CN114634596A - Preparation method of polyacrylate polymer microspheres - Google Patents
Preparation method of polyacrylate polymer microspheres Download PDFInfo
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- CN114634596A CN114634596A CN202210227479.7A CN202210227479A CN114634596A CN 114634596 A CN114634596 A CN 114634596A CN 202210227479 A CN202210227479 A CN 202210227479A CN 114634596 A CN114634596 A CN 114634596A
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- polymer microspheres
- microspheres
- oil phase
- emulsifier
- swelling
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- 239000004005 microsphere Substances 0.000 title claims abstract description 104
- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012071 phase Substances 0.000 claims description 79
- 230000008961 swelling Effects 0.000 claims description 57
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 39
- 239000012498 ultrapure water Substances 0.000 claims description 39
- 239000000839 emulsion Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- -1 liquid paraffin Chemical compound 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 14
- 230000001804 emulsifying effect Effects 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010511 deprotection reaction Methods 0.000 claims description 8
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 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 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 5
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- 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 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 239000012875 nonionic emulsifier Substances 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 235000011078 sorbitan tristearate Nutrition 0.000 claims description 4
- 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 3
- 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 3
- 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 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- DMAXMXPDVWTIRV-UHFFFAOYSA-N 2-(2-phenylethyl)phenol Chemical compound OC1=CC=CC=C1CCC1=CC=CC=C1 DMAXMXPDVWTIRV-UHFFFAOYSA-N 0.000 claims description 2
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 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 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000001116 FEMA 4028 Substances 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 2
- 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 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 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 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 2
- 229960004853 betadex Drugs 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
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229940071826 hydroxyethyl cellulose Drugs 0.000 claims description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 2
- 229940071676 hydroxypropylcellulose Drugs 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- SRXOCFMDUSFFAK-UHFFFAOYSA-N dimethyl peroxide Chemical group COOC SRXOCFMDUSFFAK-UHFFFAOYSA-N 0.000 claims 1
- 239000003361 porogen Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 238000000967 suction filtration Methods 0.000 description 21
- 239000004793 Polystyrene Substances 0.000 description 18
- 229920002223 polystyrene Polymers 0.000 description 18
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 229920002125 Sokalan® Polymers 0.000 description 7
- 239000004584 polyacrylic acid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004945 emulsification Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 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 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005563 spheronization Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to the technical field of high molecular materials, and provides a preparation method of polyacrylate polymer microspheres.
Description
Technical Field
The invention relates to the technical field of high molecular materials, in particular to a preparation method of polyacrylate polymer microspheres.
Background
Because the side chain of the homo-or cross-linked copolymerized microsphere of poly (hydroxyethyl (meth) acrylate) or poly (hydroxypropyl (meth) acrylate contains hydroxyl, the microsphere not only has stronger hydrophilicity, good biocompatibility and stable mechanical strength, but also is convenient for chemical modification, and has attracted great attention of researchers in the fields of biology, materials, pharmacy and the like in recent years, and becomes one of the research hotspots. The literature reports that the suspension polymerization method is mainly used for synthesizing the microspheres of poly (hydroxyethyl (meth) acrylate or the microspheres of poly (hydroxypropyl) (US4224427), but because the microspheres of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate are miscible with water, in order to reduce the solubility of the monomers of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate in water, a large amount of salt such as sodium chloride or sodium sulfate is usually added to reduce the water solubility of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate by salting-out effect, so as to realize the phase separation of the monomers of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate from water, and the water content in the monomer phase is gradually reduced along with the increase of the salt content in water, so that self-polymerization or copolymerization with a crosslinking agent to form crosslinked microspheres can be realized. In addition, when the monomer conversion rate is about 20% during suspension polymerization, a certain amount of polymer is dissolved in the droplets to swell, the viscosity of the droplets increases, and the two droplets collide during this stage and easily stick together. Suspension polymerization also has limitations such as large droplets, the size and size distribution of oil droplets must be controlled by the stirring rate, which results in non-uniform size distribution of oil droplets, coalescence between oil droplets and break-up of oil droplets during polymerization, resulting in poor sphericity, low spheronization rate, etc.
Disclosure of Invention
Therefore, in view of the above-mentioned shortcomings of the prior art, the present invention is directed to a method for preparing polyacrylate polymer microspheres.
The invention adopts a seed swelling method to prepare polyacrylate polymer microspheres, and the principle is that firstly, dispersion polymerization or soap-free emulsion polymerization and other methods are utilized to prepare polymer microspheres with small uniform particle size, then the polymer microspheres are used as seed microspheres, emulsion of monomers and initiators enters the original seed microspheres through one-step or multi-step swelling, so that the seed spheres are uniformly enlarged, and polymerization is initiated after the swelling balance is reached, so that porous polymer microspheres can be prepared, and the original particle size uniformity of the seed spheres is maintained.
However, hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate is mutually soluble with water, and is difficult to completely swell into the seed microspheres, and difficult to control the swelling and polymerization processes. The invention needs a proper reagent, and the hydroxyl in the side chain of the hydroxyethyl (meth) acrylate or the hydroxypropyl (meth) acrylate is protected by a protecting group, so that the solubility of the hydroxyethyl (meth) acrylate or the hydroxypropyl (meth) acrylate in water is reduced, the hydrophobicity of the hydroxyethyl (meth) acrylate or the hydroxypropyl (meth) acrylate is increased, and the process of controlling and swelling the hydroxyl to the seed microsphere is realized; after the post-polymerization is finished, the hydroxyl protecting groups in the side chains of the poly (hydroxyethyl (meth) acrylate) microspheres or the poly (hydroxypropyl (meth) acrylate) microspheres are removed through deprotection, so that the poly (hydroxyethyl (meth) acrylate) microspheres or the poly (hydroxypropyl methacrylate) microspheres are obtained.
A preparation method of polyacrylate polymer microspheres comprises the following steps:
(1) preparing an oil phase: weighing a proper amount of oil phase monomer M1, pore-forming agent P4 cross-linking agent C2, emulsifier S3 and the like, and emulsifying for 2-15min for later use;
(2) preparation of an aqueous phase: weighing a proper amount of stabilizer, adding deionized water, heating to dissolve, and cooling to room temperature after the stabilizer is completely dissolved to obtain a water phase;
(3) swelling an oil phase: adding the oil-phase emulsion in the step (1) into the seed polymer microspheres, uniformly stirring, and keeping the system temperature at 10-70 ℃ for 30-200 min;
(4) swelling of an initiator: mixing a proper amount of initiator I4, emulsifier S3 and water, emulsifying for 2-15min, and adding into the mixture in the step (3);
(5) polymerization: adding the (2) into the (3), uniformly stirring, heating to 60-90 ℃, and preserving heat for 6-24 hours; after the reaction is finished, cooling to room temperature for cleaning;
(6) cleaning: pumping the polymer microspheres obtained in the step (5), cleaning with ethanol or methanol or acetone, and drying for later use;
(7) deprotection: dispersing the microspheres obtained in the step (6) in a solvent, removing hydroxyl protecting groups by using a deprotection agent, and cleaning to obtain polyacrylate polymer microspheres with hydroxyl on the surfaces.
Wherein the monomer M1 is of the structural formula
Wherein R1 is H, or CH 3; r2 is
Wherein the pore-foaming agent P4 in the step (1) is toluene, or n-hexanol, or heptane, or dodecanol, or cyclohexanol, or liquid paraffin, or isobutanol, or any mixture thereof.
Wherein the cross-linking agent C2 is any one or a mixture of more of divinylbenzene, ethylene glycol dimethacrylate, pentaerythritol triacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate and 1, 4-butanediol dimethacrylate.
Wherein the emulsifier S3 is an ionic emulsifier, a nonionic emulsifier or an ionic and nonionic compound emulsifier: wherein the ionic emulsifier is: alkyl benzene sulfonates, alkyl succinate sulfonates, alkyl diphenyl ether sulfonates, such as SDS, SDBS; wherein the non-ionic emulsifier is alkylphenol polyoxyethylene, or benzyl phenol polyoxyethylene, or phenethyl phenol polyoxyethylene, or fatty alcohol polyoxyethylene, or fatty amine polyoxyethylene, such as Tween 80, Tween 40, Tween 20, Tween 60, span 65, span 85, span 80, Tritro X-401, Tritro X-405, or Tritro X-100.
The initiator I4 is any one or a mixture of more of benzoyl peroxide, diisobutyronitrile, dimethyl azobisisobutyrate and azobisisobutylamidine.
The stabilizer is polyvinyl alcohol, or polyethylene glycol, or polyvinylpyrrolidone, or hydroxymethyl cellulose, or hydroxypropyl cellulose, or hydroxyethyl cellulose, or carboxymethyl cellulose, or beta-cyclodextrin, or beta-methyl cyclodextrin, or hydroxyapatite, or a mixture of any two or more thereof, and the like, and the combination can be selected by the skilled person according to the actual situation.
Wherein the deprotection reagent is a hydrochloric acid/methanol mixture, a hydrochloric acid/dioxane mixture or an acetic acid/tetrahydrofuran mixture.
Wherein the particle size of the microsphere is 5-150 um; the pore diameter of the microspheres is
The invention has the characteristics that:
the poly (methyl) acrylate polymer microsphere is prepared by adopting a seed swelling method, namely swelling an acrylate monomer protected by hydroxyl into the seed microsphere, synthesizing a sphere through free radicals, and then deprotecting a protecting group through a deprotection reagent to obtain the polyacrylate polymer microsphere with a large number of hydroxyl on the surface. The invention can realize the range of 3-200 microns to obtain the polymer microsphere product with uniform particle size, and the CV value is less than 3 percent. In addition, the method has the following advantages: the synthetic method has the advantages of simplicity, easy control, convenience for amplification production and the like, and has potential application value in the fields of bioseparation, biomedical detection and the like.
Drawings
FIG. 1 is an SEM image of polymethacrylate polymer microspheres prepared in example V
Detailed Description
The following detailed description will be provided for the embodiments of the present invention with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques used in the examples are conventional and well known to those skilled in the art, and the reagents and products used are also commercially available. The source, trade name and if necessary the constituents of the reagent used are indicated at the first appearance.
The seed polymer microspheres are polystyrene microspheres, are prepared by a suspension polymerization method or a swelling method, the preparation method is determined according to the particle size of the needed seed polymer microspheres, and when the particle size of the seed polymer microspheres is less than 5 mu m, suspension polymerization is adopted; the swelling method is adopted when the particle size of the seed polymer microsphere is larger than 5 mu m.
Suspension polymerization process
160mL of ethanol and 20mL of ultrapure water are weighed and added into a 500mL round-bottom flask, a reflux condenser tube, mechanical stirring, a nitrogen ventilating duct and a thermometer are arranged on a reaction bottle, 2.0g of dispersant PVP and 1.0g of auxiliary dispersant dodecanol are added, stirring and mixing are carried out uniformly, nitrogen is introduced into the flask, and the system is heated to 60 ℃; weighing 1.0g of dodecanethiol and 0.14g of azobisisobutyronitrile, dissolving in 20g of styrene, adding into the reaction flask, keeping the temperature for reaction for 20 hours to obtain a homogeneous polystyrene seed solution, cleaning, and testing the molecular weight Mn of the seed to be 3284 and the particle size to be 2.4 mu m.
Swelling seed preparation
Weighing 2.5g of polystyrene seed microspheres with the particle size of 4.2 mu m prepared by the method into a 250mL round-bottom flask; weighing 0.11g of azobisisobutyronitrile, 30g of styrene, 0.4g of dodecanethiol, 0.1g of SDS and 20mL of ultrapure water into a 100mL beaker, emulsifying to obtain an emulsion with the particle size of about 10 microns, adding the emulsion into the flask, heating to 60 ℃, keeping the temperature for reaction for 3 hours, adding 0.5g of PEG4000/40g of ultrapure water solution, reacting for 20 hours at 80 ℃ to obtain a homogeneous polystyrene seed solution, and after cleaning, testing the molecular weight Mn of the seed to be 10448 and the particle size to be 26.2 microns.
Example one
A preparation method of polymer microspheres by using polyacrylic acid microspheres comprises the following steps:
mixing a monomer M1, isobutanol, divinylbenzene, SDS and ultrapure water according to a mass ratio of 5: 1: mixing at a ratio of 1:0.02:10, and homogenizing and emulsifying for 5min by a homogenizer to obtain an oil phase emulsion;
wherein the structure of M1 is:
r1 is H; r2 is
Adding an oil phase emulsion into a reaction bottle containing polystyrene microspheres (26.2 mu m), wherein the mass ratio of the oil phase emulsion to the polystyrene microspheres is 40:1, swelling at 40 ℃ for 2h to obtain an oil phase swelling substance, mixing azobisisobutyronitrile, SDS and ultrapure water according to the mass ratio of 0.05:0.05:1, ultrasonically emulsifying for 10min, adding the emulsion into the oil phase swelling substance, adding 1% of the oil phase swelling substance, and continuing to swell for 40 min;
dissolving PVA in ultrapure water to prepare a water phase with the mass fraction of 0.8%, adding the water phase and the oil phase swelling material into the reaction bottle, wherein the mass ratio of the water phase to the oil phase swelling material is 5:1, uniformly stirring and mixing, heating to 75 ℃, carrying out polymerization reaction for 16h, cooling to room temperature after the reaction is finished, carrying out suction filtration on a sand core, and respectively cleaning for 3 times by using ethanol and ultrapure water;
adding the polymer microspheres into a hydrochloric acid/methanol solution, stirring for 8 hours at 40 ℃, after the reaction is finished, carrying out suction filtration on a sand core, and alternately cleaning ethanol and ultrapure water for 3 times; and carrying out suction filtration and drying to obtain the polyacrylate polymer microspheres. The diameter of microsphere is 85.2 um, (C.V ═ 2.1%), pore diameter
Example two
A preparation method of polymer microspheres by using polyacrylic acid microspheres comprises the following steps:
mixing a monomer M1, an isobutanol/toluene mixture (mass ratio of 60:40), ethylene glycol dimethacrylate, SDBS and ultrapure water according to a mass ratio of 5: 0.8: mixing at a ratio of 1.5:0.02:15, and homogenizing and emulsifying for 5min by a homogenizer to obtain oil phase emulsion;
wherein the structure of M1 is:
r1 is CH 3; r2 is
Adding an oil phase emulsion into a reaction bottle containing polystyrene microspheres (26.2 microns), wherein the mass ratio of the oil phase emulsion to the polystyrene microspheres is 20:1, swelling is carried out at 40 ℃ for 2 hours to obtain an oil phase swelling material, mixing benzoyl peroxide, SDBS and ultrapure water according to the mass ratio of 0.1:0.06:2.5, carrying out ultrasonic emulsification for 10 minutes, adding the emulsion into the oil phase swelling material, wherein the addition amount of the emulsion is 1% of that of the oil phase swelling material, and continuing swelling for 40 minutes;
dissolving hydroxymethyl cellulose in ultrapure water to prepare a water phase with the mass fraction of 1.5%, adding the water phase and the oil phase swelling substance into the reaction bottle, uniformly stirring and mixing, heating to 75 ℃, carrying out polymerization reaction for 16h, cooling to room temperature after the reaction is finished, carrying out suction filtration on a sand core, and respectively cleaning for 3 times by using ethanol and ultrapure water;
adding the polymer microspheres into a hydrochloric acid/dioxane solution, stirring for 8 hours at 40 ℃, after the reaction is finished, carrying out suction filtration on a sand core, and alternately cleaning with ethanol and ultrapure water for 3 times; and carrying out suction filtration and drying to obtain the polyacrylate polymer microspheres. Microsphere size 67.6 μm, (C.V ═ 2.5%) and pore size
EXAMPLE III
A preparation method of polymer microspheres by using polyacrylic acid microspheres comprises the following steps:
mixing a monomer M1, isobutanol, divinylbenzene, Tween 40 and ultrapure water according to a mass ratio of 5: 5: 3:0.02:20, and homogenizing and emulsifying for 5min by a homogenizer to obtain oil phase emulsion;
wherein the structure of M1 is:
r1 is CH 3; r2 is
Adding an oil phase emulsion into a reaction bottle containing polystyrene microspheres (26.2 microns), wherein the mass ratio of the oil phase emulsion to the polystyrene microspheres is 64:1, swelling is carried out at 40 ℃ for 2 hours to obtain an oil phase swelling material, mixing azobisisobutyronitrile, tween 40 and ultrapure water according to the mass ratio of 0.15:0.1:5, carrying out ultrasonic emulsification for 10 minutes, adding the emulsion into the oil phase swelling material, wherein the addition amount of the emulsion is 1% of that of the oil phase swelling material, and continuing swelling for 40 minutes;
dissolving hydroxyethyl cellulose in ultrapure water to prepare a water phase with the mass fraction of 1.5%, adding the water phase and the oil phase swelling material into the reaction bottle, uniformly stirring and mixing, heating to 75 ℃, carrying out polymerization reaction for 16h, cooling to room temperature after the reaction is finished, carrying out suction filtration on a sand core, and respectively cleaning for 3 times by using ethanol and ultrapure water;
adding the polymer microspheres into a hydrochloric acid/methanol solution, stirring for 8 hours at 40 ℃, after the reaction is finished, carrying out suction filtration on a sand core, and alternately cleaning ethanol and ultrapure water for 3 times; and carrying out suction filtration and drying to obtain the polyacrylate polymer microspheres. The particle diameter of the microsphere is 101.8 mu m, (C.V ═ 2.5%), and the pore diameter
Example four
A preparation method of polymer microspheres by using polyacrylic acid microspheres comprises the following steps:
mixing a monomer M1, a cyclohexanol/heptane mixture (mass ratio of 70:30), triethylene glycol dimethacrylate, SDBS and ultrapure water according to a mass ratio of 5: 1.5: mixing at a ratio of 1.2:0.05:10, and homogenizing and emulsifying for 5min by a homogenizer to obtain oil phase emulsion;
wherein the structure of M1 is:
r1 is H; r2 is
Adding an oil phase emulsion into a reaction bottle containing polystyrene microspheres (26.2 microns), wherein the mass ratio of the oil phase emulsion to the polystyrene microspheres is 40:1, swelling is carried out at 40 ℃ for 2 hours to obtain an oil phase swelling material, mixing azobisisobutyronitrile, SDS and ultrapure water according to the mass ratio of 0.05:0.08:2, carrying out ultrasonic emulsification for 10 minutes, adding the emulsion into the oil phase swelling material, wherein the addition amount of the emulsion is 1% of that of the oil phase swelling material, and continuing swelling for 40 minutes;
dissolving hydroxyethyl cellulose in ultrapure water to prepare a water phase with the mass fraction of 1.5%, adding the water phase and the oil phase swelling material into the reaction bottle, uniformly stirring and mixing, heating to 75 ℃, carrying out polymerization reaction for 16h, cooling to room temperature after the reaction is finished, carrying out suction filtration on a sand core, and respectively cleaning for 3 times by using ethanol and ultrapure water;
adding the polymer microspheres into a hydrochloric acid/methanol solution, stirring for 8 hours at 40 ℃, after the reaction is finished, carrying out suction filtration on a sand core, and alternately cleaning ethanol and ultrapure water for 3 times; and carrying out suction filtration and drying to obtain the polyacrylate polymer microspheres. Microsphere diameter 86.8 μm, (C.V ═ 2.5%), pore diameter
EXAMPLE five
A preparation method of polymer microspheres by using polyacrylic acid microspheres comprises the following steps:
mixing a monomer M1, an isobutanol/cyclohexanol mixture (mass ratio is 50:50), diethylene glycol dimethacrylate, Tritro X-405 and ultrapure water according to a mass ratio of 5: 3: 2.4:0.05:15, and homogenizing and emulsifying for 5min by a homogenizer to obtain oil phase emulsion;
wherein the structure of M1 is:
r1 is H; r2 is
Adding an oil phase emulsion into a reaction bottle containing polystyrene microspheres (26.2 mu m), wherein the mass ratio of the oil phase emulsion to the polystyrene microspheres is 20:1, swelling is carried out for 2h at 40 ℃ to obtain an oil phase swelling material, benzoyl peroxide, Tritro X-405 and ultrapure water are mixed according to the mass ratio of 0.1:0.12:3, ultrasonic emulsification is carried out for 10min, the emulsion is added into the oil phase swelling material, the addition amount is 1% of the oil phase swelling material, and swelling is continuously carried out for 40 min;
dissolving hydroxypropyl cellulose in ultrapure water to prepare a water phase with the mass fraction of 1.2%, adding the water phase and the oil phase swelling substance into the reaction bottle, uniformly stirring and mixing, heating to 75 ℃, carrying out polymerization reaction for 16h, cooling to room temperature after the reaction is finished, carrying out suction filtration on a sand core, and respectively cleaning for 3 times by using ethanol and ultrapure water;
adding the polymer microspheres into a hydrochloric acid/dioxane solution, stirring for 8 hours at 40 ℃, after the reaction is finished, carrying out suction filtration on a sand core, and alternately cleaning with ethanol and ultrapure water for 3 times; and carrying out suction filtration and drying to obtain the polyacrylate polymer microspheres. The diameter of microsphere is 64.8 um, (C.V ═ 2.5%), pore diameter
EXAMPLE six
A preparation method of polymer microspheres by using polyacrylic acid microspheres comprises the following steps:
mixing a monomer M1, n-dodecanol, tetraethylene glycol dimethacrylate, span 65 and ultrapure water according to a mass ratio of 5: 5: 3.6:0.05:18, and homogenizing and emulsifying for 5min by a homogenizer to obtain oil phase emulsion;
wherein the structure of M1 is:
r1 is CH 3; r2 is
Adding an oil phase emulsion into a reaction bottle containing polystyrene microspheres (4.2 mu m), wherein the mass ratio of the oil phase emulsion to the polystyrene microspheres is 12:1, swelling is carried out at 40 ℃ for 2h to obtain an oil phase swelling material, mixing dimethyl azodiisobutyrate, span 65 and ultrapure water according to the mass ratio of 0.1:0.12:3, carrying out ultrasonic emulsification for 10min, adding the emulsion into the oil phase swelling material, wherein the addition amount of the emulsion is 1% of that of the oil phase swelling material, and continuing swelling for 40 min;
dissolving polyvinylpyrrolidone in ultrapure water to prepare a water phase with the mass fraction of 1.5%, adding the water phase and the oil phase swelling material into the reaction bottle, uniformly stirring and mixing, heating to 75 ℃, carrying out polymerization reaction for 16h, cooling to room temperature after the reaction is finished, carrying out suction filtration on a sand core, and respectively cleaning for 3 times by using ethanol and ultrapure water;
adding the polymer microspheres into a hydrochloric acid/methanol solution, stirring for 8 hours at 40 ℃, after the reaction is finished, carrying out suction filtration on a sand core, and alternately cleaning ethanol and ultrapure water for 3 times; and carrying out suction filtration and drying to obtain the polyacrylate polymer microspheres. The microsphere has a particle size of 5.2 μm, (C.V ═ 2.5%) and a pore size of 1500.
EXAMPLE seven
A preparation method of polymer microspheres by using polyacrylic acid microspheres comprises the following steps:
mixing a monomer M1, an isobutanol/cyclohexanol mixture (mass ratio is 50:50), 1, 3-butanediol dimethacrylate, Tritro X-100 and ultrapure water according to a mass ratio of 5: 3: 3.6:0.05:18, and homogenizing and emulsifying for 5min by a homogenizer to obtain oil phase emulsion;
wherein the structure of M1 is:
r1 is H; r2 is
Adding an oil phase emulsion into a reaction bottle containing polystyrene microspheres (4.2 mu m), wherein the mass ratio of the oil phase emulsion to the polystyrene microspheres is 64:1, swelling is carried out for 2h at 40 ℃ to obtain an oil phase swelling material, mixing azodiisobutyl amidine, Tritro X-100 and ultrapure water according to the mass ratio of 0.16:0.18:2, carrying out ultrasonic emulsification for 10min, adding the emulsion into the oil phase swelling material, wherein the addition amount of the emulsion is 1% of that of the oil phase swelling material, and continuing swelling for 40 min;
dissolving polyethylene glycol in ultrapure water to prepare a water phase with the mass fraction of 1.5%, adding the water phase and the oil phase swelling substance into the reaction bottle, wherein the mass ratio of the water phase to the oil phase swelling substance is 12:1, uniformly stirring and mixing, heating to 75 ℃, carrying out polymerization reaction for 16h, cooling to room temperature after the reaction is finished, carrying out suction filtration on a sand core, and respectively cleaning for 3 times by using ethanol and ultrapure water;
adding the polymer microspheres into acetic acid/tetrahydrofuran solutionStirring for 8h at 40 ℃, after the reaction is finished, carrying out suction filtration on the sand core, and alternately cleaning the ethanol and ultrapure water for 3 times; and carrying out suction filtration and drying to obtain the polyacrylate polymer microspheres. The diameter of microsphere is 8.5 um, (C.V ═ 2.5%), pore diameter
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (9)
1. A preparation method of polyacrylate polymer microspheres is characterized by comprising the following steps: based on the swellable seed polymer microsphere, a specific polymerizable monomer, a pore-forming agent, a cross-linking agent and an initiator are swelled into the seed microsphere, and a hydroxyl protecting group is deprotected by a deprotection agent after polymerization reaction to obtain the polymethacrylate polymer microsphere which is monodisperse in particle size, has a specific pore diameter and contains a large number of hydroxyl groups on the surface.
The specific monomer is M1, and the M1 is a structural formula
Wherein R1 is H, or CH 3; r2 is
2. The method for preparing polyacrylate polymer microspheres according to claim 1, wherein: the method comprises the following steps:
(1) preparing an oil phase: weighing a proper amount of oil phase monomer M1, pore-forming agent P4, cross-linking agent C2, emulsifier S3 and ultrapure water according to the mass ratio of 5:1-5:1-3: 0.02: mixing 10-20, and emulsifying for 2-15min with homogenizer to obtain oil phase;
(2) preparation of an aqueous phase: weighing a proper amount of stabilizer, adding deionized water, heating to dissolve, and cooling to room temperature after the stabilizer is completely dissolved to obtain a water phase;
(3) swelling the oil phase: adding the oil-phase emulsion in the step (1) into the seed polymer microspheres, uniformly stirring, and keeping the system temperature at 10-70 ℃ for 30-200 min;
(4) swelling of an initiator: appropriate amount of initiator I4, emulsifier S3 and water are added according to the mass ratio of 0.05-0.15: mixing at ratio of 0.05-0.1:1-5, emulsifying for 2-15min, and adding into the mixture (3)
(5) Polymerization: adding the (2) into the (3), uniformly stirring, heating to 60-90 ℃, and preserving heat for 6-24 hours; after the reaction is finished, cooling to room temperature for cleaning;
(6) cleaning: pumping the polymer microspheres obtained in the step (5), cleaning with ethanol or methanol or acetone, and drying for later use;
(7) deprotection: dispersing the microspheres obtained in the step (6) in a solvent, removing hydroxyl protecting groups by using a deprotection agent, and cleaning to obtain polyacrylate polymer microspheres with hydroxyl on the surfaces.
3. The method of claim 2, wherein the porogen P4 is toluene, n-hexanol, heptane, dodecanol, cyclohexanol, liquid paraffin, isobutanol, or any mixture thereof.
4. The method for preparing polyacrylate polymer microspheres as claimed in claim 2, wherein the cross-linking agent C2 is any one or more of divinylbenzene, ethylene glycol dimethacrylate, pentaerythritol triacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, and 1, 4-butylene glycol dimethacrylate.
5. The method for preparing polyacrylate polymer microspheres according to claim 2, wherein the emulsifier S3 is an ionic emulsifier, a nonionic emulsifier, or an ionic and nonionic compound emulsifier: the ionic emulsifier comprises the following components: alkyl benzene sulfonates, alkyl succinate sulfonates, alkyl diphenyl ether sulfonates, such as SDS, SDBS; the nonionic emulsifier is alkylphenol polyoxyethylene, or benzyl phenol polyoxyethylene, or phenethyl phenol polyoxyethylene, or fatty alcohol polyoxyethylene, or fatty amine polyoxyethylene, such as Tween 80, Tween 40, Tween 20, Tween 60, span 65, span 85, span 80, Tritro X-401, Tritro X-405, or Tritro X-100.
6. The method for preparing polyacrylate polymer microspheres according to claim 2, wherein the initiator I4 is any one or a mixture of benzoyl peroxide, diisobutyronitrile peroxide, dimethyl azobisisobutyrate and azobisisobutylamidine.
7. The method of claim 2, wherein the stabilizer is polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, beta-cyclodextrin, beta-methyl cyclodextrin, or hydroxyapatite, or a mixture of any two or more thereof.
8. The method of claim 2, wherein the deprotecting reagent is a mixture of hydrochloric acid/methanol, hydrochloric acid/dioxane, or acetic acid/tetrahydrofuran.
9. The method of claim 2, wherein the particle size of the polyacrylate polymer microspheres is 5-150 um; the pore diameter of the microspheres is
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