconium carbonates and 6.00g polyenes amine, 0.60g 18 is added
Alkyl trimethyl ammonium bromide, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 300r/min, then falls mixed solution
Enter in hydrothermal reaction kettle (100mL), is reacted for 24 hours under the conditions of 250 DEG C.After reaction, mixed solution is naturally cooled into room
Temperature.Supernatant liquor is outwelled, lower layer's milky white precipitate object, which is carried out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid, obtains
To solid product washed with appropriate amount of deionized water, then carry out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionized water
Washing step 4 times, makes pH >=5 of centrifugal clear liquid.Solid product after washing dries 8h in 80 DEG C of baking ovens, is then scanned
Electronic Speculum observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization, result are that average grain diameter is about 1950nm, interlayer
Away from aboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:
mPP=2:98), uniform slice after mixing 15min, on vulcanizing press at 170 DEG C after hot pressing 10min, room temperature cold pressing 8min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 7
The concentrated phosphoric acid of a concentration of 9mol/L of 70mL is prepared, 7.00g zirconium oxychlorides and 7.00g polyenes amine, 0.80g 12 is added
Sodium alkyl benzene sulfonate, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 300r/min, and mixed solution is then poured into water
In thermal response kettle (100mL), reacted for 24 hours under the conditions of 200 DEG C.After reaction, by mixed solution cooled to room temperature.
Fall supernatant liquor, lower layer's milky white precipitate object, which is carried out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid, obtains
Solid product is washed with appropriate amount of deionized water, then carries out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionized water washing
Step 3 time makes pH >=5 of centrifugal clear liquid.Solid product after washing dries 12h in 80 DEG C of baking ovens, is then scanned electricity
Sem observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization, result are that average grain diameter is about 2300nm, interlamellar spacing
AboutRegular hexagon flake nano basic zirconium phosphate.Obtain layered nanometer basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:
mPP=2:98), uniform slice after mixing 15min, on vulcanizing press at 190 DEG C after hot pressing 10min, room temperature cold pressing 8min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 8
The disodium hydrogen phosphate of a concentration of 9mol/L of 65mL is prepared, 6.50g zirconium oxychlorides and 6.50g polyenes amine, 0.43g is added
Neopelex, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 300r/min, then falls mixed solution
Enter in hydrothermal reaction kettle (100mL), is reacted for 24 hours under the conditions of 200 DEG C.After reaction, mixed solution is naturally cooled into room
Temperature.Supernatant liquor is outwelled, lower layer's milky white precipitate object, which is carried out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid, obtains
To solid product washed with appropriate amount of deionized water, then carry out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionized water
Washing step 3 times, makes pH >=5 of centrifugal clear liquid.Solid product after washing dries 12h in 80 DEG C of baking ovens, is then swept
Electronic Speculum observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization are retouched, result is that average grain diameter is about 2300nm, layer
It is spaced aboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill and is added three times the nanometer basic zirconium phosphate (m of 5wt% after it melts packet rollerZrP:
mPP=5:95), uniform slice after mixing 15min, hot pressing 10min, room temperature are cold-pressed 12min at 180 DEG C on vulcanizing press
Slice afterwards prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 9
The sodium phosphate of a concentration of 12mol/L of 60mL is prepared, 6.00g zirconium oxychlorides and 8.00g polyetheramines, 0.60g ten is added
Eight alkyl trimethyl ammonium bromides, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 300r/min, then by mixed solution
It pours into hydrothermal reaction kettle (100mL), reacts 72h under the conditions of 200 DEG C.After reaction, mixed solution is naturally cooled to
Room temperature.Supernatant liquor is outwelled, lower layer's milky white precipitate object, which is carried out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid,
Obtained solid product is washed with appropriate amount of deionized water, then carries out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionization
Water wash step 4 times, makes pH >=5 of centrifugal clear liquid.Solid product after washing dries 12h in 80 DEG C of baking ovens, then carries out
Scanning electron microscopic observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization, result are that average grain diameter is about 2427nm,
Interlamellar spacing is aboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:
mPP=2:98), uniform slice after mixing 15min, on vulcanizing press at 180 DEG C after hot pressing 10min, room temperature cold pressing 8min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Embodiment 10
The concentrated phosphoric acid of a concentration of 9mol/L of 60mL is prepared, 6.00g zirconium oxychlorides and 10.00g polyetheramines, 0.60g ten is added
Eight alkyl trimethyl ammonium bromides, mechanical agitation 20min keeps its fully dispersed under the rotating speed of 300r/min, then by mixed solution
It pours into hydrothermal reaction kettle (100mL), reacts 72h under the conditions of 200 DEG C.After reaction, mixed solution is naturally cooled to
Room temperature.Supernatant liquor is outwelled, lower layer's milky white precipitate object, which is carried out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid,
Obtained solid product is washed with appropriate amount of deionized water, then carries out centrifugal treating again.Repeat above-mentioned centrifugal treating and deionization
Water wash step 4 times, makes pH >=5 of centrifugal clear liquid.Solid product after washing dries 12h in 80 DEG C of baking ovens, then carries out
Scanning electron microscopic observation, X-ray diffraction analysis and Fourier transform infrared spectroscopy characterization, result are that average grain diameter is about 3000nm,
Interlamellar spacing is aboutRegular hexagon flake nano basic zirconium phosphate.
Obtained nanometer basic zirconium phosphate and polypropylene is 6 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, the nanometer basic zirconium phosphate (m of point 2 addition 2wt%ZrP:
mPP=2:98), uniform slice after mixing 15min, on vulcanizing press at 180 DEG C after hot pressing 10min, room temperature cold pressing 8min
Slice prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, the results are shown in Table 1.
Comparative example 1
The concentrated phosphoric acid of a concentration of 9mol/L of 60mL is prepared, 6.00g zirconium oxychlorides are added, mechanical agitation 20min makes oxychlorination
Zirconium is fully dispersed, then pours into mixed solution in the hydrothermal reaction kettle (100mL) with polyparaphenylene liner, in 200 DEG C of items
12h is reacted under part.After reaction, by mixed solution cooled to room temperature.Supernatant liquor is outwelled, by lower layer's milky white precipitate
Object, which carries out centrifugal treating (10000r/min, 10min), makes separation of solid and liquid, and obtained solid product is washed with appropriate amount of deionized water,
Then centrifugal treating is carried out again.Above-mentioned centrifugal treating and deionized water washing step 4 times are repeated, pH >=5 of centrifugal clear liquid are made.It washes
Solid product after washing dries 12h in 80 DEG C of baking ovens, is then scanned Electronic Speculum observation, X-ray diffraction analysis and Fourier
Transform infrared spectroscopy characterizes, and result is that average grain diameter is about 1400nm, and interlamellar spacing is aboutRegular hexagon flake nano phosphorus
Sour zirconium.
Obtained nanometer basic zirconium phosphate and polypropylene is 12 hours dry at 100 DEG C, the opening for being 170 DEG C in double roller temperature
The polypropylene after drying is first added on formula warm-up mill, after it melts packet roller, point 2 nanometer phosphoric acid being added after 2wt% dryings
Zirconium (mZrP:mPP=2:98), uniform slice after mixing 15min, hot pressing 10min, room temperature are cold at 180 DEG C on vulcanizing press
Slice after pressure 8min, prepares various standard specimens on universal sampling machine, carries out flame retardant property test and thermogravimetric analysis, as a result such as table 1
It is shown.
Test specification
1. scanning electron microscope (SEM) is observed：Sample is adhered on sample stage by conducting resinl, and is carried out at the metal spraying of surface
Reason.It is the electron beam scanning imagery of 5kV with accelerating potential, observes sample surface morphology and measure diameter.
Fig. 1 is the basic zirconium phosphate SEM figures of 1 conventional method of comparative example synthesis, it can be seen from the graph that the basic zirconium phosphate lamella of synthesis is in heap
Overlapping state, and size is inhomogenous.
2. Fourier transform infrared spectroscopy：Sample is mixed and tabletted with potassium bromide powder, uses infrared interference light
Through sample and collect the interference signal of sample.Wave-number range is 4000-400cm-1, precision 4cm-1。
Fig. 2 is the easy-stripping type nanometer basic zirconium phosphate Fourier transform infrared spectroscopy figure that embodiment 1,2,5,9 obtains.From Fig. 2
In it can be seen that, the infrared signature absorption peak of different size basic zirconium phosphates is substantially consistent, wherein 3595cm-1And 3510cm-1The characteristic absorption peak at place belongs to the interlayer crystallization water, 3155cm-1And 1617cm-1The characteristic absorption peak at place belongs to pair of-OH
Claim stretching vibration and bending vibration, 1120cm-1And 1042cm-1The characteristic absorption peak at place is that the symmetrical and asymmetric stretch of P-O is shaken
Dynamic peak, and 593cm-1And 533cm-1The characteristic absorption peak at place belongs to Zr-O keys.
3.X x ray diffraction analysis xs (XRD)：Sample dispersion in solvent and is applied on monocrystalline silicon piece, natural drying allows
Solvent volatilizees.Use Cu-K alpha rays with the rate scanning sample of 4 °/min, accelerating potential and accelerate electric current be respectively 40kV and
20mA collects the diffraction information that 2 angles θ of sample are 1-80 °, obtains its interlamellar spacing.
4. thermogravimetric analysis (TGA)：In air atmosphere, take 5mg~10mg samples in thermogravimetric analyzer (TG209F1) into
Row test, ranging from 30-800 DEG C of analysis temperature, heating rate are 20 DEG C/min, and the weightless temperature of starting is calculated by analysis
Degree, maximum heat weight loss rate temperature, maximum heat weight loss rate and 800 DEG C of carbon yields.
5. flame retardant property is tested：Limit oxygen index (LOI) executes test according to ASTM D2863 standards, and specimen size is
120mm×6.5mm×3mm。
The size, interlamellar spacing of basic zirconium phosphate prepared by 1 different process of table and its influence to PP oxygen index (OI)s and thermal stability
It can be seen from Table 1 that with the raising of phosphoric acid (or metal phosphate) concentration, the lamella size of nanometer basic zirconium phosphate
(such as embodiment 2 and 5) in rising trend, but phosphoric acid (or metal phosphate) concentration be more than after 9mol/L lamella size can gradually subtract
Small (such as embodiment 6 and 7).This is because in the environment of high temperature and pressure, the growth of Zirconium phosphate crystal there are lateral magnification and is indulged
To stack two kinds of forms, when phosphoric acid (or phosphate) concentration is relatively low, the growth of Zirconium phosphate crystal based on lateral magnification, with
The increase of phosphoric acid (or metal phosphate) concentration, the basic zirconium phosphate lamella size of synthesis gradually increase.When phosphoric acid (or phosphate) is dense
When degree further increases, it is more advantageous to the vertical stack of lamella, and reduction trend is presented in diameter.
It can be seen from Table 1 that with the extension in reaction time, the increase of dosage of surfactant, the nanometer phosphoric acid of synthesis
Zirconium size gradually increases.Such as embodiment 2 and 4, when reacted between from 12h extend to 72h, dosage of surfactant increases from 0.2g
When to 0.6g, the average platelet diameter of basic zirconium phosphate increases 1500nm from 450nm.This is because with the extension of time, phosphorus
The crystal form of sour zirconium crystal tends to be perfect, and lamella diameter gradually increases；Meanwhile the addition of surfactant can promote the life of crystal
It is long, so that the size of basic zirconium phosphate is increased.
Can be seen that the addition intercalator in basic zirconium phosphate building-up process by the comparison of embodiment and comparative example can increase
The interlamellar spacing of laminar nano basic zirconium phosphate；And with the increase of intercalator dosage, interlamellar spacing increases, such as embodiment 2~5, with second
Diamines dosage increases to 10.0g from 6.0g, the interlamellar spacing of basic zirconium phosphate fromIt increases toWith intercalator chain length
Increase, interlamellar spacing increases, and such as embodiment 6~10, when intercalator is polyetheramine or polyene amine, interlamellar spacing significantly improves, highest
It can reach
It is compared with comparative example 1 as can be seen that easy-stripping type nanometer basic zirconium phosphate, which is added, to be carried by 1 Examples 1 to 10 of table
The flame retardant property and thermal stability of high polypropylene material.This is because basic zirconium phosphate can catalytic polymer crosslinking in combustion
At charcoal, fine and close protective layer, the propagation of blocking oxygen and heat are formed；Meanwhile basic zirconium phosphate lamella also can be in polymer combustion mistake
Play the role of physical barrier in journey.In the case where basic zirconium phosphate dosage keeps 2wt% constant, when basic zirconium phosphate size increases from 100nm
Greatly arrive 2300nm, interlamellar spacing fromIt increases toWhen, becoming of gradually being promoted is presented in the flame retardant property and thermal stability of PP
Gesture, still, with further increasing for basic zirconium phosphate size, flame retardant property and improved thermo stability unobvious, this may be because,
With the increase of basic zirconium phosphate size, lamella blocking effect is also promoted therewith, and the flame retardant property of PP is caused to improve.But work as phosphorus
One timing of additive amount of sour zirconium, with the increase of lamella size, piece layer number is reduced, limited to the contribution of blocking effect, therefore,
The flame retardant property of PP is not obviously improved.
It can be seen from Table 1 that with the increase of zirconium phosphate layer spacing, the flame retardant property and thermal stability of PP are on the whole
Existing ascendant trend.This is because the interlamellar spacing of basic zirconium phosphate is bigger, dispersibility in a polymer matrix is better, can play a role
Basic zirconium phosphate it is more, the anti-flammability and thermal stability of polymer are better.
Can be seen that with comparative example by 1 embodiment of table be not added intercalator basic zirconium phosphate it is poor to the flame retardant effect of PP.
This is because the basic zirconium phosphate surface that intercalator is not added is contained, a large amount of hydroxyl, interlaminar action power is larger, lamella is in stacked state,
Easily reunite in PP matrixes, is dispersed poor.
The prior art carries out intercalation to basic zirconium phosphate to be reachedOr more, but the prior art (Chen L, Sun
D,Li J,et al.Exfoliation of layered zirconium phosphate nanoplatelets by melt
compounding[J].Materials&Design,2017,122:It is 247-254.) first to synthesize unstripped basic zirconium phosphate then
Intercalation is carried out, which is relatively difficult, and the present invention is that intercalator, surfactant etc. are added in the synthesis process to pass through
The easy-stripping type nanometer basic zirconium phosphate of one-step synthesis method, this basic zirconium phosphate have apparent advantage in technique and in performance.
The basic zirconium phosphate size of conventional method synthesis is inhomogenous, and lamella stacks, and limits its application.Side through the invention
Method, the dosage and other reaction conditions for regulating and controlling raw material can obtain required size and interlamellar spacing, these different sizes and layer
The basic zirconium phosphate of spacing has a great impact to PP flame retardant effects.
Claims (10)
1. a kind of preparation method for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable, it is characterised in that include the following steps：
1) phosphoric acid or metal phosphate are add to deionized water to the solution for being made into a concentration of 3~12mol/L, added water-soluble
Property inorganic zirconium salts, surfactant and intercalator, 20~30min of mechanical agitation under 200~500r/min rotating speeds, fully point
It dissipates；The surfactant is dodecyl sodium sulfate, neopelex, dodecyl dimethyl benzyl ammonium bromide
With it is one or more in Cetyltrimethylammonium bromide；The intercalator is methylamine, ethamine, ethylenediamine, tetrabutylammonium hydrogen
One or more of amine-oxides, polyene amine and polyetheramine；
2) mixed liquor is transferred in hydrothermal reaction kettle, 3~72h is reacted at 150~250 DEG C；After reaction, it will mix molten
Liquid cooled to room temperature；
3) supernatant liquor is outwelled, white depositions centrifugation, washing control pH >=5.0 of final cleaning solution, dry, obtain size
Controllable easy-stripping type laminar nano basic zirconium phosphate.
2. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that described
Metal phosphate be Na3PO4、Na2HPO4、K3PO4、K2HPO4And KH2PO4One or more of.
3. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that described
Inorganic zirconium salts be one or more of zirconium oxychloride, zirconium carbonate, zirconium sulfate and zirconium nitrate.
4. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that described
Zirconates addition be 0.02~0.2 times of phosphoric acid or metal phosphate mole.
5. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that described
Surfactant dosage be zirconates mole 5%~20%.
6. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that described
Intercalator and zirconates molar ratio be 1:1~4:1.
7. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that described
Mixed liquor in hydrothermal reaction kettle charge be kettle serve as a contrast volume 3/5~3/4.
8. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that described
Centrifugation be that lower layer's milky white precipitate object is centrifuged into 10~15min under the rotating speed of 9000~12000r/min；The washing
It is to be washed with deionized, centrifuges and wash repetition 3~5 times.
9. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that described
Drying be vacuum drying, temperature is at 80~100 DEG C, and the time is 8~12h.
10. according to the preparation method of the controllable easy-stripping type laminar nano basic zirconium phosphate of claim 1 size, which is characterized in that institute
A diameter of 100~the 3000nm for the easy-stripping type laminar nano basic zirconium phosphate stated, interlamellar spacing are
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| CN109535481A (en) * | 2018-11-22 | 2019-03-29 | 南京林业大学 | Laminated inorganic matter alpha zirconium phosphate it is twice-modified and its preparation method and application |
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| CN109535481A (en) * | 2018-11-22 | 2019-03-29 | 南京林业大学 | Laminated inorganic matter alpha zirconium phosphate it is twice-modified and its preparation method and application |
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