CN110090634A - A kind of preparation method of organic inorganic hybridization integral post - Google Patents
A kind of preparation method of organic inorganic hybridization integral post Download PDFInfo
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- CN110090634A CN110090634A CN201910362032.9A CN201910362032A CN110090634A CN 110090634 A CN110090634 A CN 110090634A CN 201910362032 A CN201910362032 A CN 201910362032A CN 110090634 A CN110090634 A CN 110090634A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000009396 hybridization Methods 0.000 title claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000005060 rubber Substances 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims 8
- 235000019241 carbon black Nutrition 0.000 claims 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 6
- 229920000800 acrylic rubber Polymers 0.000 claims 5
- 150000001721 carbon Chemical class 0.000 claims 5
- 229920000058 polyacrylate Polymers 0.000 claims 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims 4
- 239000000203 mixture Substances 0.000 claims 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 3
- 229920000459 Nitrile rubber Polymers 0.000 claims 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims 3
- 235000021355 Stearic acid Nutrition 0.000 claims 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 3
- 239000004917 carbon fiber Substances 0.000 claims 3
- 235000011187 glycerol Nutrition 0.000 claims 3
- 229910017604 nitric acid Inorganic materials 0.000 claims 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims 3
- 239000008117 stearic acid Substances 0.000 claims 3
- 239000005864 Sulphur Substances 0.000 claims 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- 239000006210 lotion Substances 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 28
- 239000002184 metal Substances 0.000 abstract description 28
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 15
- 238000001514 detection method Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 239000012621 metal-organic framework Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000560 biocompatible material Substances 0.000 abstract description 2
- 239000013256 coordination polymer Substances 0.000 abstract description 2
- 229920001795 coordination polymer Polymers 0.000 abstract description 2
- 239000013110 organic ligand Substances 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 56
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 30
- 239000000741 silica gel Substances 0.000 description 30
- 229910002027 silica gel Inorganic materials 0.000 description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 29
- 235000019441 ethanol Nutrition 0.000 description 28
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 22
- 230000001476 alcoholic effect Effects 0.000 description 19
- 239000011806 microball Substances 0.000 description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910021529 ammonia Inorganic materials 0.000 description 15
- 239000012071 phase Substances 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- 239000000908 ammonium hydroxide Substances 0.000 description 12
- 229920000877 Melamine resin Polymers 0.000 description 11
- 235000015165 citric acid Nutrition 0.000 description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 10
- 229910001431 copper ion Inorganic materials 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 150000007974 melamines Chemical class 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- -1 silicane alkane Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000252254 Catostomidae Species 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Substances CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940121657 clinical drug Drugs 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- KVYSDWGALSSAEM-UHFFFAOYSA-N copper perchloric acid Chemical compound [Cu].Cl(=O)(=O)(=O)O KVYSDWGALSSAEM-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002651 drug therapy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005220 pharmaceutical analysis Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- YJQZYXCXBBCEAQ-UHFFFAOYSA-N ractopamine Chemical compound C=1C=C(O)C=CC=1C(O)CNC(C)CCC1=CC=C(O)C=C1 YJQZYXCXBBCEAQ-UHFFFAOYSA-N 0.000 description 1
- 229940074095 ractopamine Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/283—Porous sorbents based on silica
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/86—Sorbents applied to inner surfaces of columns or capillaries
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of organic inorganic hybridization integral post, belong to detection technique field.The present invention is using methyl methacrylate and polyethylene glycol as organic material, and add copper metal organogel, prepare a kind of organic inorganic hybridization integral post, polyethylene glycol is due to its special structure, it is acted on protein and other small, it is a kind of generally acknowledged biocompatible materials, metal organogel be used to prepare the organic polymer material of macropore open type as a kind of novel pore template, it is the gel state of metal organic framework, metal organic framework is a kind of porous material with periodic network structure formed by organic ligand and metal ion by self assembling process, be otherwise known as coordination polymer, the preparation of metal organogel is simple, with good porosity, structure diversity, the features such as good chemical stability and thermal stability, and the metal in gel can effectively improve the rigidity of integral post, increase The mechanical performance of strong integral post.
Description
Technical field
The present invention relates to a kind of preparation methods of organic inorganic hybridization integral post, belong to detection technique field.
Background technique
Currently, high performance liquid chromatography-is ultraviolet or Mass Spectrometer Method (HPLC-UV/MS) has become the main of internal Pharmaceutical Analysis
Means.However, quick, the accurate chromatography of drug component faces always humoral sample (especially blood sample) pre-treatment in vivo
The bottleneck that restrict.In recent years, multiple research fields such as pharmacology, clinical pharmacology and clinical drug therapy detection are faced with
The detection of the increasingly huge physiological fluid sample of quantity, development are enriched with, only for the quick, efficient of target components in body fluid
Change means are just particularly important.
It is excellent that Solid Phase Extraction (SPE) has that easy to operate, using flexible, the rate of recovery are high, consumption solvent is few, are easy to automate etc.
Point is widely used to the pretreatment process of sample.Mature SPE technology mostly uses greatly on surface with various function bases at present
Silica gel (or macromolecule) granular filler of group (such as C18 or C8).Generally by SPE column on special solid-phase extracting instrument, benefit
Mobile phase is set to flow through SPE column with the mode of vacuumizing.Under negative pressure of vacuum effect, mobile phase passes through granular filler gap and passes through SPE
Column.Target components in mobile phase are mainly mobile to filler surface in a manner of diffusion mass transfer, and the functional group with its surface
Interaction occurs and is adsorbed.With the raising of flow velocity, diffusion mass transfer effect variation causes separative efficiency to reduce.Therefore, make
Very high operation flow velocity cannot be used to shorten the SPE operating time with the SPE of granular filler.In addition, SPE packing material size is relatively
Greatly, there are larger gap between particle, relatively thin filling thickness is easy to cause " pipe effect " in filler, makes target to be enriched with
Component quickly flows out SPE column with mobile phase and effective interaction does not occur with fixed phase stuffing, this just influences the extraction of SPE
Efficiency.
Compared with granular filler, polymer or monolithic silica column medium are with back pressure is low, permeability is good, convective mass transfer speed
Fastly, the series of advantages such as easy are prepared, are had a good application prospect in chromatographic isolation field, future is expected to replace particles filled
Chromatographic column realization is quick, efficiently separates.The advantages of based on above-mentioned integral post medium, Recent study personnel are to integral post in SPE
The application in field gives very big concern.
Integral post preparation is easy, can especially prepare entirety of different shapes in the container of arbitrary shape as needed
Column, to adapt to a variety of different purposes.In addition, integral post intrinsic permeability is good, the solute in mobile phase is in a manner of convective mass transfer
Main, the efficiency that solute is adsorbed to fixed phase surface is influenced smaller by flow velocity raising.Therefore, integral post SPE can using compared with
High flow rate quickly handles a large amount of fluid sample, greatly shortens sample processing time, while the efficiency of its adsorbed target object and energy
It is maintained at satisfactory state.Under high flow velocities, mobile phase can reach all gaps in integral post, therefore by object
The effluent volume consumed when eluting is smaller, convenient for the operation of remaining processing sequences.On this basis, integral post SPE is filled
Automatic operation can be accomplished by setting, and realize the quick pretreatment to batch samples solution.
Compared with polyalcohol integral pole medium, monolithic silica column has more mesoporous, thus internal whole surface area will be more
Greatly.However silica gel is not resistant to hot environment, high ph-values mobile phase, and when general environment temperature > 60 DEG C, mobile phase pH > 8.5, silicon
Glue material matter stability itself decline, will lead to its SPE effect reduction, and high molecular polymer Monolithic Columns be resistant to it is higher
Environment temperature, broader pH value range are adapted to more stringent mobile phase condition.In addition, the preparation of polyalcohol integral pole
Method is more simpler than silica gel material, conveniently, and the polymer monomer type with different function group is more, Ke Yitong
Cross simple in situ, one-step polymerization reaction preparation Solid Phase Extraction entirety column device on demand.Therefore, polyalcohol integral pole material
SPE has more advantages, is also more paid close attention to by researcher.
In face of enormous amount and the SPE pre-treatment of single sample human blood sample small in size, integral post medium SPE is not
It is only advantageous in preparation method, and accordingly elute, elute and etc. consumption liquor capacity it is also relatively fewer.It can basis
Need to prepare miniature integral post SPE device in small size or micro device, such as in pipettor sucker, capillary, chip channel
Deng whole column device, SPE pre-treatment is carried out to realize being separated efficiently and rapidly and being enriched with to target components to sample.Wherein, it moves
Liquid device suction pipe integral post can connect use with pipettor, (or dynamic by other auxiliary by the suction of pipettor, drain pressure
Power) separation and enrichment procedure to object in sample can be realized, without special vacuum solid-phase extracting instrument.In addition, this
Kind " offline (off-line) " SPE mode of operation allows each step operation of the characteristic flexible choice SPE for different target object
Condition reaches best effect of extracting.It is following multiple pipettor sucker devices to be operated simultaneously using special manipulator, it is real
Now to the synchronization Solid Phase Extraction of multiple samples, it can greatly accelerate the speed of sample pre-treatments.Therefore, for micro human blood
For sample pre-treatments, pipettor sucker integral post has great advantage.
Polymer suction pipe integral post in the prior art is prepared in 10~550 μ L pipettor suckers mostly, Er Qiezhu
Bed volume is generally smaller, and the polymer fluid volume for synthesizing integral post is 0.6~10 μ L, and some will be gathered using capillary force
It closes liquid and is drawn into pipette tip position.Smaller bed volume is restricted integral post load capacity, is suitable for liquid chromatogram-matter
The sample pretreatment of spectrum detection (HPLC-MS), and be not suitable for using the liquid phase more universal, detector sensitivity is relatively low
Chromatography-ultraviolet detection (HPLC-UV) detection means.Therefore, existing whole rod structure significantly limits it in detection field
In application.
Summary of the invention
The technical problems to be solved by the invention: for the swelling blockage effect one of polyalcohol integral pole in organic solvent
Determine that its stability and mechanical performance can be reduced in degree, because skeleton is pure organic polymer, rigidity is inadequate, heat-resistant stability
The problem of difference, organic solvent-resistant is not swollen, provide a kind of preparation method of water lubriucated bearing composite rubber material.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) dehydrated alcohol is added in n-butanol, 8 ~ 10min is stirred with 80 ~ 100r/min revolving speed under room temperature, obtains mixed alcohol
Solution；
(2) mixing alcoholic solution is added in methyl methacrylate, polyethylene glycol, polyoxyethylene ether, vinyltriethoxysilane
In, 15 ~ 20min is stirred with 200 ~ 240r/min revolving speed under 30 ~ 40 DEG C of water-bath air-proof condition, room temperature cooling obtains polymer
Alcoholic solution；
(3) copper metal organogel, silica gel microball, azodiisobutyronitrile are added in polymer alcoholic solution, under room temperature with 600 ~
800r/min revolving speed quickly stirs 4 ~ 8min, then is placed in 40 ~ 60min of ultrasonic disperse in ultrasonic dispersing machine, obtains dispersion liquid；
(4) quartz capillary is taken, is washed 3 ~ 5 times with the sodium hydroxide solution of mass concentration 1%, then be washed with deionized 3
~ 5 times, with the dry 40 ~ 60min of 60 ~ 80 DEG C of temperature in nitrogen atmosphere, room temperature cooling obtains pretreated capillary；
(5) dispersion liquid is injected in pretreated capillary, be placed under 60 ~ 70 DEG C of water bath condition stand reaction 20 ~ for 24 hours, often
Temperature is cooling, obtains organic inorganic hybridization integral post.
The copper metal organogel, silica gel microball, methyl methacrylate, polyethylene glycol, polyoxyethylene ether, ethylene
Ethyl triethoxy silicane alkane, azodiisobutyronitrile, dehydrated alcohol, n-butanol parts by weight be 10 ~ 20 parts of copper metal organogels, 8 ~
12 parts of silica gel microballs, 16 ~ 24 parts of methyl methacrylates, 20 ~ 40 parts of polyethylene glycol, 4 ~ 8 parts of polyoxyethylene ether, 2 ~ 4 parts of ethylene
Ethyl triethoxy silicane alkane, 0.6 ~ 1.2 part of azodiisobutyronitrile, 20 ~ 40 parts of dehydrated alcohols, 20 ~ 40 parts of n-butanols.
The power of ultrasonic disperse described in step (3) is 500 ~ 600W.
The internal diameter of quartz capillary described in step (4) is 200 ~ 300 μm.
The specific preparation step of silica gel microball described in step (3) are as follows:
(1) dehydrated alcohol, ammonium hydroxide are added in deionized water, 10 ~ 12min is stirred with 120 ~ 160r/min revolving speed under room temperature, is obtained
Alcohol ammonia hydrolyzate；
(2) 1/3 ethyl orthosilicate is added in 1/3 alcohol ammonia hydrolyzate, is turned under 0 ~ 2 DEG C of refrigerated condition with 240 ~ 280r/min
Speed 30 ~ 40min of stirring, obtains silica gel nucleus liquid；
(3) remaining 2/3 ethyl orthosilicate and 2/3 alcohol ammonia hydrolyzate are slowly added in silica gel nucleus liquid, are placed in 18 ~ 22 DEG C
12 ~ 16h is stirred to react with 200 ~ 240r/min revolving speed under water bath condition, obtains reaction solution；
(4) it by the still aging 2 ~ 6h of reaction solution, then is placed in decompression suction filtration machine, filters, take under conditions of -0.4 ~ -0.2MPa
Filter cake is washed with deionized 3 ~ 5 times, is placed in 100 ~ 120 DEG C of baking oven dry 4 ~ 8h, and room temperature cooling obtains silica gel microball.
The ethyl orthosilicate, dehydrated alcohol, ammonium hydroxide, deionized water parts by weight be 20 ~ 30 parts of ethyl orthosilicates, 8 ~
12 parts of dehydrated alcohols, the ammonium hydroxide of 16 ~ 24 parts of mass concentrations 25%, 20 ~ 30 parts of deionized waters.
The drop rate of ethyl orthosilicate described in step (3) and alcohol ammonia hydrolyzate is respectively 2mL/min and 5mL/min.
The specific preparation step of copper metal organogel described in step (3) are as follows:
(1) cupric perchlorate, melamine, citric acid are added in n,N-Dimethylformamide, with 180 ~ 200r/min under room temperature
Revolving speed is stirred 10 ~ 12min, stand 20 ~ for 24 hours, obtain copper ion mixed liquor；
(2) copper ion mixed liquor is placed in 15 ~ 20min of ultrasonic vibration in ultrasonic dispersing machine, obtains copper metal organogel.
The cupric perchlorate, melamine, citric acid, n,N-Dimethylformamide parts by weight be 5 ~ 10 parts of perchloric acid
Copper, 10 ~ 20 parts of melamines, 1 ~ 2 part of citric acid, 20 ~ 40 parts of n,N-Dimethylformamide.
The power of ultrasonic vibration described in step (2) is 400 ~ 500W.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention prepares a kind of organic inorganic hybridization integral post, silica gel high mechanical strength, silica gel using silica gel microball as raw material
Chemical component be silica, physicochemical properties are extremely stable, the silica gel as carrier of separating matrix have mechanical strength
High, large specific surface area and surface are easy to modify the characteristics of with control, and excellent physics, chemistry and mechanical property become function
The irreplaceable matrix of one kind of carrier of separating can be changed, packed bed works under very high operating pressure for a long time, and column effect is still protected
Hold constant, rigidity, high-intensitive particle also make the back-pressure of column lower, and service life is longer, physical property such as particle diameter distribution, hole
Structure, specific surface area are easily controllable, and surface is easily modified, and there is siloxanes key-Si-O-Si- and silicone hydroxyl-on Silica Surface
Si-O-Si-OH, wherein siloxanes is hydrophobic grouping, and silicone hydroxyl is strong adsorbtive sites, and silicone hydroxyl is lived with stronger reaction
Property, it is the active function groups being bonded, free silicone hydroxyl acidity is very strong, energy strong adsorption alkali solute, therefore, containing certainly
Often increase alkali compounds retention by, the acid highly concentrated stationary phase of silicone hydroxyl, peak broadens, trails, silica gel carrier
Purity is also extremely important to the separation of many polar compounds, a small amount of metal impurities in silica gel, can cause with chelating solute complexing
Asymmetric or tailing peak or even compound are retained completely, cannot be eluted, the metal in silica gel lattice can make surface silanol group
The polar binding of increased activity, acidity enhancing, silica gel itself or silica gel carrier mutually can be used as stationary phase.It is solid in Silica Surface bonding
It is fixed mutually to can be used for separating, and being bonded protein, cyclodextrin, carbohydrate, macrocyclic antibiotic etc., obtain the fixation of different clastotypes
Phase.Silica gel particle can be divided into ball-type and two kinds unformed, and spherical silica gel is conducive to mass transfer, and can since its permeability is strong
Reduce operating pressure, thus is suitable as high phase liquid chromatography stuffing；
(2) present invention is using methyl methacrylate and polyethylene glycol as organic material, and adds copper metal organogel, preparation one
Kind of organic inorganic hybridization integral post, polyethylene glycol act on small due to its special structure with protein and other, are one
The generally acknowledged biocompatible materials of kind, metal organogel be used to prepare macropore open type as a kind of novel pore template
Organic polymer material, is the gel state of metal organic framework, metal organic framework be it is a kind of by organic ligand and metal from
The porous material with periodic network structure that son is formed by self assembling process, be otherwise known as coordination polymer, and metal has
The preparation of machine gel is simple, has the spies such as good porosity, structure diversity, good chemical stability and thermal stability
Point, and the metal in gel can effectively improve the rigidity of integral post, enhance the mechanical performance of integral post.
Specific embodiment
According to parts by weight, 5 ~ 10 parts of cupric perchlorates, 10 ~ 20 parts of melamines, 1 ~ 2 part of citric acid, 20 ~ 40 are weighed respectively
Cupric perchlorate, melamine, citric acid are added in n,N-Dimethylformamide for part n,N-Dimethylformamide, under room temperature with
180 ~ 200r/min revolving speed is stirred 10 ~ 12min, stand 20 ~ for 24 hours, copper ion mixed liquor is obtained, copper ion mixed liquor is placed in
In ultrasonic dispersing machine, 15 ~ 20min of ultrasonic vibration under conditions of 400 ~ 500W obtains copper metal organogel；Again by weight
Number meter weighs 20 ~ 30 parts of ethyl orthosilicates, 8 ~ 12 parts of dehydrated alcohols, the ammonium hydroxide of 16 ~ 24 parts of mass concentrations 25%, 20 ~ 30 respectively
Dehydrated alcohol, ammonium hydroxide are added in deionized water for part deionized water, under room temperature with 120 ~ 160r/min revolving speed stirring 10 ~
12min obtains alcohol ammonia hydrolyzate, by 1/3 ethyl orthosilicate be added 1/3 alcohol ammonia hydrolyzate in, under 0 ~ 2 DEG C of refrigerated condition with
240 ~ 280r/min revolving speed stirs 30 ~ 40min, obtains silica gel nucleus liquid, by remaining 2/3 ethyl orthosilicate and 2/3 alcohol ammonia hydrolyzate
It is slowly added in silica gel nucleus liquid with the drop rate of 2mL/min and 5mL/min respectively, is placed in 18 ~ 22 DEG C of water bath condition
Under 12 ~ 16h is stirred to react with 200 ~ 240r/min revolving speed, obtain reaction solution, by the still aging 2 ~ 6h of reaction solution, then be placed in decompression and take out
It in filter, is filtered under conditions of -0.4 ~ -0.2MPa, takes filter cake, be washed with deionized 3 ~ 5 times, be placed in 100 ~ 120 DEG C
Dry 4 ~ 8h, room temperature cooling obtain silica gel microball in baking oven；Again according to parts by weight, it is organic solidifying that 10 ~ 20 parts of copper metals are weighed respectively
Glue, 8 ~ 12 parts of silica gel microballs, 16 ~ 24 parts of methyl methacrylates, 20 ~ 40 parts of polyethylene glycol, 4 ~ 8 parts of polyoxyethylene ether, 2 ~ 4 parts
Vinyltriethoxysilane, 0.6 ~ 1.2 part of azodiisobutyronitrile, 20 ~ 40 parts of dehydrated alcohols, 20 ~ 40 parts of n-butanols, will be anhydrous
Ethyl alcohol is added in n-butanol, is stirred 8 ~ 10min under room temperature with 80 ~ 100r/min revolving speed, obtains mixing alcoholic solution, by methyl-prop
E pioic acid methyl ester, polyethylene glycol, polyoxyethylene ether, vinyltriethoxysilane are added in mixing alcoholic solution, in 30 ~ 40 DEG C of water
It bathes and 15 ~ 20min is stirred with 200 ~ 240r/min revolving speed under air-proof condition, room temperature cooling obtains polymer alcoholic solution, copper metal is had
Machine gel, silica gel microball, azodiisobutyronitrile are added in polymer alcoholic solution, are quickly stirred under room temperature with 600 ~ 800r/min revolving speed
4 ~ 8min is mixed, then is placed in ultrasonic dispersing machine, 40 ~ 60min of ultrasonic disperse, obtains dispersion liquid under conditions of 500 ~ 600W, takes
The quartz capillary that piece internal diameter is 200 ~ 300 μm, is washed 3 ~ 5 times with the sodium hydroxide solution of mass concentration 1%, then spend from
Sub- water washing 3 ~ 5 times, with the dry 40 ~ 60min of 60 ~ 80 DEG C of temperature in nitrogen atmosphere, room temperature cooling obtains pretreated capillary
Pipe, dispersion liquid is injected in pretreated capillary, be placed under 60 ~ 70 DEG C of water bath condition stand reaction 20 ~ for 24 hours, room temperature is cold
But, organic inorganic hybridization integral post is obtained.
According to parts by weight, 5 parts of cupric perchlorates, 10 parts of melamines, 1 part of citric acid, 20 parts of N, N- diformazan are weighed respectively
Cupric perchlorate, melamine, citric acid are added in n,N-Dimethylformamide, are turned under room temperature with 180r/min by base formamide
Speed is stirred 10min, stands 20h, obtains copper ion mixed liquor, copper ion mixed liquor is placed in ultrasonic dispersing machine,
Ultrasonic vibration 15min under conditions of 400W obtains copper metal organogel；Again according to parts by weight, 20 parts of positive silicic acid are weighed respectively
Deionization is added in dehydrated alcohol, ammonium hydroxide by ethyl ester, 8 parts of dehydrated alcohols, the ammonium hydroxide of 16 parts of mass concentrations 25%, 20 parts of deionized waters
In water, 10min is stirred with 120r/min revolving speed under room temperature, obtains alcohol ammonia hydrolyzate, 1/3 alcohol ammonium hydroxide is added in 1/3 ethyl orthosilicate
It solves in liquid, 30min is stirred with 240r/min revolving speed under 0 DEG C of refrigerated condition, obtains silica gel nucleus liquid, by remaining 2/3 positive silicic acid
Ethyl ester and 2/3 alcohol ammonia hydrolyzate are slowly added in silica gel nucleus liquid with the drop rate of 2mL/min and 5mL/min respectively, juxtaposition
12h is stirred to react with 200r/min revolving speed under 18 DEG C of water bath condition, obtains reaction solution, by the still aging 2h of reaction solution, then is set
In decompression suction filtration machine, is filtered under conditions of -0.4MPa, take filter cake, be washed with deionized 3 times, be placed in 100 DEG C of baking oven
Middle dry 4h, room temperature cooling obtain silica gel microball；Again according to parts by weight, 10 parts of copper metal organogels, 8 parts of silicon are weighed respectively
Glue microballoon, 16 parts of methyl methacrylates, 20 parts of polyethylene glycol, 4 parts of polyoxyethylene ether, 2 parts of vinyltriethoxysilane,
0.6 part of azodiisobutyronitrile, 20 parts of dehydrated alcohols, 20 parts of n-butanols dehydrated alcohol are added in n-butanol, with 80r/ under room temperature
Min revolving speed is stirred 8min, obtains mixing alcoholic solution, by methyl methacrylate, polyethylene glycol, polyoxyethylene ether, vinyl
Triethoxysilane is added in mixing alcoholic solution, stirs 15min under 30 DEG C of water-bath air-proof condition with 200r/min revolving speed, often
Temperature is cooling, obtains polymer alcoholic solution, and polymer alcoholic solution is added in copper metal organogel, silica gel microball, azodiisobutyronitrile
In, 4min is stirred quickly with 600r/min revolving speed under room temperature, then be placed in ultrasonic dispersing machine, the ultrasound point under conditions of 500W
40min is dissipated, dispersion liquid is obtained, taking an internal diameter is 200 μm of quartz capillary, is washed with the sodium hydroxide solution of mass concentration 1%
3 times, then be washed with deionized 3 times, with the dry 40min of 60 DEG C of temperature in nitrogen atmosphere, room temperature cooling is obtained pretreated
Capillary injects dispersion liquid in pretreated capillary, is placed under 60 DEG C of water bath condition and stands reaction 20h, room temperature cooling,
Obtain organic inorganic hybridization integral post.
According to parts by weight, 7 parts of cupric perchlorates, 15 parts of melamines, 1.5 parts of citric acids, 30 parts of N, N- bis- are weighed respectively
Methylformamide cupric perchlorate, melamine, citric acid is added in n,N-Dimethylformamide, with 190r/min under room temperature
Revolving speed is stirred 11min, stands 22h, obtains copper ion mixed liquor, copper ion mixed liquor is placed in ultrasonic dispersing machine,
Ultrasonic vibration 17min under conditions of 450W obtains copper metal organogel；Again according to parts by weight, 25 parts of positive silicic acid are weighed respectively
Ethyl ester, 10 parts of dehydrated alcohols, the ammonium hydroxide of 20 parts of mass concentrations 25%, 25 parts of deionized waters, by dehydrated alcohol, ammonium hydroxide addition go from
In sub- water, 11min is stirred with 140r/min revolving speed under room temperature, obtains alcohol ammonia hydrolyzate, 1/3 alcohol ammonia is added in 1/3 ethyl orthosilicate
In hydrolyzate, 35min is stirred with 260r/min revolving speed under 1 DEG C of refrigerated condition, obtains silica gel nucleus liquid, by remaining 2/3 positive silicon
Acetoacetic ester and 2/3 alcohol ammonia hydrolyzate are slowly added in silica gel nucleus liquid with the drop rate of 2mL/min and 5mL/min respectively, and
It is placed under 20 DEG C of water bath condition and 14h is stirred to react with 220r/min revolving speed, obtain reaction solution, by the still aging 4h of reaction solution, then
It is placed in decompression suction filtration machine, is filtered under conditions of -0.3MPa, take filter cake, be washed with deionized 4 times, be placed in 110 DEG C of baking
Dry 6h, room temperature cooling obtain silica gel microball in case；Again according to parts by weight, 15 parts of copper metal organogels, 10 parts are weighed respectively
Silica gel microball, 20 parts of methyl methacrylates, 30 parts of polyethylene glycol, 6 parts of polyoxyethylene ether, 3 parts of vinyltriethoxysilane,
0.9 part of azodiisobutyronitrile, 30 parts of dehydrated alcohols, 30 parts of n-butanols dehydrated alcohol are added in n-butanol, with 90r/ under room temperature
Min revolving speed is stirred 9min, obtains mixing alcoholic solution, by methyl methacrylate, polyethylene glycol, polyoxyethylene ether, vinyl
Triethoxysilane is added in mixing alcoholic solution, stirs 17min under 35 DEG C of water-bath air-proof condition with 220r/min revolving speed, often
Temperature is cooling, obtains polymer alcoholic solution, and polymer alcoholic solution is added in copper metal organogel, silica gel microball, azodiisobutyronitrile
In, 6min is stirred quickly with 700r/min revolving speed under room temperature, then be placed in ultrasonic dispersing machine, the ultrasound point under conditions of 550W
50min is dissipated, dispersion liquid is obtained, taking an internal diameter is 250 μm of quartz capillary, is washed with the sodium hydroxide solution of mass concentration 1%
4 times, then be washed with deionized 4 times, with the dry 50min of 70 DEG C of temperature in nitrogen atmosphere, room temperature cooling is obtained pretreated
Capillary injects dispersion liquid in pretreated capillary, is placed under 65 DEG C of water bath condition and stands reaction 22h, room temperature cooling,
Obtain organic inorganic hybridization integral post.
According to parts by weight, 10 parts of cupric perchlorates, 20 parts of melamines, 2 parts of citric acids, 40 parts of N, N- diformazan are weighed respectively
Cupric perchlorate, melamine, citric acid are added in n,N-Dimethylformamide, are turned under room temperature with 200r/min by base formamide
Speed is stirred 12min, stands for 24 hours, obtains copper ion mixed liquor, copper ion mixed liquor is placed in ultrasonic dispersing machine,
Ultrasonic vibration 20min under conditions of 500W obtains copper metal organogel；Again according to parts by weight, 30 parts of positive silicic acid are weighed respectively
Ethyl ester, 12 parts of dehydrated alcohols, the ammonium hydroxide of 24 parts of mass concentrations 25%, 30 parts of deionized waters, by dehydrated alcohol, ammonium hydroxide addition go from
In sub- water, 12min is stirred with 160r/min revolving speed under room temperature, obtains alcohol ammonia hydrolyzate, 1/3 alcohol ammonia is added in 1/3 ethyl orthosilicate
In hydrolyzate, 40min is stirred with 280r/min revolving speed under 2 DEG C of refrigerated condition, obtains silica gel nucleus liquid, by remaining 2/3 positive silicon
Acetoacetic ester and 2/3 alcohol ammonia hydrolyzate are slowly added in silica gel nucleus liquid with the drop rate of 2mL/min and 5mL/min respectively, and
It is placed under 22 DEG C of water bath condition and 16h is stirred to react with 240r/min revolving speed, obtain reaction solution, by the still aging 6h of reaction solution, then
It is placed in decompression suction filtration machine, is filtered under conditions of -0.2MPa, take filter cake, be washed with deionized 5 times, be placed in 120 DEG C of baking
Dry 8h, room temperature cooling obtain silica gel microball in case；Again according to parts by weight, 20 parts of copper metal organogels, 12 parts are weighed respectively
Silica gel microball, 24 parts of methyl methacrylates, 40 parts of polyethylene glycol, 8 parts of polyoxyethylene ether, 4 parts of vinyltriethoxysilane,
1.2 parts of azodiisobutyronitriles, 40 parts of dehydrated alcohols, 40 parts of n-butanols, by dehydrated alcohol be added n-butanol in, under room temperature with
100r/min revolving speed is stirred 10min, obtains mixing alcoholic solution, by methyl methacrylate, polyethylene glycol, polyoxyethylene ether,
Vinyltriethoxysilane is added in mixing alcoholic solution, with the stirring of 240r/min revolving speed under 40 DEG C of water-bath air-proof condition
20min, room temperature cooling obtain polymer alcoholic solution, and polymerization is added in copper metal organogel, silica gel microball, azodiisobutyronitrile
In object alcoholic solution, 8min is stirred quickly with 800r/min revolving speed under room temperature, then be placed in ultrasonic dispersing machine, in the condition of 600W
Lower ultrasonic disperse 60min, obtains dispersion liquid, and taking an internal diameter is 300 μm of quartz capillary, with the sodium hydroxide of mass concentration 1%
Solution washs 5 times, then is washed with deionized 5 times, and with the dry 60min of 80 DEG C of temperature in nitrogen atmosphere, room temperature cooling is obtained
Pretreated capillary injects dispersion liquid in pretreated capillary, is placed under 70 DEG C of water bath condition and stands reaction for 24 hours,
Room temperature cooling obtains organic inorganic hybridization integral post.
Organic inorganic hybridization integral post prepared by the present invention is detected, specific testing result is as follows:
Performance test:
Application Example 1-3 preparation organic inorganic hybridization integral post, be with potassium dihydrogen phosphate (5mmol/L)-acetonitrile (23:77)
Mobile phase, UV detector, Detection wavelength 276nm, flow velocity 1.0mL/min；Sample volume: 20 μ L, column temperature: room temperature, acquisition time:
10min.The Ractopamine of trace is enriched with, its enrichment times is recorded.
1 organic inorganic hybridization integral post performance characterization of table
| Performance characterization | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Enrichment times | 98.9 | 99.7 | 100.5 |
Organic inorganic hybridization integral post prepared by the present invention as shown in Table 1, bioaccumulation efficiency is high, excellent combination property.
Claims (9)
1. a kind of preparation method of organic inorganic hybridization integral post, which is characterized in that specific preparation step are as follows:
(1) by acrylic rubber, nitrile rubber, modified carbon black, carbon fiber, copper powder, glycerine, stearic acid, antioxidant 1010
It is placed in blender, 30 ~ 40min is stirred with 200 ~ 240r/min revolving speed under room temperature, obtains mixture；
(2) mixture is placed in two-roll mill, 15 ~ 20min of mill under conditions of 100 ~ 120 DEG C obtains mill rubber；
(3) mill rubber is placed in vulcanizing press, sulphur is added, vulcanize 20 ~ 40min, room temperature cooling obtains water lubriucated bearing
Use composite rubber material.
2. a kind of preparation method of water lubriucated bearing composite rubber material according to claim 1, which is characterized in that institute
The acrylic rubber stated, nitrile rubber, modified carbon black, carbon fiber, copper powder, glycerine, stearic acid, antioxidant 1010, sulphur
Parts by weight be 40 ~ 60 parts of acrylic rubber, 20 ~ 30 parts of nitrile rubbers, 12 ~ 18 parts of modified carbon blacks, 8 ~ 12 parts of carbon fibers, 6 ~
9 parts of copper powders, 4 ~ 6 parts of glycerine, 2 ~ 3 parts of stearic acid, 0.4 ~ 0.6 part of antioxidant 1010,2 ~ 3 parts of sulphur.
3. a kind of preparation method of water lubriucated bearing composite rubber material according to claim 1, which is characterized in that step
Suddenly conditions of vulcanization described in (3) is 160 ~ 200 DEG C, 16 ~ 18MPa.
4. a kind of preparation method of water lubriucated bearing composite rubber material according to claim 1, which is characterized in that step
Suddenly the specific preparation step of modified carbon black described in (1) are as follows:
(1) carbon black is added in nitric acid, 40 ~ 60min is stirred with 400 ~ 500r/min revolving speed under room temperature, obtains mixed liquor；
(2) mixed liquor is placed in ultrasonic oscillator, 1 ~ 2h of ultrasonic disperse obtains dispersion liquid；
(3) dispersion liquid is placed in centrifugal separator, 10 ~ 15min is centrifugated with 4000 ~ 4500r/min revolving speed under room temperature, is gone
Lower layer's solid is washed with deionized 3 ~ 5 times, is placed in 40 ~ 50 DEG C of baking ovens dry 40 ~ 60min, obtains modified carbon black.
5. a kind of preparation method of water lubriucated bearing composite rubber material according to claim 4, which is characterized in that institute
The parts by weight of the carbon black, nitric acid stated are the nitric acid of 30 ~ 40 parts of carbon blacks, 120 ~ 160 parts of mass concentrations 10%.
6. a kind of preparation method of water lubriucated bearing composite rubber material according to claim 4, which is characterized in that step
Suddenly the power of ultrasonic disperse described in (2) is 400 ~ 500W.
7. a kind of preparation method of water lubriucated bearing composite rubber material according to claim 1, which is characterized in that step
Suddenly the specific preparation step of acrylic rubber described in (1) are as follows:
(1) butyl acrylate, ethyl acrylate, methyl methacrylate, lauryl sodium sulfate are added in deionized water,
10 ~ 12min is stirred with 200 ~ 250r/min revolving speed under 50 ~ 60 DEG C of water bath condition, keeps the temperature, obtains crylic acid ester mixture liquid；
(2) sodium dithionite, ammonium persulfate are added in crylic acid ester mixture liquid, nitrogen protection are passed through, in 50 ~ 60 DEG C of water
1 ~ 2h is stirred to react with 240 ~ 280r/min revolving speed under the conditions of bath, obtains reaction lotion；
(3) by dehydrated alcohol be added reaction lotion in, under room temperature with 180 ~ 200r/min revolving speed stir 8 ~ 10min, stand 30 ~
40min, filtering, takes solid, obtains reaction polymer；
(4) reaction polymer is washed 2 ~ 4 times with dehydrated alcohol, then be washed with deionized 1 ~ 3 time, be placed in 60 ~ 70 DEG C of baking
Dry 40 ~ 60min, room temperature cooling obtain acrylic rubber in case.
8. a kind of preparation method of water lubriucated bearing composite rubber material according to claim 7, which is characterized in that institute
Butyl acrylate, ethyl acrylate, methyl methacrylate, lauryl sodium sulfate, sodium dithionite, the persulfuric acid stated
Ammonium, dehydrated alcohol, deionized water parts by weight be 20 ~ 40 parts of butyl acrylates, 20 ~ 40 parts of ethyl acrylates, 20 ~ 40 parts of methyl
Methyl acrylate, 0.6 ~ 1.2 part of lauryl sodium sulfate, 0.1 ~ 0.2 part of sodium dithionite, 0.1 ~ 0.2 part of ammonium persulfate, 10
~ 20 parts of dehydrated alcohols, 40 ~ 80 parts of deionized waters.
9. a kind of preparation method of water lubriucated bearing composite rubber material according to claim 7, which is characterized in that step
Suddenly the rate that is passed through of nitrogen described in (2) is 30 ~ 40mL/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112827471A (en) * | 2020-12-29 | 2021-05-25 | 南京凯创微锌环境技术有限公司 | A kind of preparation method of deodorant for sheep farm |
| CN112973655A (en) * | 2019-12-02 | 2021-06-18 | 中国科学院大连化学物理研究所 | Ion exchange chromatography stationary phase and preparation and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973655A (en) * | 2019-12-02 | 2021-06-18 | 中国科学院大连化学物理研究所 | Ion exchange chromatography stationary phase and preparation and application thereof |
| CN112973655B (en) * | 2019-12-02 | 2022-07-19 | 中国科学院大连化学物理研究所 | An ion exchange chromatography stationary phase and its preparation and application |
| CN112827471A (en) * | 2020-12-29 | 2021-05-25 | 南京凯创微锌环境技术有限公司 | A kind of preparation method of deodorant for sheep farm |
| CN112827471B (en) * | 2020-12-29 | 2023-10-31 | 南京凯创微锌环境技术有限公司 | Preparation method of deodorant for sheep farms |
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