CN113583296B - Modified magnesium hydroxide, flame retardant, preparation and application thereof - Google Patents
Modified magnesium hydroxide, flame retardant, preparation and application thereof Download PDFInfo
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- CN113583296B CN113583296B CN202110795939.1A CN202110795939A CN113583296B CN 113583296 B CN113583296 B CN 113583296B CN 202110795939 A CN202110795939 A CN 202110795939A CN 113583296 B CN113583296 B CN 113583296B
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- magnesium hydroxide
- modified
- flame retardant
- modified magnesium
- ammonium chloride
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 104
- 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 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003063 flame retardant Substances 0.000 title abstract description 46
- 239000012267 brine Substances 0.000 claims abstract description 31
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000003607 modifier Substances 0.000 claims abstract description 22
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 239000011591 potassium Substances 0.000 claims abstract description 13
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 43
- 239000000347 magnesium hydroxide Substances 0.000 claims description 30
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims description 22
- 159000000002 lithium salts Chemical class 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003011 anion exchange membrane Substances 0.000 claims description 12
- 239000007772 electrode material Substances 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 9
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 8
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 230000001788 irregular Effects 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims 2
- 239000011777 magnesium Substances 0.000 abstract description 69
- 229920000307 polymer substrate Polymers 0.000 abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 abstract description 11
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 6
- 125000002091 cationic group Chemical group 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004886 process control Methods 0.000 abstract description 6
- 230000006378 damage Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000008569 process Effects 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000005708 Sodium hypochlorite Substances 0.000 description 5
- 239000000645 desinfectant Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010900 secondary nucleation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/18—Alkaline earth metal compounds or magnesium compounds
- C25B1/20—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
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- Inorganic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to the technical field of electrochemical synthesis, in particular to modified magnesium hydroxide and a flame retardant, and preparation and application thereof. The scheme has the following characteristics: 1) By addition of Li + And proper PH, current intensity and other process control to finish small-particle-size Mg (OH) 2 Controlling the sheet shape; 2) Preparation of Mg (OH) by introduction of cationic modifier 2 Meanwhile, hydrophobic modification is completed, the compatibility with a high polymer substrate is improved, and the agglomeration resistance is greatly improved; 3) Mg (OH) 2 The dispersion is better, and a better effect is achieved in a flame retardant property test; 4) The brine after the potassium is extracted from the salt lake is used as a magnesium source, so that the problem of magnesium damage is effectively solved, the raw material source is wide, the cost is low, a new way for brine utilization is developed, and byproducts can be recycled.
Description
Technical Field
The invention relates to the technical field of electrochemical synthesis, in particular to modified magnesium hydroxide, a flame retardant, and preparation and application thereof.
Background
Inorganic flame retardants are the most used environmental-friendly flame retardants, and currently, industrially applied products mainly include hydroxides of metals such as aluminum, magnesium, and molybdenum, ammonium phosphates, boric acid, and the like. The magnesium hydroxide is used as a good inorganic flame retardant, has triple functions of flame retardance, a filling agent and smoke suppression, and has wide application prospect. The inventors of the present invention found that: prior art preparation of superfine Mg (OH) 2 The flame retardant is industrially prepared by calcium hydroxide precipitation process, the Mg (OH) prepared by the process 2 Often contain a large amount of calcium impurities, and Mg (OH) 2 The material is irregular in shape, easy to agglomerate, difficult to control the particle size and difficult to be used as a high-end flame retardant material; simultaneously preparing Mg (OH) with controllable shape and grain diameter by laboratory or emulsion synthesis method 2 More toxic reagents are often used, the control process is complex and difficult to industrialize; with Mg (OH) 2 The flame retardant has poor compatibility when used together with plastics and the like due to extremely strong hydrophilicity, so that the problem of poor mechanical property of the material is caused. China has abundant seawater and brine resources, a large amount of bischofite (the component is magnesium chloride) in the brine of the salt lake after potassium extraction cannot be reasonably utilized, so that resource waste and environmental pollution are caused, if the bischofite resources can be prepared into the high-purity superfine magnesium hydroxide flame retardant by an electrodeposition technology through a method which is simple in process, controllable in shape, free of any addition and easy to realize industrialization and does not need to consume water resources, the economy of the whole process is improved, the resources are fully utilized, and the additional value of products is improved.
Disclosure of Invention
Traditional preparation of Mg (OH) from seawater and brine 2 Simple filtering, and precipitating with calcium hydroxide to obtain impurity-containing Mg (OH) 2 After dissolution and purification, sodium hydroxide is addedThen precipitating and refining again, wasting a large amount of chemical agents and energy, and the defect of the chemical precipitation method determines that Mg (OH) which has controllable appearance, is not easy to agglomerate and has good compatibility with high polymer materials cannot be prepared 2 。
To solve at least one of the problems mentioned in the background art, an object of an embodiment of the present invention is to provide a modified magnesium hydroxide having a microstructure including magnesium hydroxide and an outer modified layer; the median particle size of the magnesium hydroxide is 5-50 mu m; the contact angle of 10g/L aqueous solution of the modified magnesium hydroxide is 60-80 degrees.
Preferably, the modified magnesium hydroxide shape includes a flake shape, a granular shape and an irregular shape.
Preferably, the outer modification layer comprises one or more of (3-acrylamidopropyl) trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, 4-vinylpyridine, and N, N-dimethylaminoethyl acrylate.
A preparation method of modified magnesium hydroxide comprises the following steps:
step one, standing brine obtained after potassium extraction in a salt lake, and filtering to obtain a mixed solution I;
step two, adding soluble carbonate, soluble lithium salt and hydrochloric acid into the mixed solution I in sequence, and removing calcium ions and carbonate to obtain a mixed solution II;
step three, dividing the electrolytic cell into an anode area and a cathode area by a diaphragm, injecting the mixed solution II into the anode area and the cathode area of the electrolytic cell, and adding a modifier into the anode area of the electrolytic cell;
step four, the current density is electrified to be 0.025-0.0040A/cm 2 Electrolyzing at 20-35 deg.C to obtain white precipitate;
and fifthly, washing the white precipitate with deionized water, filtering and drying to obtain the modified magnesium hydroxide.
Preferably, the modifier comprises one or more of (3-acrylamidopropyl) trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
Preferably, the soluble lithium salt includes lithium carbonate and lithium chloride; the concentration of the soluble lithium salt is 0-0.5wt%.
Preferably, the standing time is 6-24h; the electrolysis time is 2-4h; the drying temperature is 60-80 ℃; the drying time is 6-24h.
Preferably, the anode region electrode material is any one of graphite, titanium alloy subjected to surface oxidation treatment, copper subjected to surface oxidation treatment and chromium subjected to surface oxidation treatment; the cathode electrode material is any one of copper, aluminum, titanium, silver, platinum and graphite.
Preferably, the separator material is an anion permeable membrane.
Preferably, the anion permeable membrane comprises a modified polyethersulfone anion exchange membrane, a modified perfluorinated anion exchange membrane, and a modified metafluoro anion exchange membrane.
Preferably, the pH value of the cathode area of the electrolytic cell is 5-6.
A modified flame retardant comprises the modified magnesium hydroxide or the modified magnesium hydroxide prepared by the method.
A preparation method of a modified flame retardant is characterized by comprising the preparation steps of modified magnesium hydroxide.
A magnesium hydroxide flame retardant system comprising the modified magnesium hydroxide, the modified magnesium hydroxide prepared by the above method, the flame retardant or the flame retardant prepared by the above method; comprises 15 to 70 percent of polymer base material and 5 to 80 percent of modified magnesium hydroxide or flame retardant.
Preferably, the polymer substrate includes plastic, resin, and fiber.
Cl produced by anodic electrolysis 2 Easy reaction with water:
Cl - +e-→Cl 2
Cl 2 +H 2 O→NaClO+NaCl
a small amount of NaOH solution in the cathode chamber enters the anode chamber and hypochlorous acid due to the functions of permeation, diffusion and migration
Or generation by reaction of chlorineSodium chlorate: the modifier transfers to the cathode but, since the electric field strength does not reach its redox potential, it simply transfers charge to H 2 O
2R + +2H 2 O+4e - →2R+H 2 +2OH -
Simultaneous cathode water self-ionization
2H 2 O+2e - →H 2 +2OH -
While the vicinity of the cathode
Mg+2OH - →Mg(OH) 2
The electrolyte contains hydrogen ions which readily dissolve Mg (OH) 2 The appearance of the product is complete and the defects are small due to the tiny crystal nuclei on the surface; when the pH value of the system is larger, OH is contained in the electrolysis - Ions, which accelerate Mg (OH) 2 Easily generate fine crystal nuclei, resulting in Mg (OH) as a product 2 The defect of (2) becomes large. Mg (OH) 2 When the surface is positively charged and the system is acidic, the potential of the MH surface is increased, so that particles are positively charged and mutually repelled, the product agglomeration is prevented, and the obtained product has smaller particle size; when the pH value of the system is larger, mg (OH) 2 The potential of the surface is reduced, and OH is generated on the cathode plate after the electrolysis is started - Ions, the ions and Mg 2+ Ion binding to form Mg (OH) 2 Precipitation, the surface of the substrate can be used as nucleation core with a large nucleation probability, so that Mg (OH) is generated 2 Nucleation on the substrate first, with OH - Further generation of ions, the primary nuclei on the cathode plate begin to grow rapidly in the same direction at the same speed in the direction perpendicular to the cathode plate, forming porous Mg (OH) 2 A substrate. As the reaction proceeds, mg near the cathode plate 2+ The content is reduced and needs to move from the free space of the system to the vicinity of the cathode plate, due to Li + The ions are not consumed and are concentrated in the Mg (OH) just formed 2 The substrate surface, forming new dislocation dew points, becomes a new source of growth, which will be at Mg (OH) 2 Forming secondary nucleation on the substrate. Due to Li + Ionic radius of ion (0.83A) and Mg 2+ Has an ionic radius of very close (0.81A), li + Ions continuously enter Mg (OH) 2 In the crystal lattice, the crystal lattice can be adsorbed at the growth step of the crystal face, the surface energy and the growth speed of each crystal face are changed, the energy ratio of the crystal face to the edge can be reduced, the broadening of a growth layer is accelerated, the polar growth in the C axis direction is inhibited, the anisotropy is increased, the co-growth in the direction parallel to the electrode is realized, and therefore the flaky Mg (OH) is formed 2 The morphology of (2).
Meanwhile, the modifier is taken as a cation unit and is also enriched at the cathode under the action of an electric field, and due to the mutual exclusion of cations, the modifier is enriched at Mg 2+ Nucleation of Mg (OH) 2 Can not enter Mg (OH) 2 Inside the substrate, mg (OH) to be porous 2 The substrate is adsorbed with Mg (OH) 2 The surface, forming a hydrophobic end-out structure, greatly reduces Mg (OH) 2 Hydrophilic polarity greatly improves the compatibility with non-polar materials.
Meanwhile, the modified magnesium hydroxide enters a high molecular group composite system, and the outer side acrylate group reacts with the carbon-carbon double bond and the carboxyl and hydroxyl of the high molecular base material to generate chemical bond connection, so that the mechanical property is further improved, and the tensile strength is improved.
The invention relates to the technical field of electrochemical synthesis, in particular to modified magnesium hydroxide, a flame retardant, and preparation and application thereof, and the modified magnesium hydroxide and the flame retardant have the following characteristics: 1) By addition of Li + And proper PH, current intensity and other process control are carried out to complete the small-particle-size Mg (OH) 2 Controlling the sheet shape; 2) Preparation of Mg (OH) by introduction of cationic modifier 2 Meanwhile, hydrophobic modification is completed, the compatibility with a high polymer substrate is improved, and the agglomeration resistance is greatly improved; 3) Mg (OH) 2 The dispersion is better, and a better effect is achieved in a flame retardant property test; 4) The brine obtained after the potassium is extracted from the salt lake is used as a magnesium source, so that the problem of magnesium harm is effectively solved, the raw material source is wide, the cost is low, and a new way for brine utilization is developed; 5) Electrolyzing the brine, generating hydrogen and magnesium hydroxide precipitates at a cathode, generating chlorine at an anode, and absorbing the generated chlorine by adopting a sodium hydroxide solution to obtain a byproduct sodium hypochlorite which can be used as a raw material of a disinfectant; 6) The brine is electrolyzed by the electrodeposition method, the process is simple, the product appearance is controllable, the industrialization is easy to realize, and in addition, the method does not need to be carried outWater resources are consumed, the production difficulty is reduced, the economy of the whole process is improved, and a new preparation process of a high-end magnesium hydroxide flame retardant is developed; 7) The outside acrylate group reacts with the carbon-carbon double bond of the polymer substrate and the carboxyl and hydroxyl to generate chemical bond connection, so that the mechanical property is further improved, and the tensile strength is improved.
Drawings
FIG. 1 is a view of hydrophobically modified Mg (OH) 2 A preparation flow chart;
FIG. 2 is a hydrophobically modified Mg (OH) 2 Testing a contact angle;
FIG. 3 shows unmodified Mg (OH) 2 Testing the contact angle;
FIG. 4 shows preparation of modified Mg (OH) in example 1 2 SEM picture;
FIG. 5 is a schematic diagram showing preparation of modified Mg (OH) in Experimental example 2 2 SEM picture;
FIG. 6 shows preparation of modified Mg (OH) in Experimental example 3 2 SEM image.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
An object of an embodiment of the present invention is to provide a modified magnesium hydroxide having a microstructure including magnesium hydroxide and an outer modified layer; the median particle size of the magnesium hydroxide is 5-50 mu m; the contact angle of 10g/L aqueous solution of the modified magnesium hydroxide is 60-80 degrees.
Preferably, the modified magnesium hydroxide shape includes a flake shape, a granular shape and an irregular shape.
Preferably, the outer modification layer comprises one or more of (3-acrylamidopropyl) trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, 4-vinylpyridine, and N, N-dimethylaminoethyl acrylate.
A preparation method of modified magnesium hydroxide is shown in figure 1 and comprises the following steps:
step one, standing brine obtained after potassium extraction in a salt lake, and filtering to obtain a mixed solution I;
step two, adding soluble carbonate, soluble lithium salt and hydrochloric acid into the mixed solution I in sequence, and removing calcium ions and carbonate to obtain a mixed solution II;
step three, dividing the electrolytic cell into an anode area and a cathode area by a diaphragm, injecting the mixed solution II into the anode area and the cathode area of the electrolytic cell, and adding a modifier into the anode area of the electrolytic cell;
step four, the current density is electrified to be 0.025-0.0040A/cm 2 Electrolyzing at 20-35 deg.C to obtain white precipitate;
and fifthly, washing the white precipitate with deionized water, filtering and drying to obtain the modified magnesium hydroxide.
Preferably, the modifier comprises one or more of (3-acrylamidopropyl) trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
Preferably, the soluble lithium salt includes lithium carbonate and lithium chloride; the concentration of the soluble lithium salt is 0-0.5wt%.
Preferably, the standing time is 6-24h; the electrolysis time is 2-4h; the drying temperature is 60-80 ℃; the drying time is 6-24h.
Preferably, the anode region electrode material is any one of graphite, titanium alloy subjected to surface oxidation treatment, copper subjected to surface oxidation treatment and chromium subjected to surface oxidation treatment; the cathode electrode material is any one of copper, aluminum, titanium, silver, platinum and graphite.
Preferably, the separator material is an anion permeable membrane.
Preferably, the anion permeable membrane comprises a modified polyethersulfone anion exchange membrane, a modified perfluorinated anion exchange membrane, and a modified metafluoro anion exchange membrane.
Preferably, the pH value of the cathode area of the electrolytic cell is 5-6.
A modified flame retardant comprises the modified magnesium hydroxide or the modified magnesium hydroxide prepared by the method.
A preparation method of a modified flame retardant is characterized by comprising the steps of preparing modified magnesium hydroxide.
A magnesium hydroxide flame retardant system comprising the modified magnesium hydroxide, the modified magnesium hydroxide prepared by the above method, the flame retardant or the flame retardant prepared by the above method; comprises 15 to 70 percent of high molecular base material and 5 to 80 percent of modified magnesium hydroxide or flame retardant.
Preferably, the polymer substrate comprises plastics, resins and fibers.
To better characterize the hydrophobic modification of the modified magnesium hydroxide, a contact angle measuring instrument and the standard test method for measuring the surface wettability and the absorbency of the covering material using an automatic contact angle tester according to ASTM D5725-1999 (2003) were introduced.
In order to better represent the influence of modified magnesium hydroxide on the mechanical property of the material, a GB1040-92 plastic tensile property test method is introduced to test the breaking elongation and tensile strength of the polymer base material added with the flame retardant.
In order to better represent the influence of modified magnesium hydroxide on the flame retardant property of the material after modification, an oxygen index method GB/T406-93 of the national calibration plastic combustion property test method of the people's republic of China is introduced.
In some alternative embodiments, addition of Li is used + And proper PH, current intensity and other process control to finish small-particle-size Mg (OH) 2 Controlling the sheet shape;
in some alternative embodiments, mg (OH) is prepared by incorporating a cationic modifier 2 Meanwhile, hydrophobic modification is completed, so that the compatibility with a high-molecular base material is improved, and the agglomeration resistance is greatly improved;
in some alternative embodiments, mg (OH) 2 The dispersion is better, and a better effect is achieved in a flame retardant property test;
in some optional embodiments, the brine obtained after potassium extraction in the salt lake is used as a magnesium source, so that the problem of magnesium damage is effectively solved, the raw material source is wide, the cost is low, and a new way for brine utilization is developed;
in some optional embodiments, brine is electrolyzed, hydrogen and magnesium hydroxide precipitate are generated at a cathode, chlorine is generated at an anode, and the generated chlorine is absorbed by a sodium hydroxide solution to obtain a byproduct sodium hypochlorite which can be used as a raw material of a disinfectant;
in some optional embodiments, brine is electrolyzed by an electrodeposition method, so that the process is simple, the product appearance is controllable, industrialization is easy to realize, water resources are not required to be consumed, the production difficulty is reduced, the economy of the whole process is improved, and a new process for preparing a high-end magnesium hydroxide flame retardant is developed;
in some optional embodiments, the outer acrylate group reacts with the carbon-carbon double bond of the polymer substrate and the carboxyl and hydroxyl to generate chemical bond connection, so that the mechanical property is further improved, and the tensile strength is improved.
Example 1
On the basis of the disclosed embodiments, a modified magnesium hydroxide is disclosed, the microstructure of which comprises magnesium hydroxide and an external modified layer; the median particle size of the magnesium hydroxide is 5 mu m; the contact angle of the modified magnesium hydroxide 10g/L aqueous solution is 60 degrees as shown in FIG. 2.
As shown in fig. 4, the modified magnesium hydroxide is in the shape of a sheet.
Preferably, the outer modified layer is (3-acrylamidopropyl) trimethylammonium chloride.
A preparation method of modified magnesium hydroxide comprises the following steps:
step one, standing brine obtained after potassium extraction in a salt lake, and filtering to obtain a mixed solution I;
step two, adding soluble carbonate, soluble lithium salt and hydrochloric acid into the mixed solution I in sequence, and removing calcium ions and carbonate to obtain a mixed solution II;
step three, dividing the electrolytic cell into an anode area and a cathode area by a diaphragm, injecting the mixed solution II into the anode area and the cathode area of the electrolytic cell, and adding a modifier into the anode area of the electrolytic cell;
step four, the current density is electrified to be 0.025A/cm 2 Electrolyzing at 20 deg.c to obtain white precipitate;
and fifthly, cleaning the white precipitate with deionized water, filtering and drying to obtain the modified magnesium hydroxide.
Preferably, the modifier is (3-acrylamidopropyl) trimethylammonium chloride.
Preferably, the soluble lithium salt is lithium carbonate; the concentration of the soluble lithium salt is 0.1wt%.
Preferably, the standing time is 6 hours; the electrolysis time is 2 hours; the drying temperature is 60 ℃; the drying time was 6h.
Preferably, the anode region electrode material is graphite; the cathode electrode material is copper.
Preferably, the diaphragm material is a modified polyether sulfone anion exchange membrane.
Preferably, the cathode region of the electrolytic cell has a pH of 5.
A modified flame retardant comprises the modified magnesium hydroxide or the modified magnesium hydroxide prepared by the method.
A preparation method of a modified flame retardant is characterized by comprising the steps of preparing modified magnesium hydroxide.
A magnesium hydroxide flame retardant system comprising the modified magnesium hydroxide, the modified magnesium hydroxide prepared by the above method, the flame retardant or the flame retardant prepared by the above method; comprises 15% of a polymer base material, 80% of the modified magnesium hydroxide, 4% of silane and 1% of KH550 of a coupling agent.
Preferably, the polymer substrate is EVA resin, and is used for preparing a flame-retardant cable material.
In some alternative embodiments, addition of Li is used + And proper PH, current intensity and other process control to finish small-particle-size Mg (OH) 2 Controlling the sheet shape;
in some alternative embodiments, mg (OH) is prepared by incorporating a cationic modifier 2 Meanwhile, hydrophobic modification is completed, the compatibility with a high polymer substrate is improved, and the agglomeration resistance is greatly improved;
in some alternative embodiments, mg (OH) 2 Has better dispersivity and flame retardanceThe better effect can be obtained in the test;
in some optional embodiments, the brine obtained after the potassium is extracted from the salt lake is used as a magnesium source, so that the problem of magnesium hazard is effectively solved, the raw material source is wide, the cost is low, and a new way for brine utilization is developed;
in some optional embodiments, brine is electrolyzed, hydrogen and magnesium hydroxide precipitate are generated at a cathode, chlorine is generated at an anode, and the generated chlorine is absorbed by a sodium hydroxide solution to obtain a byproduct sodium hypochlorite which can be used as a raw material of a disinfectant;
in some optional embodiments, brine is electrolyzed by an electrodeposition method, so that the process is simple, the product appearance is controllable, industrialization is easy to realize, water resources are not required to be consumed, the production difficulty is reduced, the economy of the whole process is improved, and a new process for preparing a high-end magnesium hydroxide flame retardant is developed;
in some optional embodiments, the outer acrylate group reacts with the carbon-carbon double bond of the polymer substrate and the carboxyl group and the hydroxyl group to generate chemical bond connection, so that the mechanical property is further improved, and the tensile strength is improved.
Example 2
On the basis of the disclosed embodiment, a modified magnesium hydroxide is disclosed, the microstructure of which comprises magnesium hydroxide and an external modified layer; the median particle size of the magnesium hydroxide is 33 mu m; the contact angle of the modified magnesium hydroxide 10g/L aqueous solution is 68 degrees.
Preferably, the modified magnesium hydroxide shape includes a flake shape, a granular shape and an irregular shape.
Preferably, the outer modified layer is methacryloyloxyethyl trimethyl ammonium chloride.
A preparation method of modified magnesium hydroxide comprises the following steps:
step one, standing brine obtained after potassium extraction in a salt lake, and filtering to obtain a mixed solution I;
step two, adding soluble carbonate, soluble lithium salt and hydrochloric acid into the mixed solution I in sequence, and removing calcium ions and carbonate to obtain a mixed solution II;
step three, dividing the electrolytic cell into an anode area and a cathode area by a diaphragm, injecting the mixed solution II into the anode area and the cathode area of the electrolytic cell, and adding a modifier into the anode area of the electrolytic cell;
step four, electrifying the current density of 0.0040A/cm 2 Electrolyzing at 35 deg.C to obtain white precipitate;
and fifthly, cleaning the white precipitate with deionized water, filtering and drying to obtain the modified magnesium hydroxide.
Preferably, the modifier is methacryloyloxyethyl trimethyl ammonium chloride.
Preferably, the soluble lithium salt is lithium chloride; the soluble lithium salt concentration is 0.5wt%.
Preferably, the standing time is 24 hours; the electrolysis time is 4h; the drying temperature is 80 ℃; the drying time was 24h.
Preferably, the anode region electrode material is a titanium alloy with an oxidized surface; the cathode electrode material is aluminum.
Preferably, the membrane material is a modified perfluorinated anion exchange membrane.
Preferably, the pH value of the cathode area of the electrolytic cell is 6.
A modified flame retardant comprises the modified magnesium hydroxide or the modified magnesium hydroxide prepared by the method.
A preparation method of a modified flame retardant is characterized by comprising the steps of preparing modified magnesium hydroxide.
A magnesium hydroxide flame retardant system comprising the modified magnesium hydroxide, the modified magnesium hydroxide prepared by the method, the flame retardant or the flame retardant prepared by the method; comprises 70% of a polymer base material, 14% of glass fiber, 5% of the modified magnesium hydroxide, 1% of KH560 of the coupling agent.
Preferably, the polymer base material is PP.
In some alternative embodiments, addition of Li is used + And proper PH, current intensity and other process control to finish small-particle-size Mg (OH) 2 Controlling the sheet shape;
in some alternative embodiments, mg (OH) is prepared by incorporating a cationic modifier 2 Meanwhile, hydrophobic modification is completed, the compatibility with a high polymer substrate is improved, and the agglomeration resistance is greatly improved;
in some alternative embodiments, mg (OH) 2 The dispersion is better, and the flame retardant property test shows better effect;
in some optional embodiments, the brine obtained after the potassium is extracted from the salt lake is used as a magnesium source, so that the problem of magnesium hazard is effectively solved, the raw material source is wide, the cost is low, and a new way for brine utilization is developed;
in some optional embodiments, brine is electrolyzed, hydrogen and magnesium hydroxide precipitate are generated at a cathode, chlorine is generated at an anode, and the generated chlorine is absorbed by a sodium hydroxide solution to obtain a byproduct sodium hypochlorite which can be used as a raw material of a disinfectant;
in some optional embodiments, brine is electrolyzed by an electrodeposition method, so that the process is simple, the product appearance is controllable, industrialization is easy to realize, water resources are not required to be consumed, the production difficulty is reduced, the economy of the whole process is improved, and a new process for preparing a high-end magnesium hydroxide flame retardant is developed;
in some optional embodiments, the outer acrylate group reacts with the carbon-carbon double bond of the polymer substrate and the carboxyl and hydroxyl to generate chemical bond connection, so that the mechanical property is further improved, and the tensile strength is improved.
Example 3
The embodiment discloses a modified magnesium hydroxide, the microstructure comprises magnesium hydroxide and an external modified layer; the median particle size of the magnesium hydroxide is 50 mu m; the contact angle of the modified magnesium hydroxide 10g/L aqueous solution is 80 degrees.
Preferably, the modified magnesium hydroxide shape includes a flake shape, a granular shape and an irregular shape.
Preferably, the outer modification layer comprises a combination of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
A preparation method of modified magnesium hydroxide comprises the following steps:
step one, standing brine obtained after potassium extraction in a salt lake, and filtering to obtain a mixed solution I;
step two, adding soluble carbonate, soluble lithium salt and hydrochloric acid into the mixed solution I in sequence, and removing calcium ions and carbonate to obtain a mixed solution II;
step three, dividing the electrolytic cell into an anode area and a cathode area by a diaphragm, injecting the mixed solution II into the anode area and the cathode area of the electrolytic cell, and adding a modifier into the anode area of the electrolytic cell;
step four, the current density is applied to the reactor to be 0.030A/cm 2 Electrolyzing at 30 deg.c to obtain white precipitate;
and fifthly, washing the white precipitate with deionized water, filtering and drying to obtain the modified magnesium hydroxide.
Preferably, the modifier comprises a combination of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
Preferably, the soluble lithium salt is lithium carbonate; the concentration of the soluble lithium salt is 0.3wt%.
Preferably, the standing time is 12 hours; the electrolysis time is 3 hours; the drying temperature is 70 ℃; the drying time was 12h.
Preferably, the anode region electrode material is chromium with an oxidized surface; the cathode electrode material is graphite.
Preferably, the membrane material is a modified metafluoro anion exchange membrane.
Preferably, the pH value of the cathode area of the electrolytic cell is 5.3.
A modified flame retardant comprises the modified magnesium hydroxide or the modified magnesium hydroxide prepared by the method.
A preparation method of a modified flame retardant is characterized by comprising the steps of preparing modified magnesium hydroxide.
A magnesium hydroxide flame retardant system comprising the modified magnesium hydroxide, the modified magnesium hydroxide prepared by the above method, the flame retardant or the flame retardant prepared by the above method; comprises 50 percent of high molecular base material, 40 percent of modified magnesium hydroxide and 10 percent of toughening agent.
Preferably, the polymer substrate is PBAT.
In some alternative embodiments, addition of Li is used + And proper PH, current intensity and other process control are carried out to complete the small-particle-size Mg (OH) 2 Controlling the sheet shape;
in some alternative embodiments, mg (OH) is prepared by incorporating a cationic modifier 2 Meanwhile, hydrophobic modification is completed, the compatibility with a high polymer substrate is improved, and the agglomeration resistance is greatly improved;
in some alternative embodiments, mg (OH) 2 The dispersion is better, and the flame retardant property test shows better effect;
in some optional embodiments, the brine obtained after the potassium is extracted from the salt lake is used as a magnesium source, so that the problem of magnesium hazard is effectively solved, the raw material source is wide, the cost is low, and a new way for brine utilization is developed;
in some optional embodiments, brine is electrolyzed, hydrogen and magnesium hydroxide precipitate are generated at a cathode, chlorine is generated at an anode, and the generated chlorine is absorbed by a sodium hydroxide solution to obtain a byproduct sodium hypochlorite which can be used as a raw material of a disinfectant;
in some optional embodiments, brine is electrolyzed by an electrodeposition method, so that the process is simple, the product appearance is controllable, industrialization is easy to realize, water resources are not required to be consumed, the production difficulty is reduced, the economy of the whole process is improved, and a new process for preparing a high-end magnesium hydroxide flame retardant is developed;
in some optional embodiments, the outer acrylate group reacts with the carbon-carbon double bond of the polymer substrate and the carboxyl group and the hydroxyl group to generate chemical bond connection, so that the mechanical property is further improved, and the tensile strength is improved.
Experimental example 1
To better validate Mg (OH) 2 The shape of the magnesium alloy is improved on the mechanical property, and an irregular shape Mg (OH) is disclosed on the basis of the disclosed embodiment 2 The preparation method comprises the following steps: mg (OH) was prepared in the same manner as in example 1, except that no soluble lithium salt was added 2 The morphology of (A) is irregular as shown in FIG. 5, but still has a better scoreAnd (4) dispersibility.
Experimental example 2
To better validate Mg (OH) 2 On the basis of the disclosed examples, a Mg (OH) which has not been hydrophobically modified is disclosed 2 Preparation method without adding any modifier, the rest of the example 1 is the same as the Mg (OH) 2 Contact angle test as shown in fig. 3, the contact angle is only 33 degrees; to obtain Mg (OH) 2 The morphology of (A) is shown in FIG. 6 as flaky, but the agglomeration is severe.
Experimental example 3
For better verification of Mg (OH) 2 The modification of (2) improves the flame retardant property, and discloses a scheme without adding a magnesium hydroxide flame retardant EVA on the basis of the disclosed embodiment: comprises 80% of the modified magnesium hydroxide, 4% of silane and 1% of KH550 coupling agent; the rest is the same as example 1.
The mechanical tests of example 1 and experimental examples 1 to 3 were carried out, and the results are shown in the following table:
example 1 comparison with addition of amorphous Mg (OH) 2 In the experimental example 1, the tensile strength and the elongation at break are remarkably improved, mainly because the sheet-shaped structure has a regular shape and uniform stress points, the stress concentration and the local damage are reduced, and the tensile strength and the elongation are improved; EXAMPLE 2 Mg (OH) which is easily agglomerated due to addition 2 The material is non-uniformly dispersed in the material and has poor compatibility, for example, although the tensile strength is improved compared with that of a non-flame-retardant filler sample in experimental example 3, the tensile strength at break is not obviously improved due to stress concentration, and the elongation at break is obviously reduced; example 1 due to the addition of Mg (OH) 2 The tensile strength is obviously improved, and simultaneously the modified Mg (OH) 2 Has good dispersibility and high polymer compatibility, so the reduction of the elongation at break is not obvious.
The flame retardant performance test was performed for example 1 and experimental examples 1 to 3, and the results are shown in the following table:
example 1 and Experimental examples 1-2 because of the addition of Mg (OH) 2 The flame retardance is far better than that of the experimental example 3; experimental example 2 the flame retardancy was significantly inferior to that of example 1 and Experimental example 1 because of Mg (OH) 2 Poor agglomerate dispersion results in reduced overall flame retardant performance.
| Residual mass/%) | Example 1 | Experimental example 1 | Experimental example 2 | Experimental example 3 |
| Oxygen index | 36 | 35 | 29 | 16 |
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (9)
1. A modified magnesium hydroxide comprising magnesium hydroxide and an outer modifying layer; the median particle size of the magnesium hydroxide is 5-50 mu m; the contact angle of the 10g/L aqueous solution of the modified magnesium hydroxide is 60-80 degrees; the raw materials for preparing the modified magnesium hydroxide also comprise soluble lithium salt; the external modification layer comprises one or more of (3-acrylamide propyl) trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate; the soluble lithium salt comprises lithium carbonate and lithium chloride; the concentration of the soluble lithium salt is 0-0.5wt%.
2. The modified magnesium hydroxide according to claim 1, wherein the shape thereof includes a flake shape, a granular shape and an irregular shape.
3. A method for preparing modified magnesium hydroxide according to claim 1, comprising the steps of:
step one, standing brine obtained after potassium extraction in a salt lake, and filtering to obtain a mixed solution I;
step two, adding soluble carbonate, soluble lithium salt and hydrochloric acid into the mixed solution I in sequence, and removing calcium ions and carbonate to obtain a mixed solution II;
step three, dividing the electrolytic cell into an anode area and a cathode area by a diaphragm, injecting the mixed solution II into the anode area and the cathode area of the electrolytic cell, and adding a modifier into the anode area of the electrolytic cell;
step four, the current density is electrified to be 0.025-0.0040A/cm 2 Electrolyzing at 20-35 deg.C to obtain white precipitate;
fifthly, washing the white precipitate with deionized water, filtering and drying to obtain the modified magnesium hydroxide;
the modifier comprises one or more of (3-acrylamide propyl) trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate;
the soluble lithium salt comprises lithium carbonate and lithium chloride; the concentration of the soluble lithium salt is 0-0.5wt%.
4. The method according to claim 3, wherein the standing time is 6 to 24 hours; the electrolysis time is 2-4h; the drying temperature is 60-80 ℃; the drying time is 6-24h.
5. The preparation method according to claim 3, wherein the anode region electrode material is any one of graphite, titanium alloy subjected to surface oxidation treatment, copper subjected to surface oxidation treatment and chromium subjected to surface oxidation treatment; the cathode electrode material is any one of copper, aluminum, titanium, silver, platinum and graphite.
6. The production method according to claim 3, wherein the separator material is an anion permeable membrane.
7. The method of claim 3, wherein the anion permeable membrane comprises a modified polyethersulfone anion exchange membrane, a modified perfluorinated anion exchange membrane, and a modified metafluoro anion exchange membrane.
8. The preparation method according to claim 3, wherein the pH value of the cathode area of the electrolytic cell is 5 to 6.
9. A modified flame retardant material comprising the modified magnesium hydroxide according to any one of claims 1 to 2 or the modified magnesium hydroxide prepared by the method according to any one of claims 3 to 8.
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| JP2002265948A (en) * | 2001-03-06 | 2002-09-18 | Konoshima Chemical Co Ltd | Magnesium hydroxide flame retardant coated with silane coupling agent, its production method, and flame- retardant resin composition |
| CN104592789A (en) * | 2013-12-27 | 2015-05-06 | 江苏艾特克阻燃材料有限公司 | Method for preparing magnesium hydrate flame retardant |
| CN109137032A (en) * | 2018-09-18 | 2019-01-04 | 中国科学院青海盐湖研究所 | Super-hydrophobic film layer of magnesium hydroxide and the preparation method and application thereof |
| CN111807393A (en) * | 2020-07-17 | 2020-10-23 | 青岛科技大学 | Method for improving compatibility of aluminum hydroxide |
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| CN109336142B (en) * | 2018-12-26 | 2020-06-05 | 北京化工大学 | Method for extracting lithium from salt lake brine and preparing aluminum hydroxide simultaneously |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002265948A (en) * | 2001-03-06 | 2002-09-18 | Konoshima Chemical Co Ltd | Magnesium hydroxide flame retardant coated with silane coupling agent, its production method, and flame- retardant resin composition |
| CN104592789A (en) * | 2013-12-27 | 2015-05-06 | 江苏艾特克阻燃材料有限公司 | Method for preparing magnesium hydrate flame retardant |
| CN109137032A (en) * | 2018-09-18 | 2019-01-04 | 中国科学院青海盐湖研究所 | Super-hydrophobic film layer of magnesium hydroxide and the preparation method and application thereof |
| CN111807393A (en) * | 2020-07-17 | 2020-10-23 | 青岛科技大学 | Method for improving compatibility of aluminum hydroxide |
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