CN114524896B - 一种表面褶皱微球的制备方法 - Google Patents
一种表面褶皱微球的制备方法 Download PDFInfo
- Publication number
- CN114524896B CN114524896B CN202111566184.4A CN202111566184A CN114524896B CN 114524896 B CN114524896 B CN 114524896B CN 202111566184 A CN202111566184 A CN 202111566184A CN 114524896 B CN114524896 B CN 114524896B
- Authority
- CN
- China
- Prior art keywords
- preparation
- sodium
- total mass
- parts
- transferring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 238000003756 stirring Methods 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 238000005303 weighing Methods 0.000 claims description 30
- 239000012071 phase Substances 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 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 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229920000858 Cyclodextrin Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 5
- CURNJKLCYZZBNJ-UHFFFAOYSA-M sodium;4-nitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1 CURNJKLCYZZBNJ-UHFFFAOYSA-M 0.000 claims description 5
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000001116 FEMA 4028 Substances 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 4
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 4
- 229960004853 betadex Drugs 0.000 claims description 4
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 230000037303 wrinkles Effects 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000012875 nonionic emulsifier Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000005992 Sodium p-nitrophenolate Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229940071826 hydroxyethyl cellulose Drugs 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 229940071676 hydroxypropylcellulose Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims 1
- XVCYJJSHYKJNHB-UHFFFAOYSA-L calcium;octadecyl phosphate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCOP([O-])([O-])=O XVCYJJSHYKJNHB-UHFFFAOYSA-L 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 4
- 238000000053 physical method Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 9
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 5
- PQKMPXAXUORKSU-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].C(CCCCCCCCCCCCCCCCC)[Ca+].C(CCCCCCCCCCCCCCCCC)[Ca+].C(CCCCCCCCCCCCCCCCC)[Ca+] Chemical compound P(=O)([O-])([O-])[O-].C(CCCCCCCCCCCCCCCCC)[Ca+].C(CCCCCCCCCCCCCCCCC)[Ca+].C(CCCCCCCCCCCCCCCCC)[Ca+] PQKMPXAXUORKSU-UHFFFAOYSA-K 0.000 description 4
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- -1 glycerol triester Chemical class 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 description 1
- DMAXMXPDVWTIRV-UHFFFAOYSA-N 2-(2-phenylethyl)phenol Chemical compound OC1=CC=CC=C1CCC1=CC=CC=C1 DMAXMXPDVWTIRV-UHFFFAOYSA-N 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 description 1
- OHOAUIQLNRLXJP-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(C(=O)OCCCCCCOC(C(=C)C)=O)=C.CC(C(=O)OCCCCOC(C(=C)C)=O)=C OHOAUIQLNRLXJP-UHFFFAOYSA-N 0.000 description 1
- SPNDNMBDJADMRL-UHFFFAOYSA-N C=CC.C=CC.C1=CC=CC=C1 Chemical compound C=CC.C=CC.C1=CC=CC=C1 SPNDNMBDJADMRL-UHFFFAOYSA-N 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000000925 erythroid effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/166—Magnesium halide, e.g. magnesium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- 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
本发明涉及高分子材料技术领域，提供一种表面褶皱微球的制备方法，包括以下步骤：(1)纳米颗粒的制备；(2)稳定相的制备；(3)聚合等过程。此法利用纳米颗粒在单体及交联剂聚合过程中，通过物理性方法占据微球乳液表面的区域，形成凹凸褶皱，具有合成方法简单，容易控制、便于放大生产等优点。
Description
技术领域
本发明涉及高分子材料技术领域，尤其涉及一种表面褶皱微球的制备方法。
背景技术
具有不同组成和形态的聚合物微球近年来受到越来越多的科学家的关注，且可以根据其自身材料的不同性质制备出不同尺寸、不同结构、不同形态的微球：如无孔、多孔微球，表面光滑微球，表面褶皱微球，红细胞状微球，洋葱型微球，哑铃型微球等。其中表面褶皱微球在调节生物材料和生物体系之间的相互作用方面起着十分重要的作用，如：表面褶皱结构的微球因其表面粗糙与具有特定的形状、表面的细胞及微生物在结构上有相似之处，所以会对细胞的吸附、增长等方面具有特殊的益处。但，目前很少有相关专利报道。
本发明专利，选用悬浮聚合方法，采用含有纳米颗粒的稳定剂作为稳定相，合成出一种表面褶皱的聚合物微球。
发明内容
针对特殊使用要求，本专利发明一种表面不光滑，含有褶皱形状的聚合物微球。
本发明提供一种表面褶皱微球的制备方法。
为达到上述目的，本发明是通过以下技术方案实现的：
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备：
称取0.5-20份的物质W1于容器中混合均匀，加入一定量的浓度为20-40％的氢氧化钠溶液，剧烈搅拌混合均匀；将此转移至研磨器中，研磨30min；
(2)稳定相的制备：
将0.5-5份的稳定剂P1加入到20份的去离子水，升温至50～80℃，待稳定剂完全溶解后，即得到含稳定剂P1的水相溶液；
将(1)中得到的的纳米颗粒加入到含有P1的稳定剂水相中；搅拌均匀，即得到稳定相。
(3)聚合及清洗
称取2-100份的可聚合单体M1，2-100份的交联剂M2，0.5-5份的引发剂I1于烧杯中，混合均匀，备用；称取5-20份盐S1，0.01-0.1份的阻聚剂Z1于烧杯中，加入300份的去离子水，溶解完全；加入0.5-5份的乳化剂S2，分散均匀，转移至反应瓶中；将(2)中得到的稳定性转移至反应瓶中；搅拌均匀；将含有M1、M2、I1的油相转移至反应瓶中，50-1000rpm搅拌转速下，升温至65-90℃，保温反应8-18h；反应结束后，降至室温，抽滤掉反应液，依次用含有0.1-5％稀盐酸水溶液清洗，去离子水清洗，即可得到表面含有褶皱的聚合物微球。
进一步的改进是：所述物质W1为硬脂酸钙或十八烷基磷酸钙与磷酸氢钙、或氯化镁、或碳酸钙、或碳酸氢钙或其任意组合。
进一步的改进是：所述稳定剂P1是聚乙烯醇、聚乙二醇、聚乙烯吡咯烷酮、羟甲基纤维素、羟丙基纤维素、羟乙基纤维素、羧甲基纤维素、β-环糊精、β-甲基环糊精中的任意一种或两种以上的混合物。
进一步的改进是：所述可聚合单体M1为苯乙烯、或甲基丙烯酸缩水甘油酯、或丙烯酸缩水甘油酯。
进一步的改进是：所述交联剂M2为二乙烯基苯、二丙烯苯、双甲基丙烯酸乙二醇酯、三乙烯酸甘油酯、三羟甲基丙基三甲基丙烯酸、季戊四醇三丙烯酸酯、二乙二醇二甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯、三缩四乙二醇二甲基丙烯酸酯、1，3-丁二醇二甲基丙烯酸酯、1，4-丁二醇二甲基丙烯酸酯六亚甲基双甲基丙烯酰胺、二乙烯基苯基甲烷、三甲基丙烯酸甘油酯、亚甲基丙烯酰胺中的任意一种或两种以上的混合物。
进一步的改进是：所述乳化剂S1为离子型乳化剂、非离子型乳化剂中的任意一种或二者以任意比混合而成。所述离子型乳化剂为烷基苯磺酸盐、烷基磺酸盐、烷基丁二酸酯磺酸盐或烷基联苯基醚磺酸盐。所述非离子型乳化剂为烷基酚聚氧乙烯醚、苄基酚聚氧乙烯醚、苯乙基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚或脂肪胺聚氧乙烯醚。
进一步的改进是：所述的阻聚剂Z1为亚硝酸钠、对苯二酚、对硝基苯酚钠中的一种或两种以上的混合物。
进一步的改进是：所述的盐S2为氯化钠、硫酸钠、硝酸钠、磷酸钠、磷酸氢二钠、磷酸二氢钠中的任意一种或两种以上的混合物。
进一步的改进是：所述引发剂I1为过氧化苯甲酰、偶氮二异丁腈、偶氮二异丁酸二甲酯、偶氮二异丁基脒中的任意一种或两种以上的混合物。
本发明的特点：
通过采用前述技术方案，本发明的有益效果是：
本发明制备一种表面褶皱的微球，首先合成纳米颗粒，其次将纳米颗粒与稳定剂混合，形成复合型稳定相，即稳定剂的水溶液包裹此纳米颗粒；油相在复合型稳定相中，在搅拌情况下，形成水包油乳液；纳米颗粒均匀分散于稳定剂水溶液中，因此纳米颗粒表面含有烷基，增加了其表面的疏水、亲油性，可与水包油乳液接触，占据乳液表面的位置，单体及交联剂经过聚合后，在乳液表面形成凹凸褶皱。
此法具有如下优点：利用纳米颗粒在单体及交联剂聚合过程中，通过物理性方法占据微球乳液表面的区域，形成凹凸褶皱，合成方法简单，容易控制、便于放大生产等优点，在生物医药及体外诊断方面具有潜在的应用价值。
附图说明
实施例2中的得到的表面褶皱微球扫描电子显微镜图。
具体实施方式
以下将结合具体实施例来详细说明本发明的实施方式，借此对本发明如何应用技术手段来解决技术问题，并达成技术效果的实现过程能充分理解并据以实施。
若未特别指明，实施例中所采用的技术手段为本领域技术人员所熟知的常规手段，所采用的试剂和产品也均为可商业获得的。所用试剂的来源、商品名以及有必要列出其组成成分者，均在首次出现时标明。
实施例一
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取0.45g硬脂酸钙，7.5g 20％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入0.2g的聚乙烯醇，升温至80℃，搅拌至聚乙烯醇完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取20g苯乙烯，2.5g的二乙烯基苯，0.19g的过氧化苯甲酰于烧杯中，搅拌至过氧化苯甲酰完全溶解；称取10g的氯化钠、0.05的亚硝酸钠于烧杯中，加入100g的去离子水，加入0.37g的SDS，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌220rpm下，体系升温至80℃，保温反应8h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为40.8μm的表面褶皱微球。
实施例二
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取6g十八烷基磷酸钙，60g 30％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入0.83g的羟丙基纤维素，升温至80℃，搅拌至羟丙基纤维素完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取10g甲基丙烯酸缩水甘油酯，10g的二乙二醇二甲基丙烯酸酯，0.2g的过氧化苯甲酰于烧杯中，搅拌至过氧化苯甲酰完全溶解；称取1g的氯化钠、0.008的对苯二酚于烧杯中，加入280g的去离子水，加入0.9g的SDBS，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌320rpm下，体系升温至80℃，保温反应8h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为2.5μm的表面褶皱微球。
实施例三
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取10.5g硬脂酸钙，2.1g的碳酸氢钙及105g的35％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入0.75g的β-环糊精，升温至80℃，搅拌至β-环糊精完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取10g甲基丙烯酸缩水甘油酯，25g的二乙二醇二甲基丙烯酸酯，0.18g的偶氮二异丁腈于烧杯中，搅拌至偶氮二异丁腈完全溶解；称取3.5g的氯化钠、0.002的对苯二酚于烧杯中，加入300g的去离子水，加入0.35g的曲拉通X-104，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌180rpm下，体系升温至70℃，保温反应12h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为28.8μm的表面褶皱微球。
实施例四
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取12.6g硬脂酸钙，2.1g碳酸氢钙及138.6g的35％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入0.315g的聚乙烯醇，升温至80℃，搅拌至聚乙烯醇完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取10g苯乙烯，32g的二乙烯基苯，1.23g的偶氮二异丁基脒于烧杯中，搅拌至偶氮二异丁基脒完全溶解；称取10.5g的氯化钠、0.28g的磷酸二氢钠、0.036g的对硝基苯酚钠于烧杯中，加入600g的去离子水，加入0.21g的SDS，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌180rpm下，体系升温至70℃，保温反应12h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为64.1μm的表面褶皱微球。
实施例五
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取4.5g硬脂酸钙，1.1g碳酸钙及81.6g的30％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入0.75g的聚乙烯吡咯烷酮，升温至80℃，搅拌至聚乙烯吡咯烷酮完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取10g丙烯酸缩水甘油酯，5g的季戊四醇三丙烯酸酯，0.08g的偶氮二异丁腈于烧杯中，搅拌至偶氮二异丁腈完全溶解；称取3.3g的硫酸钠、0.03g的对硝基苯酚钠于烧杯中，加入100g的去离子水，加入0.15g的曲拉通X-104，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌160rpm下，体系升温至70℃，保温反应12h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为58.4μm的表面褶皱微球。
实施例六
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取3.0g硬脂酸钙，54g的30％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入0.3g的聚乙烯醇，升温至80℃，搅拌至聚乙烯醇完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取10g丙烯酸缩水甘油酯，10g的二乙烯基苯，0.1g的偶氮二异丁腈于烧杯中，搅拌至偶氮二异丁腈完全溶解；称取2.3g的氯化钠、0.02g的亚硝酸钠于烧杯中，加入100g的去离子水，加入0.2g的曲拉通X-104，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌160rpm下，体系升温至70℃，保温反应12h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为62.4μm的表面褶皱微球。
实施例七
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取3.78g硬脂酸钙，68g的25％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入0.9g的聚乙烯基吡咯烷酮，升温至80℃，搅拌至聚乙烯基吡咯烷酮完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取10g苯乙烯，8g的二乙烯基苯，0.09g的偶氮二异丁基脒于烧杯中，搅拌至偶氮二异丁基脒完全溶解；称取5.4g的硝酸钠、0.03g的亚硝酸钠于烧杯中，加入120g的去离子水，加入0.18g的曲拉通X-104，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌80rpm下，体系升温至65℃，保温反应18h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为84.7μm的表面褶皱微球。
实施例八
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取4.68g十八烷基磷酸钙，84.3g的25％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入0.78g的聚乙烯醇，升温至80℃，搅拌至聚乙烯醇完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取10g甲基丙烯酸缩水甘油酯，16g的二缩三乙二醇二甲基丙烯酸酯，0.13g的过氧化苯甲酰于烧杯中，搅拌至过氧化苯甲酰完全溶解；称取2.08g的氯化钠、0.036g的亚硝酸钠于烧杯中，加入180g的去离子水，加入0.18g的SDBS，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌380rpm下，体系升温至75℃，保温反应12h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为24.4μm的表面褶皱微球。
实施例九
一种表面褶皱微球的制备方法，包括以下步骤：
(1)纳米颗粒的制备
称取40.g十八烷基磷酸钙，700g的25％的氢氧化钠溶液，剧烈搅拌后，转移至研磨器中，研磨30min；
(2)稳定相的制备：
称取20g的去离子水于反应瓶中，继续加入48g的聚乙烯醇，升温至80℃，搅拌至聚乙烯醇完全溶解；将上述(1)中的纳米颗粒加上上述反应瓶中，继续搅拌至完全分散均匀，备用。
(3)聚合
称取10g丙烯酸缩水甘油酯，90g的二缩三乙二醇二甲基丙烯酸酯，0.5g的过氧化苯甲酰于烧杯中，搅拌至过氧化苯甲酰完全溶解；称取6.0g的氯化钠、0.24g的亚硝酸钠于烧杯中，加入920g的去离子水，加入58g的曲拉通X-104，搅拌至完全溶解，转移至反应瓶中；将上述的稳定相转移至反应瓶中；搅拌均匀；继续将上述的油性单体转移至反应瓶中，在搅拌460rpm下，体系升温至75℃，保温反应12h；反应结束后，降至室温，滤布过滤，分别用10倍量的12％的盐酸水溶液，去离子水清洗，即得平均粒径为8.3μm的表面褶皱微球。
Claims (4)
1.一种表面褶皱微球的制备方法，其特征在于：包括以下步骤：
(1)纳米颗粒的制备：
称取0.5-20份的物质W1于容器中混合均匀，加入一定量的浓度为20-40％的氢氧化钠溶液，剧烈搅拌混合均匀；将此转移至研磨器中，研磨30min；
(2)稳定相的制备：
将0.5-5份的稳定剂P1加入到20份的去离子水，升温至50～80℃，待稳定剂完全溶解后，即得到含稳定剂P1的水相溶液；
将(1)中得到的纳米颗粒加入到含有P1的稳定剂水相中；搅拌均匀，即得到稳定相；
(3)聚合及清洗
称取2-100份的可聚合单体M1，2-100份的交联剂M2，0.5-5份的引发剂I1于烧杯中，混合均匀，备用；称取5-20份盐S1，0.01-0.1份的阻聚剂Z1于烧杯中，加入300份的去离子水，溶解完全；加入0.5-5份的乳化剂S2，分散均匀，转移至反应瓶中；将(2)中得到的稳定相转移至上述反应瓶中；搅拌均匀；将含有M1、M2、I1的油相转移至反应瓶中，50-1000rpm搅拌转速下，升温至65-90℃，保温反应8-18h；反应结束后，降至室温，抽滤掉反应液，依次用含有0.1-5％稀盐酸水溶液清洗，去离子水清洗，即可得到表面含有褶皱的聚合物微球；
其中步骤(1)中W1为硬脂酸钙或十八烷基磷酸钙，任选含有磷酸氢钙、或氯化镁、或碳酸钙、或碳酸氢钙的一种或多种；
其中步骤(3)中可聚合单体M1为苯乙烯、或甲基丙烯酸缩水甘油酯、或丙烯酸缩水甘油酯。
2.根据权利要求1所述的制备方法，其特征在于：所述步骤(2)中稳定剂P1是聚乙烯醇、聚乙二醇、聚乙烯吡咯烷酮、羟甲基纤维素、羟丙基纤维素、羟乙基纤维素、羧甲基纤维素、β-环糊精、β-甲基环糊精中的任意一种或两种以上的混合物；所述步骤(3)中交联剂M2为二乙烯基苯、二甲基丙烯酸乙二醇酯、季戊四醇三丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、1，3-丁二醇二甲基丙烯酸酯、1，4-丁二醇二甲基丙烯酸酯中的任意一种或两种以上的混合物；所述步骤(3)中乳化剂S2为离子型乳化剂、非离子型乳化剂中的任意一种或二者以任意比混合而成；所述步骤(3)中盐S1为氯化钠、硫酸钠、硝酸钠、磷酸钠、磷酸氢二钠、磷酸二氢钠中的任意一种或两种以上的混合物；所述步骤(3)中引发剂I1为过氧化苯甲酰、偶氮二异丁腈、偶氮二异丁酸二甲酯、偶氮二异丁基脒中的任意一种或两种以上的混合物；所述步骤(3)中阻聚剂Z1为亚硝酸钠、对苯二酚、对硝基苯酚钠中的一种或两种以上的混合物。
3.根据权利要求1所述的制备方法，其特征在于：所述的步骤(1)中，所述的W1与氢氧化钠质量比为1∶10-30；所述的步骤(2)中P1与M1及M2的总质量的比为0.5-5∶100；所述的步骤(3)中的M1与M2的质量比为2-90∶10；所述步骤(3)中的引发剂I1与M1及M2的总质量的比为0.5-5∶100；所述步骤(3)中的盐S1与M1及M2的总质量的比为5-30∶100；所述步骤(3)中的阻聚剂Z1与M1及M2的总质量的比为0.01-0.3∶100；所述步骤(3)中的乳化剂S2与M1及M2的总质量的比为0.5-5∶100；所述的M1及M2的总质量与水的比为5-25∶100。
4.根据权利要求1所述的一种表面褶皱微球的制备方法，其特征在于得到的微球的粒径为：0.5μm～100μm间。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111566184.4A CN114524896B (zh) | 2021-12-20 | 2021-12-20 | 一种表面褶皱微球的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111566184.4A CN114524896B (zh) | 2021-12-20 | 2021-12-20 | 一种表面褶皱微球的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114524896A CN114524896A (zh) | 2022-05-24 |
| CN114524896B true CN114524896B (zh) | 2024-05-24 |
Family
ID=81618429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111566184.4A Active CN114524896B (zh) | 2021-12-20 | 2021-12-20 | 一种表面褶皱微球的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114524896B (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009029953A (ja) * | 2007-07-27 | 2009-02-12 | Jsp Corp | ビニル系樹脂粒子の製造方法 |
| JP2010149087A (ja) * | 2008-12-26 | 2010-07-08 | Kao Corp | ナノ粒子の製造方法 |
| CN103992421A (zh) * | 2014-05-16 | 2014-08-20 | 三棵树涂料股份有限公司 | Pickering丙烯酸聚合物乳液的制备方法 |
| CN106749930A (zh) * | 2016-12-09 | 2017-05-31 | 江南大学 | 一种具有表面褶皱的非球形微粒的制备方法 |
| CN108117619A (zh) * | 2016-11-26 | 2018-06-05 | 天津城建大学 | 一种PMMA/Mg(OH)2复合材料的制备方法 |
-
2021
- 2021-12-20 CN CN202111566184.4A patent/CN114524896B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009029953A (ja) * | 2007-07-27 | 2009-02-12 | Jsp Corp | ビニル系樹脂粒子の製造方法 |
| JP2010149087A (ja) * | 2008-12-26 | 2010-07-08 | Kao Corp | ナノ粒子の製造方法 |
| CN103992421A (zh) * | 2014-05-16 | 2014-08-20 | 三棵树涂料股份有限公司 | Pickering丙烯酸聚合物乳液的制备方法 |
| CN108117619A (zh) * | 2016-11-26 | 2018-06-05 | 天津城建大学 | 一种PMMA/Mg(OH)2复合材料的制备方法 |
| CN106749930A (zh) * | 2016-12-09 | 2017-05-31 | 江南大学 | 一种具有表面褶皱的非球形微粒的制备方法 |
Non-Patent Citations (4)
| Title |
|---|
| Suspension Polymerization of Styrene with Pickering Emulsifiers;D. Wolters, et al.;Macromol. Mater. Eng.(第2期);第94–106页 * |
| Xiaokun Ma,et al..The Influence of the Different Modifying Agents on the Synthesis of Poly(methylmethacrylate)-Calcium Carbonate Nanocomposites via Soapless Emulsion Polymerization.Journal of Applied Polymer Science.2008,第108卷第1421–1425页. * |
| 基于纳米氢氧化镁稳定的Pickering 乳液悬浮聚合制备盔甲结构 聚苯乙烯@氢氧化镁复合微球;朱佩等;高等学校化学学报;第41卷(第3期);第556- 564页 * |
| 颗粒乳化剂的研究及应用;易成林等;化学进展;第23卷(第1期);第65-79页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114524896A (zh) | 2022-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4849484A (en) | Polymeric particles, their manufacture and uses | |
| CN1038756C (zh) | 粒度可均匀控制在1到50微米范围的颗粒的制造方法 | |
| CN103374143A (zh) | 一种超大孔聚合物微球及其制备方法 | |
| US5856409A (en) | Method of making hydrophobic copolymers hydrophilic | |
| CN107973873B (zh) | 一种超疏水高抗压苯乙烯-二乙烯基苯共聚物催化剂载体的制备方法 | |
| CN114524896B (zh) | 一种表面褶皱微球的制备方法 | |
| US5652292A (en) | Suspension polymerized aqueous absorbent polymer particles | |
| CN1045610C (zh) | 液相色谱用粒度单分散大孔交联聚苯乙烯微球的制备 | |
| US4898913A (en) | Method of making hydrophobic copolymers hydrophilic | |
| Yu et al. | Diazoresin modified monodisperse porous poly (glycidylmethacrylate-co-divinylbenzene) microspheres as the stationary phase for high performance liquid chromatography | |
| CN1137531A (zh) | 聚合物的水乳浊液 | |
| JPH04266913A (ja) | 微細な水膨潤性多糖−グラフトポリマーの製造方法 | |
| US20240207817A1 (en) | Agarose-cellulose nanocomposite porous gel microsphere, preparation method, and application | |
| CA2384824A1 (en) | Single stage seed polymerisation for the production of large polymer particles with a narrow size distribution | |
| US5169904A (en) | Method of making hydrophobic copolymers hydrophilic | |
| KR20230049566A (ko) | 다공성 입자 및 그 제조방법 | |
| JP5207815B2 (ja) | セルロース含有樹脂組成物及び成形体 | |
| US5041475A (en) | Method for production of inclusion water for hardening gypsum, method for production of shaped article of gypsum, and shaped article of gypsum | |
| CN1036068C (zh) | 表面多孔的交联共聚物微球的制备方法 | |
| Shevchenko et al. | Influence of the structure of a surface layer of methyl methacrylate-based cationic particles on adsorption of biomolecules | |
| CN115873170B (zh) | 两亲性聚磷腈稳定含氟乳液制备含氟多孔材料和纳米微球 | |
| JP2890481B2 (ja) | 親水性架橋共重合体粒子の製造方法 | |
| JPH01172412A (ja) | ボリマー粒子体の製造方法 | |
| Liao et al. | Effect of swelling process on monodispersity of porous polystyrene-divinylbenzene microspheres prepared by two-step swelling polymerization methods | |
| CN102558440A (zh) | 新颖的聚合物珠组合物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |