CN113278102A - Preparation method of functional colorful PS microspheres - Google Patents
Preparation method of functional colorful PS microspheres Download PDFInfo
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- CN113278102A CN113278102A CN202110643430.5A CN202110643430A CN113278102A CN 113278102 A CN113278102 A CN 113278102A CN 202110643430 A CN202110643430 A CN 202110643430A CN 113278102 A CN113278102 A CN 113278102A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 158
- 239000004793 Polystyrene Substances 0.000 claims abstract description 85
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003999 initiator Substances 0.000 claims abstract description 56
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 41
- 229920002223 polystyrene Polymers 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 238000004945 emulsification Methods 0.000 claims abstract description 9
- 239000000975 dye Substances 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000000502 dialysis Methods 0.000 claims description 17
- -1 amino, hydroxyl Chemical group 0.000 claims description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 239000012874 anionic emulsifier Substances 0.000 claims description 10
- 239000000987 azo dye Substances 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000012875 nonionic emulsifier Substances 0.000 claims description 10
- 239000000985 reactive dye Substances 0.000 claims description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000001001 arylmethane dye Substances 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 5
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 239000001000 anthraquinone dye Substances 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 5
- 239000001005 nitro dye Substances 0.000 claims description 5
- 239000001007 phthalocyanine dye Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 5
- 239000000988 sulfur dye Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- VFTKIWJJPDJBKD-UHFFFAOYSA-N OCCC[Na] Chemical compound OCCC[Na] VFTKIWJJPDJBKD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical group CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 24
- 238000010586 diagram Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 7
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000000427 antigen Substances 0.000 description 4
- 102000036639 antigens Human genes 0.000 description 4
- 108091007433 antigens Proteins 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- 239000000986 disperse dye Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003550 marker Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VQTGUFBGYOIUFS-UHFFFAOYSA-N nitrosylsulfuric acid Chemical compound OS(=O)(=O)ON=O VQTGUFBGYOIUFS-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- MQIUMARJCOGCIM-UHFFFAOYSA-N 1,5-dichloroanthracene-9,10-dione Chemical compound O=C1C2=C(Cl)C=CC=C2C(=O)C2=C1C=CC=C2Cl MQIUMARJCOGCIM-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- KWMDHCLJYMVBNS-UHFFFAOYSA-N 2-bromo-4,6-dinitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1[N+]([O-])=O KWMDHCLJYMVBNS-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000009967 direct dyeing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to the technical field of colored polymers, and particularly discloses a preparation method of functional colored PS microspheres, which comprises the following steps of (a1) mixing a proper amount of functional monomers, a proper amount of non-functional monomers, a proper amount of dye monomers containing unsaturated double bonds and a proper amount of styrene monomers; (b1) adding the mixture obtained in the step (a1) into an aqueous solution containing an emulsifying agent for emulsification; (c1) adding an aqueous solution containing an initiator to the mixed solution emulsified in the step (b1) for dispersion; (d1) under the protection of nitrogen, dropwise adding the mixed solution dispersed in the step (c1) into water at the temperature of 70-90 ℃; (e1) and (d1) adding a proper amount of initiator solution into the mixed solution in the step (d1) after the dropwise addition is completed, and standing at the temperature of 70-90 ℃ for 3-12 h to obtain the functionalized colored polystyrene microsphere emulsion. The invention has the characteristics of simple preparation process, good stability and good color development.
Description
Technical Field
The invention relates to the technical field of colored polymers, in particular to a preparation method of functional colored PS microspheres.
Background
With the rapid development of lateral chromatography, the system integration of quantitative, high-sensitivity, multi-element detection and chromatography begins to become a new research direction in this field. The color microsphere, the fluorescent microsphere and the magnetic bead become a new generation of antigen/antibody markers after the colloidal gold, and compared with the traditional colloidal gold, the latex microsphere has good stability, wide linear range and high sensitivity, and is very suitable for quantitative lateral chromatography detection; the polystyrene microsphere has the characteristics of a high-molecular microsphere material, such as small particle size, large specific surface area, strong adsorbability, good dispersibility, easiness in modification and the like, and is widely applied to the fields of biochemistry, electrochemical detection, catalysts, adsorbents, chromatographic fillers, coatings and the like.
At present, the preparation method of the colorful PS microspheres mainly comprises coating or direct dyeing of disperse dyes. For example, patent document CN101633709A discloses a method for preparing colored polystyrene particles synthesized by in-situ suspension polymerization one-step method, but the method has complicated preparation process and many synthesis steps. In the patent document with publication number CN105199117A, a method for preparing hollow colored polystyrene-acrylic microspheres is also disclosed, in which disperse dyes with different structures are used to directly dye the hollow colored polystyrene-acrylic microspheres to obtain the hollow colored polymer microspheres with high glossiness and bright color, but the method has a complicated preparation process, requires screening of disperse dyes with different structures, dyeing at different proportions and different temperatures for different times, and then cooling, separating and purifying, and is also complicated.
Therefore, the existing preparation of the colorful PS microspheres has the problem of complex preparation process.
Disclosure of Invention
The invention provides a preparation method of functional colorful PS microspheres with simple preparation process, good stability and good color development property, aiming at solving the technical problems existing in the existing preparation of colorful PS microspheres.
The first technical scheme of the invention is as follows: a method for preparing functional colorful PS microspheres comprises the following steps,
(a1) taking a proper amount of functional monomer, a proper amount of non-functional monomer, a proper amount of unsaturated double bond-containing dye monomer and a proper amount of styrene monomer, and then mixing;
(b1) adding the mixture obtained in the step (a1) into an aqueous solution containing an emulsifying agent for emulsification;
(c1) adding an aqueous solution containing an initiator to the mixed solution emulsified in the step (b1) for dispersion;
(d1) under the protection of nitrogen, dropwise adding the mixed solution dispersed in the step (c1) into water at the temperature of 70-90 ℃;
(e1) adding a proper amount of initiator solution into the mixed solution obtained in the step (d1) after the dropwise addition is finished, and standing at the temperature of 70-90 ℃ for 3-12 hours to obtain the functionalized colored polystyrene microsphere emulsion;
(f1) and (3) cooling the temperature of the functionalized colored polystyrene microsphere emulsion to room temperature, placing the emulsion in a dialysis bag for dialysis, and removing unreacted monomers to obtain the functionalized colored polystyrene microsphere.
According to the invention, four types of monomers, namely a functional monomer, a non-functional monomer, a dye monomer containing an unsaturated double bond and a styrene monomer, are selected as raw materials, and are placed at the temperature of 70-90 ℃ for 3-12 h for polymerization reaction, so that the dye monomer containing the unsaturated double bond is added into a styrene chain in a covalent bond combination mode, and the finally prepared polystyrene microsphere has color, compared with the color PS microsphere prepared by the traditional coating method, the polystyrene microsphere has higher stability because of covalent bond combination, a large amount of emulsifier is not needed to be used for stabilizing the PS microsphere, and the process synthesis step is simplified; wherein, the dye monomer with unsaturated double bond is randomly and evenly added into the styrene chain, thereby having better color rendering property; the invention firstly adds the aqueous solution containing the emulsifier to emulsify in the whole reaction, so that the whole mixed solution is uniformly mixed, and the aqueous solution containing the initiator is added twice to disperse, thereby improving the conversion rate of the monomer, increasing the dispersibility of the monomer, ensuring that the particle size distribution of each particle in the finally prepared functionalized colored polystyrene microsphere is more uniform, and having higher sensitivity in the aspect of being used as an antigen/antibody marker.
The second technical scheme of the invention is as follows: a method for preparing functional colorful PS microspheres comprises the following steps,
(a2) taking a proper amount of functional monomer, a proper amount of non-functional monomer and a proper amount of styrene monomer and then mixing;
(b2) adding the mixture obtained in the step (a2) into an aqueous solution containing an emulsifier and a dye monomer containing an unsaturated double bond for emulsification;
(c2) adding an aqueous solution containing an initiator to the mixed solution emulsified in the step (b2) for dispersion;
(d2) under the protection of nitrogen, dropwise adding the mixed solution dispersed in the step (c2) into water at the temperature of 70-90 ℃;
(e2) adding a proper amount of initiator solution into the mixed solution obtained in the step (d2) after the dropwise addition is finished, and standing at the temperature of 70-90 ℃ for 3-12 hours to obtain the functionalized colored polystyrene microsphere emulsion;
(f2) and (3) cooling the temperature of the functionalized colored polystyrene microsphere emulsion to room temperature, placing the emulsion in a dialysis bag for dialysis, and removing unreacted monomers to obtain the functionalized colored polystyrene microsphere.
According to the invention, four types of monomers, namely a functional monomer, a non-functional monomer, a dye monomer containing an unsaturated double bond and a styrene monomer, are selected as raw materials, and are placed at the temperature of 70-90 ℃ for 3-12 h for polymerization reaction, so that the dye monomer containing the unsaturated double bond is added into a styrene chain in a covalent bond combination mode, and the finally prepared polystyrene microsphere has color, compared with the color PS microsphere prepared by the traditional coating method, the polystyrene microsphere has higher stability because of covalent bond combination, a large amount of emulsifier is not needed to be used for stabilizing the PS microsphere, and the process synthesis step is simplified; wherein, the dye monomer with unsaturated double bond is randomly and evenly added into the styrene chain, thereby having better color rendering property; the invention firstly adds the aqueous solution containing the emulsifier to emulsify in the whole reaction, so that the whole mixed solution is uniformly mixed, and the aqueous solution containing the initiator is added twice to disperse, thereby improving the conversion rate of the monomer, increasing the dispersibility of the monomer, ensuring that the particle size distribution of each particle in the finally prepared functionalized colored polystyrene microsphere is more uniform, and having higher sensitivity in the aspect of being used as an antigen/antibody marker.
Preferably, the functional monomer is at least one selected from a carboxyl group-containing unsaturated monomer, an amino group-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer, a chloromethyl group-containing unsaturated monomer, a sulfonic acid group-containing unsaturated monomer, and an amide group-containing unsaturated monomer. The functional monomer is used to enable the finally prepared functionalized colored polystyrene microsphere to contain a functional group, and the functional group can react with a crosslinking agent to form a crosslinking structure, so that the functionalized colored polystyrene microsphere has the functional characteristics of pollution resistance, solvent resistance, water resistance, light and color retention and the like.
Preferably, the amount of the functional monomer is 0.1 to 15% by mass of styrene. More preferably, the amount of the functional monomer is 0.5 to 10% by mass of styrene. More preferably, the amount of the functional monomer is 1 to 5% by mass of styrene. The dosage of the functional monomer is limited, so that the functionalized colored polystyrene microsphere has good functional characteristics, and the grafting of the dye monomer containing unsaturated double bonds in a styrene chain cannot be influenced.
Preferably, the non-functional monomer is at least one selected from the group consisting of methyl acrylate, butyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and hydroxyethyl acrylate. The polarity, solubility and hardness of the finally prepared functionalized colored polystyrene microspheres can be improved by utilizing copolymerization of a plurality of non-functional monomers and through synergistic interaction, and the functionalized colored polystyrene microspheres have better performance.
Preferably, the amount of the non-functional monomer is 1 to 40% by mass of the styrene monomer. More preferably, the amount of the non-functional monomer is 5 to 30% by mass of the styrene monomer. More preferably, the amount of the non-functional monomer is 10 to 25% by mass of the styrene monomer. More preferably, the amount of the non-functional monomer is 15 to 20% by mass of the styrene monomer. The dosage of the non-functional monomer is limited, so that the functionalized colored polystyrene microsphere has good characteristics and can not affect the grafting of the dye monomer containing unsaturated double bonds in a styrene chain.
Preferably, the unsaturated double bond-containing dye monomer is at least one selected from azo dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, nitro dyes, polymethine dyes, arylmethane dyes, reactive dyes and sulfur dyes. The dye monomer containing unsaturated double bonds can be added with a colored group in a styrene chain by a polymerization method so as to have color, and the chromophore in the dye monomer containing unsaturated double bonds is combined with the polystyrene microsphere microspheres through covalent bonds, so that the dye monomer has more sensitive and stable color rendering property.
Preferably, the amount of the unsaturated double bond-containing dye monomer is 0.5-20% of the mass of the styrene monomer. More preferably, the amount of the unsaturated double bond-containing dye monomer is 1 to 15 percent of the mass of the styrene monomer. More preferably, the amount of the unsaturated double bond-containing dye monomer is 5 to 10 percent of the mass of the styrene monomer. The amount of the dye monomer containing the unsaturated double bond is limited, so that the dye monomer containing the unsaturated double bond can be grafted in a styrene chain better, and the color rendering property is better.
Preferably, the unsaturated double bond-containing dye monomer is of a water-soluble monomer structure and/or an oil-soluble monomer structure. The types of the dye monomers containing unsaturated double bonds can be flexibly selected, and different selections can lead the finally prepared functionalized colored polystyrene microspheres to have different performances and more selectivity.
Preferably, the emulsifier is selected from at least one of an anionic emulsifier, a nonionic emulsifier, or a polymerizable emulsifier. The emulsifier has more selectivity, can more fully and evenly mix all components in the mixed solution, and enables the particle size distribution of all particles in the microspheres to be more even.
Preferably, the anionic emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium stearate or sodium dodecyl diphenyl ether disulfonate.
Preferably, the nonionic emulsifier is polyoxyethylene octylphenol ether and/or polyoxyethylene nonylphenol ether.
Preferably, the polymerizable emulsifier is at least one of 2-acrylamide-2-methylpropanesulfonic acid, sodium allyloxypropanesulfonate, or Japanese SE-10N.
Preferably, the amount of the emulsifier is 0.3-2% of the mass of the styrene monomer. More preferably, the amount of the emulsifier is 0.5 to 1.5% by mass of the styrene monomer. More preferably, the amount of the emulsifier is 0.8 to 1.1 percent of the mass of the styrene monomer. The emulsifier is limited, so that the uniform mixing of the components can be better ensured, and the preparation is prepared for the later polymerization reaction.
Preferably, the initiator is a water-soluble initiator. The initiator can be flexibly selected according to actual needs so as to better improve the monomer conversion rate.
Preferably, the water-soluble initiator is a water-soluble inorganic salt initiator and/or a water-soluble hydrogen peroxide initiator.
Preferably, the water-soluble inorganic salt initiator is at least one of ammonium persulfate, sodium persulfate and potassium persulfate.
Preferably, the water-soluble hydrogen peroxide initiator is hydrogen peroxide and/or tert-butyl hydroperoxide.
Preferably, the emulsifying time is 15-60 min. More preferably, the emulsifying time is 20-45 min. More preferably, the emulsifying time is 25-35 min. Can be mixed more uniformly.
Preferably, the dispersing time is 5 to 30 min. More preferably, the dispersing time is 10-25 min. More preferably, the dispersing time is 15-20 min. So that the reaction of each monomer is more complete and faster.
The invention has the following beneficial effects:
(1) the method comprises the following steps of selecting four monomers of a functional monomer, a non-functional monomer, a dye monomer containing an unsaturated double bond and a styrene monomer as raw materials, placing the raw materials at the temperature of 70-90 ℃ for 3-12 h for polymerization reaction, and adding the dye monomer containing the unsaturated double bond into a styrene chain in a covalent bond combination mode, so that the finally prepared polystyrene microsphere has color, compared with the color PS microsphere prepared by the traditional coating method, the method has higher stability because the dye monomer containing the unsaturated double bond is combined through the covalent bond, and the PS microsphere is not required to be stabilized by using a large amount of emulsifier, so that the process synthesis step is simplified; wherein, the dye monomer with unsaturated double bond is randomly and evenly added into the styrene chain, thereby having better color rendering property;
(2) in the whole reaction, the aqueous solution containing the emulsifier is added for emulsification, so that the whole mixed solution is uniformly mixed, and the aqueous solution containing the initiator is added for dispersion twice, so that the conversion rate of the monomer is improved, the dispersibility of the monomer is increased, the particle size distribution of each particle in the finally prepared functionalized colored polystyrene microsphere is uniform, and the functionalized colored polystyrene microsphere has higher sensitivity in the aspect of being used as an antigen/antibody marker.
Drawings
FIG. 1 is a molecular structural diagram of a first anthraquinone-based dye according to the present invention;
FIG. 2 is a molecular structure diagram of a first azo dye according to the present invention;
FIG. 3 is a molecular structural diagram of a second anthraquinone-based dye according to the present invention;
FIG. 4 is a molecular structure diagram of a second azo dye according to the present invention;
FIG. 5 is a molecular structure diagram of a third azo dye according to the present invention;
FIG. 6 is a molecular structure diagram of an arylmethane dye according to the present invention;
FIG. 7 is a molecular structure diagram of a fourth azo dye according to the present invention;
FIG. 8 is a molecular structure diagram of a fifth azo dye according to the present invention;
FIG. 9 is a molecular structure diagram of a first reactive dye in the present invention;
FIG. 10 is a molecular structural diagram of a second reactive dye in the present invention;
FIG. 11 is a molecular structural diagram of a third reactive dye according to the present invention;
FIG. 12 is a molecular structural diagram of a fourth reactive dye in the present invention.
FIG. 13 is a molecular structural diagram of a fifth reactive dye in the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited thereto.
A method for preparing functional colorful PS microspheres comprises the following steps,
(a1) taking a proper amount of functional monomer, a proper amount of non-functional monomer, a proper amount of unsaturated double bond-containing dye monomer and a proper amount of styrene monomer, and then mixing; the functional monomer is at least one selected from unsaturated monomers containing carboxyl, amino, hydroxyl, chloromethyl, sulfonic acid and amido. The dosage of the functional monomer is 0.1-15% of the mass of the styrene. The non-functional monomer is at least one selected from methyl acrylate, butyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate or hydroxyethyl acrylate. The dosage of the non-functional monomer is 1 to 40 percent of the mass of the styrene monomer. The unsaturated double bond-containing dye monomer is at least one selected from azo dyes shown in figures 2, 4, 5, 7 and 8, anthraquinone dyes shown in figures 1 and 3, phthalocyanine dyes, indigoid dyes, nitro dyes, polymethine dyes, arylmethane dyes shown in figure 6, reactive dyes or sulfur dyes shown in figures 9, 10, 11, 12 and 13. The dosage of the dye monomer containing unsaturated double bonds is 0.5 to 20 percent of the mass of the styrene monomer. The dye monomer containing unsaturated double bonds is of a water-soluble monomer structure and/or an oil-soluble monomer structure.
(b1) Adding the mixture obtained in the step (a1) into an aqueous solution containing an emulsifying agent for emulsification; the emulsifier is selected from at least one of anionic emulsifier, nonionic emulsifier or polymerizable emulsifier. The anionic emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium stearate or sodium dodecyl diphenyl ether disulfonate. The nonionic emulsifier is polyoxyethylene octylphenol ether and/or polyoxyethylene nonylphenol ether. The polymerizable emulsifier is at least one of 2-acrylamide-2-methylpropanesulfonic acid, sodium allyloxypropanesulfonate, or Japanese SE-10N. The dosage of the emulsifier is 0.3-2% of the mass of the styrene monomer. The emulsifying time is 15-60 min.
(c1) Adding an aqueous solution containing an initiator to the mixed solution emulsified in the step (b1) for dispersion; the initiator is a water-soluble initiator. The water-soluble initiator is water-soluble inorganic salt initiator and/or water-soluble hydrogen peroxide initiator. The water-soluble inorganic salt initiator is at least one of ammonium persulfate, sodium persulfate or potassium persulfate. The water-soluble hydrogen peroxide initiator is hydrogen peroxide and/or tert-butyl hydroperoxide. The dispersion time is 5-30 min.
(d1) Under the protection of nitrogen, dropwise adding the mixed solution dispersed in the step (c1) into water at the temperature of 70-90 ℃;
(e1) adding a proper amount of initiator solution into the mixed solution obtained in the step (d1) after the dropwise addition is finished, and standing at the temperature of 70-90 ℃ for 3-12 hours to obtain the functionalized colored polystyrene microsphere emulsion;
(f1) and (3) cooling the temperature of the functionalized colored polystyrene microsphere emulsion to room temperature, placing the emulsion in a dialysis bag for dialysis, and removing unreacted monomers to obtain the functionalized colored polystyrene microsphere.
A method for preparing functional colorful PS microspheres comprises the following steps,
(a2) taking a proper amount of functional monomer, a proper amount of non-functional monomer and a proper amount of styrene monomer and then mixing; the functional monomer is at least one selected from unsaturated monomers containing carboxyl, amino, hydroxyl, chloromethyl, sulfonic acid and amido. The dosage of the functional monomer is 0.1-15% of the mass of the styrene. The non-functional monomer is at least one selected from methyl acrylate, butyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate or hydroxyethyl acrylate. The dosage of the non-functional monomer is 1 to 40 percent of the mass of the styrene monomer.
(b2) Adding the mixture obtained in the step (a2) into an aqueous solution containing an emulsifier and a dye monomer containing an unsaturated double bond for emulsification; the dye monomer containing unsaturated double bonds is selected from at least one of azo dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, nitro dyes, polymethine dyes, aryl methane dyes, reactive dyes or sulfur dyes. The dosage of the dye monomer containing unsaturated double bonds is 0.5 to 20 percent of the mass of the styrene monomer. The dye monomer containing unsaturated double bonds is of a water-soluble monomer structure and/or an oil-soluble monomer structure. The emulsifier is selected from at least one of anionic emulsifier, nonionic emulsifier or polymerizable emulsifier. The anionic emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium stearate or sodium dodecyl diphenyl ether disulfonate. The nonionic emulsifier is polyoxyethylene octylphenol ether and/or polyoxyethylene nonylphenol ether. The polymerizable emulsifier is at least one of 2-acrylamide-2-methylpropanesulfonic acid, sodium allyloxypropanesulfonate, or Japanese SE-10N. The dosage of the emulsifier is 0.3-2% of the mass of the styrene monomer. The emulsifying time is 15-60 min.
(c2) Adding an aqueous solution containing an initiator to the mixed solution emulsified in the step (b2) for dispersion; the initiator is a water-soluble initiator. The water-soluble initiator is water-soluble inorganic salt initiator and/or water-soluble hydrogen peroxide initiator. The water-soluble inorganic salt initiator is at least one of ammonium persulfate, sodium persulfate or potassium persulfate. The water-soluble hydrogen peroxide initiator is hydrogen peroxide and/or tert-butyl hydroperoxide. The dispersion time is 5-30 min.
(d2) Under the protection of nitrogen, dropwise adding the mixed solution dispersed in the step (c2) into water at the temperature of 70-90 ℃;
(e2) adding a proper amount of initiator solution into the mixed solution obtained in the step (d2) after the dropwise addition is finished, and standing at the temperature of 70-90 ℃ for 3-12 hours to obtain the functionalized colored polystyrene microsphere emulsion;
(f2) and (3) cooling the temperature of the functionalized colored polystyrene microsphere emulsion to room temperature, placing the emulsion in a dialysis bag for dialysis, and removing unreacted monomers to obtain the functionalized colored polystyrene microsphere.
The invention provides a preparation method of functional colorful PS microspheres, which is to copolymerize styrene, functional monomers and dye monomers containing unsaturated double bonds to prepare the colorful functional microspheres, and the preparation method comprises the following two specific steps: one method is that functional monomer, non-functional monomer and unsaturated double bond containing dye monomer are mixed in styrene monomer, added into emulsifier containing water solution, stirred at high speed for emulsification for 15-60 min, added with initiator containing water solution, and dispersed at low speed for 5-30 min. And (2) under the protection of nitrogen, dropwise adding the aqueous solution into 70-90 ℃ water at a low speed, after dropwise adding, adding a small amount of initiator solution to improve the monomer conversion rate, and preserving at a constant temperature for 3-12 h to obtain the functionalized colorful PS microsphere emulsion. And the other is to mix functional unsaturated monomers, non-functional monomers and styrene monomers, add the mixture into aqueous solution containing an emulsifier and dye monomers containing unsaturated double bonds, stir and emulsify the mixture at a high speed for 15 to 60 minutes, add solution containing an initiator, disperse the mixture at a low speed for 5 to 30 minutes, drop the aqueous solution into water at a temperature of between 70 and 90 ℃ at a low speed under the protection of nitrogen, add a small amount of solution containing the initiator after the drop, and store the mixture at a constant temperature for 3 to 12 hours to prepare the functional colorful PS microsphere emulsion.
In the polymerization reaction, the functional monomer mainly comprises carboxyl-containing unsaturated monomer, amino-containing unsaturated monomer, hydroxyl-containing unsaturated monomer, chloromethyl-containing unsaturated monomer, sulfonic acid group-containing unsaturated monomer, amide group-containing unsaturated monomer and the like. The dosage of the functional monomer is 0.1-15% of the mass of the styrene.
The unsaturated double bond-containing dye monomer includes a dye monomer containing one or more double bonds. The dye structure in the unsaturated double bond-containing dye monomer may be selected from azo dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, nitro dyes, polymethine dyes, arylmethane dyes, reactive dyes and sulfur dyes. The unsaturated double bond-containing dye monomer may be any one or any several of the following dye structures, but is not limited to the following dye structures. The addition amount of the unsaturated dye monomer is 0.5-20% of the mass of the main monomer styrene. The dye monomer containing unsaturated double bond can be water-soluble monomer or oil-soluble structure.
The non-functional monomer may be selected from unsaturated esters such as methyl acrylate, butyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, butyl methacrylate, hydroxyethyl acrylate and the like. The adding amount of the non-functional monomer is 1 to 40 percent of the mass of the styrene monomer.
The emulsifier may be selected from any one or more of anionic emulsifier, nonionic emulsifier, and polymerizable emulsifier. The anionic emulsifier mainly comprises Sodium Dodecyl Sulfate (SDS), Sodium Dodecyl Benzene Sulfonate (SDBS), sodium stearate, and sodium dodecyl diphenyl ether Disulfonate (DSB); the nonionic emulsifier is mainly selected from polyoxyethylene octylphenol ether (OP-10, OP-7, OP-15, OP-20, etc.) or polyoxyethylene nonylphenol ether. The polymerizable emulsifier is selected from 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), allyloxy hydroxypropyl sodium sulfonate (COPS-1), and Japanese SE-10N. The addition amount of the emulsifier is 0.3-2% of the monomer content.
The initiator may be selected from water-soluble initiators, which mainly include water-soluble inorganic salts and water-soluble alkyl hydroperoxides. The water-soluble inorganic salt may be selected from Ammonium Persulfate (APS), Sodium Persulfate (SPS), potassium persulfate (KPS), etc. The organic water-soluble hydrogen peroxide mainly comprises hydrogen peroxide, tert-butyl hydroperoxide and the like.
Example 1:
preparation of blue PS microspheres
1. Diazotization reaction
(1) Dissolving:
100g of sulfuric acid is put into a 250ml flask, stirring is started, 18.62g (0.07mol) of 2-bromo-4, 6-dinitroaniline is slowly added into 98 percent sulfuric acid, stirring is carried out for 30 minutes, full dissolution is carried out, and the temperature is reduced to 5-10 ℃ in ice-water bath for diazotization.
(2) Preparing nitroso-sulfuric acid:
53g of 98 percent sulfuric acid is added into a 250ml flask, a stirring ice-water bath is started to cool to 5-10 ℃, 5.3g (0.0735mol) of sodium nitrite solid powder is slowly added, the process control temperature is less than 30 ℃, the water bath is heated to 60 ℃ after the addition, the temperature is reacted for 1 hour after the temperature is reached, and the temperature is cooled to 5-10 ℃.
(3) Diazotization reaction:
slowly adding the prepared nitroso-sulfuric acid into the fully dissolved diazo component, controlling the process temperature to be lower than 15 ℃, and keeping the temperature of 10-15 ℃ for reacting for 6-8 hours after the addition.
2. Coupling reaction
(1) Dissolving:
80g of ice water is added into a 250ml flask, stirring is started, 2g of 98% sulfuric acid is slowly added into the ice water, 18.83g (0.0714mol) of N, N-diallyl-2-methoxy-5-acetamidoaniline is added, and stirring is carried out until the solution is fully dissolved for coupling.
(2) Pulping by diazo salt
Adding 300g of ice water into a 1000 beaker, adding 10g of 98% sulfuric acid, adding 0.3g of urea, starting stirring, slowly adding the diazonium salt into the ice water, keeping the temperature less than 0 ℃, and stirring and dispersing for 10 minutes after the addition to prepare for next coupling.
(3) Coupling of
Slowly adding the dissolved coupling component into the dispersed diazo component, finishing the addition within about 60 minutes, controlling the temperature to be 0-5 ℃ in the process, and finishing the addition reaction for 8-10 hours until the end point is reached.
(4) Filtered water washing
And (3) heating the coupling slurry to 60 ℃, keeping the temperature for 1 hour after the coupling slurry is heated to 60 ℃, filtering, washing a filter cake with hot water at 90 ℃ for 5-6 times, washing with 200ml of hot water each time until the pH value of the filtrate is 6.5-7.0, taking out the filter cake, drying in an oven, and preparing the blue double-bond dye shown in the figure 4 for preparing the blue PS microspheres.
3. Preparation of blue PS microspheres
Dissolving 0.2g of blue double-bond dye in 10g of styrene monomer (purified), adding 0.2g of acrylic acid monomer and 2g of methyl methacrylate, and uniformly mixing for later use. Dissolving 0.2g of SDS (sodium dodecyl sulfate) as an emulsifier in 10g of water, mixing the two, stirring at a high speed for 10min, adding 10g of an aqueous solution containing 0.4g of an initiator KPS, stirring at a low speed for 10min, dropwise adding into 25g of water at 80 ℃ in a nitrogen protective atmosphere, after dropwise adding within 30min, adding 0.5g of the aqueous solution of KPS, continuing to react for 5h, taking out the emulsion, cooling to room temperature, filling into a 14000Da dialysis bag, dialyzing to remove unreacted monomers, and preparing the blue PS microspheres.
Example 2:
preparation of yellow PS microspheres
1. Condensation reaction:
150g of DMSO is added into a 250ml flask, stirring is started, 27.7g (0.1mol) of 1, 5-dichloroanthraquinone is added, stirring is carried out until the mixture is completely dissolved, and KHCO 325 (0.25) g and anhydrous Na are added2SO4Adding 31.2g (0.24mol) of hydroxyethyl methacrylate into 8g of the mixture, heating to 140 ℃, and carrying out heat preservation reflux reaction for 10-12 hours. Will react wellThe condensation product of (a) is cooled to 50 ℃. Adding 400g of ice water into a 1000ml beaker, starting stirring, slowly pouring the cooled condensation compound into water, separating out crystals, stirring for 1 hour, filtering, and washing a filter cake with hot water at 90 ℃ for 5-6 times, wherein 200ml of hot water is used each time. And drying the filter cake in a 90 ℃ oven to prepare the yellow unsaturated dye monomer shown in the figure 3.
2. Preparation of yellow PS microspheres
1g of yellow double-bond dye is dissolved in 10g of styrene monomer (purified), 0.2g of acrylic acid monomer and 3g of butyl methacrylate are added and uniformly mixed for later use. Dissolving 0.1g SDS and 0.2g OP-10 in 10g water, mixing the two, stirring at a high speed for 10min, adding 10g water solution containing 0.5g initiator KPS, stirring at a low speed for 10min, dropwise adding into 75g water at 80 ℃ in a nitrogen protection atmosphere, after completing dropwise adding within 30min, adding 0.05g KPS water solution, continuing to react for 5h, taking out the emulsion, cooling to room temperature, filling into a dialysis bag of 14000Da, dialyzing to remove unreacted monomers, and preparing the yellow PS microspheres.
Example 3:
preparation of Red PS microspheres
Preparation of red double-bond dye: adding 120g of DMSO (dimethyl sulfoxide) into a 250ml flask, starting stirring, adding 24.25g (0.1mol) of 1-chloroanthraquinone, stirring until the mixture is completely dissolved, and adding KHCO312.5(0.125mol) g of anhydrous Na2SO44g, adding 15.6g (0.12mol) of hydroxyethyl methacrylate, heating to 120 ℃, and carrying out heat preservation reflux reaction for 10-12 hours. And cooling the condensation product after reaction to 50 ℃. Adding 400g of ice water into a 1000ml beaker, starting stirring, slowly pouring the cooled condensate into water, separating out crystals, stirring for 1 hour, filtering, and washing a filter cake with hot water at 90 ℃ for 5-6 times, wherein 200ml of hot water is used each time. And drying the filter cake in a 90 ℃ oven to prepare the unsaturated red dye monomer shown in the figure 1.
0.6g of red double-bond dye is dissolved in 10g of styrene monomer (purified), 0.2g of acrylamide monomer and 4g of ethyl methacrylate are added, and the mixture is uniformly mixed for later use. Dissolving 0.1g SDS and 0.2g OP-10 in 10g water, mixing the two, stirring at a high speed for 10min, adding 10g water solution containing 0.4g initiator KPS, stirring at a low speed for 10min, dropwise adding into 75g water at 80 ℃ in a nitrogen protection atmosphere, after completing dropwise adding within 30min, adding 0.05g KPS water solution, continuing to react for 5h, taking out the emulsion, cooling to room temperature, filling into a dialysis bag of 14000Da, dialyzing to remove unreacted monomers, and preparing the red PS microspheres.
Example 4:
10g of purified styrene monomer, 0.2g of acrylamide monomer and 4g of ethyl methacrylate are added and mixed uniformly for later use. Dissolving 0.2g of reactive yellow dye (purchased and purified from the market) shown in the figure 7 and 0.1g of OP-10 in 10g of water, mixing the two, stirring at a high speed for 10min, adding 10g of aqueous solution containing 0.2g of initiator KPS, stirring at a low speed for 10min, dropwise adding the mixture into 75g of water at 80 ℃ in a nitrogen protection atmosphere, adding 0.2g of aqueous solution of KPS after completing dropwise adding in 30min, continuing to react for 5h, taking out the emulsion, cooling to room temperature, putting into a dialysis bag of 14000Da for dialysis to remove unreacted monomers, and preparing the yellow PS microspheres.
The properties of the colored PS microspheres prepared in examples 1-4 are shown in Table 1.
Table 1: performance Table of color PS microspheres prepared in examples 1 to 4
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 |
| Particle diameter Dh | 90nm | 80nm | 120nm | 200nm |
| PDI | 0.05 | 0.04 | 0.02 | 0.05 |
| Stability at room temperature (Tian) | >300 | >300 | >300 | >300 |
As can be seen from Table 1, the method can prepare the color PS microspheres with uniform particle size distribution in one step by preparing the functional dye monomers with proper structures, and the PS microspheres prepared by the method have high stability, good color development and excellent application prospect in biological diagnosis.
The invention aims to add a dye monomer containing unsaturated double bonds in the polymerization stage of styrene by a copolymerization method, so that the dye is directly grafted in a polymer chain segment, and the PS microsphere has a functional group, good dispersibility, good color development and extremely high stability.
The colorful PS microspheres prepared by the invention are prepared by a polymerization method, and the chromophoric groups are added into a styrene chain, so that the colorful PS microspheres have colors, and the chromophoric groups are combined with the microspheres through covalent bonds. Uniform particle size distribution, good monodispersity, simple process, high yield and high stability, and does not need a large amount of emulsifier to stabilize the PS microspheres.
Claims (10)
1. A preparation method of functional colorful PS microspheres is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
(a1) taking a proper amount of functional monomer, a proper amount of non-functional monomer, a proper amount of unsaturated double bond-containing dye monomer and a proper amount of styrene monomer, and then mixing;
(b1) adding the mixture obtained in the step (a1) into an aqueous solution containing an emulsifying agent for emulsification;
(c1) adding an aqueous solution containing an initiator to the mixed solution emulsified in the step (b1) for dispersion;
(d1) under the protection of nitrogen, dropwise adding the mixed solution dispersed in the step (c1) into water at the temperature of 70-90 ℃;
(e1) adding a proper amount of initiator solution into the mixed solution obtained in the step (d1) after the dropwise addition is finished, and standing at the temperature of 70-90 ℃ for 3-12 hours to obtain the functionalized colored polystyrene microsphere emulsion;
(f1) and (3) cooling the temperature of the functionalized colored polystyrene microsphere emulsion to room temperature, placing the emulsion in a dialysis bag for dialysis, and removing unreacted monomers to obtain the functionalized colored polystyrene microsphere.
2. A preparation method of functional colorful PS microspheres is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
(a2) taking a proper amount of functional monomer, a proper amount of non-functional monomer and a proper amount of styrene monomer and then mixing;
(b2) adding the mixture obtained in the step (a2) into an aqueous solution containing an emulsifier and a dye monomer containing an unsaturated double bond for emulsification;
(c2) adding an aqueous solution containing an initiator to the mixed solution emulsified in the step (b2) for dispersion;
(d2) under the protection of nitrogen, dropwise adding the mixed solution dispersed in the step (c2) into water at the temperature of 70-90 ℃;
(e2) adding a proper amount of initiator solution into the mixed solution obtained in the step (d2) after the dropwise addition is finished, and standing at the temperature of 70-90 ℃ for 3-12 hours to obtain the functionalized colored polystyrene microsphere emulsion;
(f2) and (3) cooling the temperature of the functionalized colored polystyrene microsphere emulsion to room temperature, placing the emulsion in a dialysis bag for dialysis, and removing unreacted monomers to obtain the functionalized colored polystyrene microsphere.
3. The method for preparing functional colorful PS microspheres according to claim 1 or 2, wherein: the functional monomer is selected from at least one of unsaturated monomers containing carboxyl, amino, hydroxyl, chloromethyl, sulfonic acid or amido; the dosage of the functional monomer is 0.1-15% of the mass of the styrene.
4. The method for preparing functional colorful PS microspheres according to claim 1 or 2, wherein: the non-functional monomer is selected from at least one of methyl acrylate, butyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate or hydroxyethyl acrylate; the dosage of the non-functional monomer is 1 to 40 percent of the mass of the styrene monomer.
5. The method for preparing functional colorful PS microspheres according to claim 1 or 2, wherein: the dye monomer containing unsaturated double bonds is selected from at least one of azo dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, nitro dyes, polymethine dyes, aryl methane dyes, reactive dyes or sulfur dyes; the dosage of the dye monomer containing unsaturated double bonds is 0.5 to 20 percent of the mass of the styrene monomer.
6. The method for preparing functional colorful PS microspheres according to claim 1 or 2, wherein: the dye monomer containing unsaturated double bonds is of a water-soluble monomer structure and/or an oil-soluble monomer structure; the dosage of the emulsifier is 0.3-2% of the mass of the styrene monomer.
7. The method for preparing functional colorful PS microspheres according to claim 1 or 2, wherein: the emulsifier is selected from at least one of anionic emulsifier, nonionic emulsifier or polymerizable emulsifier; the anionic emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium stearate or sodium dodecyl diphenyl ether disulfonate; the non-ionic emulsifier is octyl phenol polyoxyethylene ether and/or nonyl phenol polyoxyethylene ether; the polymerizable emulsifier is at least one of 2-acrylamide-2-methylpropanesulfonic acid, allyloxy hydroxypropyl sodium sulfonate or Japanese SE-10N.
8. The method for preparing functional colorful PS microspheres according to claim 1 or 2, wherein: the initiator is a water-soluble initiator; the water-soluble initiator is a water-soluble inorganic salt initiator and/or a water-soluble hydrogen peroxide initiator; the water-soluble inorganic salt initiator is at least one of ammonium persulfate, sodium persulfate or potassium persulfate; the water-soluble hydrogen peroxide initiator is hydrogen peroxide and/or tert-butyl hydroperoxide.
9. The method for preparing functional colorful PS microspheres according to claim 1 or 2, wherein: the emulsifying time is 15-60 min.
10. The method for preparing functional colorful PS microspheres according to claim 1 or 2, wherein: the dispersion time is 5-30 min.
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