CN103665226A - Method for preparing high molecular microspheres through light-initiated in-situ emulsion polymerization - Google Patents
Method for preparing high molecular microspheres through light-initiated in-situ emulsion polymerization Download PDFInfo
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- CN103665226A CN103665226A CN201210350798.3A CN201210350798A CN103665226A CN 103665226 A CN103665226 A CN 103665226A CN 201210350798 A CN201210350798 A CN 201210350798A CN 103665226 A CN103665226 A CN 103665226A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000839 emulsion Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 23
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- -1 methyl acrylic ester Chemical class 0.000 claims description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 15
- 229910052753 mercury Inorganic materials 0.000 claims description 15
- 230000020169 heat generation Effects 0.000 claims description 13
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 10
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 10
- 229920000053 polysorbate 80 Polymers 0.000 claims description 10
- 239000003223 protective agent Substances 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000012965 benzophenone Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- NSFGOWGWLHAJPC-UHFFFAOYSA-N COCOC.C(C=C)(=O)O Chemical compound COCOC.C(C=C)(=O)O NSFGOWGWLHAJPC-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 235000019198 oils Nutrition 0.000 claims description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229940091853 isobornyl acrylate Drugs 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 claims description 3
- DLUPHJKQEIIYAM-UHFFFAOYSA-N 1-(2-ethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCOC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 DLUPHJKQEIIYAM-UHFFFAOYSA-N 0.000 claims description 3
- RFQOPUYDLCMQCE-UHFFFAOYSA-N 1-(2-hydroxyethyl)-5-nitropyrrole-2-carboxamide Chemical compound NC(=O)C1=CC=C([N+]([O-])=O)N1CCO RFQOPUYDLCMQCE-UHFFFAOYSA-N 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical group S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 3
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- OTRIMLCPYJAPPD-UHFFFAOYSA-N methanol prop-2-enoic acid Chemical compound OC.OC.OC(=O)C=C.OC(=O)C=C OTRIMLCPYJAPPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011806 microball Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 2
- 241000723346 Cinnamomum camphora Species 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 229960000846 camphor Drugs 0.000 claims description 2
- 229930008380 camphor Natural products 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000011232 storage material Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 11
- 238000010008 shearing Methods 0.000 description 11
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- KEEXOYPZMIJIEP-UHFFFAOYSA-N diphenoxyphosphoryl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 KEEXOYPZMIJIEP-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing high molecular microspheres through ultraviolet-initiated in-situ emulsion polymerization of an acrylate or methacrylate monomer, belonging to the technical field of preparation of high molecular microsphere materials. The polymerization method for preparing high molecular microspheres is short in reaction time, and the polymerization process can be completed within 3 minutes; the method is insensitive to conditions such as temperature, air, pH value and the like during the polymerization process and is suitable for large-scale production; the reaction takes water as a medium, uses no volatile organic solvent, and is safe and environment-friendly. The prepared high molecular microspheres have a diameter of 0.2-25 mu m, are regular in shape, controllable in size and narrow in particle size distribution, and have wide application prospects in fields of information storage materials, medicine conveyance, industrial catalysis, precise electronic manufacturing and the like.
Description
Technical field
The invention discloses and a kind ofly by UV-light, cause acrylic or methacrylic esters of gallic acid monomer and carry out the method that in-situ emulsion polymerization is prepared polymer microsphere, belong to polymeric microball material preparing technical field.
background field
Polymer microsphere is as a kind of novel solid support material, and because of its special pattern and heat-resisting character, value has a wide range of applications in fields such as drug conveying, catalysis load, electronics manufacture and information storages.At present by unsaturated monomer, prepare the polymerization process that polymer microsphere generally adopts thermal initiation, this thermal-initiated polymerization long reaction time, energy consumption are high, simultaneously wayward product size.And the polyreaction energy consumption being caused by UV-light is low, the reaction times is extremely short, insensitive to environment, is more suitable for scale operation.
The preparation of polymer microsphere adopts two-phase reaction system more, according to the difference of technique, can be divided into suspension polymerization, letex polymerization, micro-emulsion polymerization, in-situ emulsion polymerization, solution polymerization etc.
In world patent WO 2012052148A1, announced a kind of UV-light and caused the method that polymer microsphere is prepared in letex polymerization, use therein initiator is water-soluble, and products therefrom size is nano level, belongs to traditional emulsion polymerisation process.
The people such as Jinbo Dou have delivered and a kind ofly by UV-light initiating polymerization of microemulsion by means, have been reacted in Colloid Polym Sci (2010) 288:1751-1756, the method of preparing nano level high molecular composite microsphere, has wherein been used indissoluble auxiliary agent to make product size be tending towards homogeneous.
In Chinese patent CN 102010476A, announced a kind of UV-light and caused the method that polymer microsphere is prepared in solution polymerization, the solvent that wherein used is alcohol water mixed system, and the reaction times is longer, and product size, between 100～800nm, also belongs to nano level.
Summary of the invention
The object of the invention is to disclose a kind of method of being prepared micron order polymer microsphere by UV-light initiation in-situ emulsion polymerization.
The technical scheme that realizes the object of the invention is: a kind of light-initiated in-situ emulsion polymerization is prepared the method for micron order polymer microsphere, and acrylate or the methyl acrylic ester monomer that is dissolved with light trigger of take is disperse phase; The aqueous solution that contains emulsifying agent and colloid protective agent of take is external phase; Disperse phase is mixed with external phase, and made emulsion is carried out polymerization and is made microballoon under high intensity ultraviolet lamp; Its method specifically comprises the following steps:
Step 1. is dissolved in oil soluble light trigger in monomer, after stirring, form disperse phase, monomer is selected from and is insoluble in water, has the composition of acrylic ester monomer, methyl acrylic ester monomer or esters of acrylic acid and the methyl acrylic ester of photocuring activity;
Step 2. is soluble in water together with colloid protective agent by emulsifying agent, after stirring, forms external phase;
Step 3. is mixed disperse phase with external phase, disperse to form stable emulsion under the effect of mulser;
Step 4. is placed in gained emulsion under ultraviolet lamp, carries out at ambient temperature polymerization, and UV light application time is less than 3 minutes, after being dried, obtains polymeric microball material.
The preferred 2-phenoxyethyl acrylate of monomer described in step 1,3,3,5-trimethylcyclohexyl acrylate, isobornyl methacrylic ester, ring TriMethylolPropane(TMP) methylal acrylate, benzyl acrylate, iso-bornyl acrylate, 1, one or more in 6-hexanediyl ester, 1,4 butanediol diacrylate, tristane dimethanol diacrylate or dioxane omega-diol diacrylate.
Oil soluble light trigger described in step 1 is selected from bitter almond oil camphor and derivative thereof, benzil derivative, a-hydroxyalkyl benzophenone, one or more in acyl group phosphorous oxides, also can be the composition of benzophenone and tertiary amine or the composition of thioxanthone and tertiary amine, the preferred 2-methyl isophthalic acid of light trigger-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone, dimethoxybenzoin, ethoxybenzoin or 2, 4, 6-trimethylbenzoyl-diphenyl phosphate oxidation, or the composition of the composition of benzophenone and 4-dimethylin ethyl benzoate or isopropyl thioxanthone and 4-dimethylin ethyl benzoate, wherein, the ratio of light trigger and monomer is 0.005 ~ 0.05g/ml, the volume ratio of monomer and water is 1:4 ~ 1:10.
Emulsifying agent described in step 2 is selected from one or more in fatty soap surfactant, sulfosalt surfactant, sulfate surfactant or polyoxyethylene nonionogenic tenside; preferred Tween 80, VH-50, NP-10, OP-10, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or sodium oleate; colloid protective agent is selected from one or more in ether of cellulose, polyvinyl alcohol, block polyether or calcium salt, preferably polyethylene alcohol, F68 type PDA polyethers, Natvosol or calcium phosphate powder.The ratio of emulsifying agent and water is 0.0001 ~ 0.05g/ml; The ratio of colloid protective agent and water is 0.001 ~ 0.05g/ml.
The light wavelength of ultraviolet described in step 4 is between 200 ~ 400nm, and the light source using can be high voltage mercury lamp, Non-polarized lamp, LED lamp or halo lamp, preferably the high voltage mercury lamp of linear heat generation rate between 80 ~ 120W/cm.
In the polymer microsphere making by described method, can contain nano inorganic particle, form organic-inorganic composite microballoons.
Nucleation place in polymerization process of the present invention is mainly small droplets, belongs to in-situ emulsion polymerization method, and products therefrom granularity, between 0.2～25 micron, belongs to micron order.
Compared with prior art, the invention has the beneficial effects as follows: the technique that the present invention prepares polymer microsphere is simple, speed of response fast (reaction times is less than 3 minutes), microballoon size is large (between 0.2～50 micron).
Accompanying drawing explanation
Fig. 1 is the photo of poly-1,6 hexanediol diacrylate microballoon under scanning electronic microscope.
Fig. 2 is the photo of poly-1,4 butanediol diacrylate microballoon under scanning electronic microscope.
Fig. 3 is the photo of the 1,6 hexanediol diacrylate microballoon containing carbon black particle under scanning electronic microscope.
Embodiment
Embodiment 1
First 0.02g Sodium dodecylbenzene sulfonate is dissolved in 70ml deionized water, then adds 0.25g polyvinyl alcohol, be heated to 80 ℃, stirring polyvinyl alcohol after 1 hour dissolves completely, be cooled to room temperature, add Tween 80 emulsifying agents of 0.5ml, after stirring, form external phase; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone 0.15g is dissolved in the 1,6 hexanediol diacrylate of 10ml, after stirring, forms dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom is through centrifugal, dry, obtain poly-1,6 hexanediol diacrylate microballoon, in all particle diameter be 3 microns, productive rate can reach 95%, and its appearance form is shown in the scanning electron picture of accompanying drawing 1.
Embodiment 2
First 0.02g sodium lauryl sulphate is dissolved in 70ml deionized water, then adds 0.25g F68 type PDA polyethet surfactant, be heated to 80 ℃, stirring PDA after 1 hour dissolves completely, be cooled to room temperature, add Tween 80 emulsifying agents of 0.5ml, after stirring, form external phase; Dimethoxybenzoin 0.15g is dissolved in the 1,4 butanediol diacrylate of 10ml, after stirring, forms dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 3 minutes, products therefrom is through centrifugal, dry, obtain poly-1,4 butanediol diacrylate microballoon, in all particle diameter be 3 microns, productive rate can reach 95%, and its appearance form is shown in the scanning electron picture of accompanying drawing 2.
Embodiment 3
First 0.05g sodium oleate is dissolved in 70ml deionized water, then adds 0.25g Natvosol, be heated to 80 ℃, stirring Natvosol after 1 hour dissolves completely, be cooled to room temperature, add the NP-10 emulsifying agent of 0.5ml, after stirring, form external phase; Ethoxybenzoin 0.25g is dissolved in the 1,6 hexanediol diacrylate of 10ml, adds again subsequently 0.30g colour black, ultrasonic dispersion 10 minutes, then after stirring, form dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiate reaction 3 minutes, products therefrom is through centrifugal, dry, obtain containing poly-1 of carbon black particle, 6-hexanediyl ester complex microsphere, in all particle diameter be 6 microns, productive rate can reach 95%, its appearance form is shown in the scanning electron picture of accompanying drawing 3.
Embodiment 4
First 0.02g sodium lauryl sulphate is dissolved in 70ml deionized water, then adds 0.05g calcium phosphate powder, after stirring, add the VH-50 emulsifying agent (being purchased from Rhodia) of 0.5ml, formation external phase stirs; 2,4,6-trimethylbenzoyl-diphenyl phosphate oxidation 0.15g is dissolved in the iso-bornyl acrylate of 10ml, after stirring, forms dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom, through centrifugal, dry, obtains poly-iso-bornyl acrylate microballoon, in all particle diameter be 15 microns.
Embodiment 5
First 0.02g Sodium dodecylbenzene sulfonate is dissolved in 70ml deionized water, then adds 0.25g polyvinyl alcohol, be heated to 80 ℃, stirring polyvinyl alcohol after 1 hour dissolves completely, be cooled to room temperature, add the OP-10 emulsifying agent of 0.5ml, after stirring, form external phase; Benzophenone 0.15g and 4-dimethylin ethyl benzoate 0.15g are dissolved in the mixing solutions of 5ml phenoxyethyl acrylate, 3ml isobornyl methacrylic ester and 2ml tristane dimethanol diacrylate, after stirring, form dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom, through centrifugal, dry, obtains polymer blended microballoon, in all particle diameter be 5 microns.
Embodiment 6
First 0.02g sodium laurylsulfonate is dissolved in 70ml deionized water, then adds 0.25g polyvinyl alcohol, be heated to 80 ℃, stirring polyvinyl alcohol after 1 hour dissolves completely, be cooled to room temperature, add Tween 80 emulsifying agents of 0.5ml, after stirring, form external phase; Isopropyl thioxanthone 0.15g and 4-dimethylin ethyl benzoate 0.15g are dissolved in the ring TriMethylolPropane(TMP) methylal acrylate of 10ml, add 0.05g beeswax, be warming up to 60 ℃, after stirring, form dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom, through centrifugal, dry, obtains poly-ring TriMethylolPropane(TMP) methylal acrylate microballoon, in all particle diameter be 2 microns.
Embodiment 7
First 0.02g sodium laurylsulfonate is dissolved in 70ml deionized water, then adds 0.25g polyvinyl alcohol, be heated to 80 ℃, stirring polyvinyl alcohol after 1 hour dissolves completely, be cooled to room temperature, add Tween 80 emulsifying agents of 0.5ml, after stirring, form external phase; Benzoin dimethylether 0.15g is dissolved in the mix monomer of 7ml benzyl acrylate and 3ml dioxane omega-diol diacrylate, after stirring, forms dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom, through centrifugal, dry, obtains polymer blended polymerizing microballoons, in all particle diameter be 16 microns.
Embodiment 8
First 0.02g Sodium dodecylbenzene sulfonate is dissolved in 70ml deionized water, then adds 0.25g polyvinyl alcohol, be heated to 80 ℃, stirring polyvinyl alcohol after 1 hour dissolves completely, be cooled to room temperature, add Tween 80 emulsifying agents of 0.5ml, after stirring, form external phase; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone 0.15g is dissolved in the 1,6 hexanediol diacrylate of 6ml and the mix monomer of 4ml ring TriMethylolPropane(TMP) methylal acrylate, after stirring, forms dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom, through centrifugal, dry, obtains the acrylate microballoon of blend, in all particle diameter be 7 microns.
Embodiment 9
First 0.02g Sodium dodecylbenzene sulfonate is dissolved in 70ml deionized water, then adds 0.25g polyvinyl alcohol, be heated to 80 ℃, stirring polyvinyl alcohol after 1 hour dissolves completely, be cooled to room temperature, add Tween 80 emulsifying agents of 0.5ml, after stirring, form external phase; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone 0.15g is dissolved in to 3,3 of the 1,6 hexanediol diacrylate of 7ml and 3ml, in the mix monomer of 5-trimethylcyclohexyl acrylate, after stirring, forms dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom, through centrifugal, dry, obtains the acrylate microballoon of blend, in all particle diameter be 12 microns.
Embodiment 10
First 0.02g Sodium dodecylbenzene sulfonate is dissolved in 70ml deionized water, then adds 0.25g polyvinyl alcohol, be heated to 80 ℃, stirring polyvinyl alcohol after 1 hour dissolves completely, be cooled to room temperature, add Tween 80 emulsifying agents of 0.5ml, after stirring, form external phase; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone 0.15g is dissolved in the mix monomer of the dioxane omega-diol diacrylate of 8ml and the benzyl acrylate of 2ml, after stirring, forms dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom, through centrifugal, dry, obtains the acrylate microballoon of blend, in all particle diameter be 11 microns.
Embodiment 11
First 0.02g Sodium dodecylbenzene sulfonate is dissolved in 70ml deionized water, then adds 0.25g polyvinyl alcohol, be heated to 80 ℃, stirring polyvinyl alcohol after 1 hour dissolves completely, be cooled to room temperature, add Tween 80 emulsifying agents of 0.5ml, after stirring, form external phase; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone 0.15g is dissolved in the mix monomer of the isobornyl methacrylic ester of 8ml and the 1,4 butanediol diacrylate of 2ml, after stirring, forms dispersed; By external phase and dispersant, be placed in high-speed shearing emulsion machine and disperse 20 minutes, form stable emulsion; Gained emulsion is placed under the high voltage mercury lamp that linear heat generation rate is 80w/cm, irradiates reaction 2 minutes, products therefrom, through centrifugal, dry, obtains the acrylate microballoon of blend, in all particle diameter be 8 microns.
Claims (10)
1. light-initiated in-situ emulsion polymerization is prepared a method for polymer microsphere, and the acrylate or the methyl acrylic ester monomer that it is characterized in that being dissolved with light trigger are disperse phase; The aqueous solution that contains emulsifying agent and colloid protective agent of take is external phase; Disperse phase is mixed with external phase, and made emulsion is carried out polymerization and is made microballoon under high intensity ultraviolet lamp; Its method specifically comprises the following steps:
Step 1. is dissolved in oil soluble light trigger in monomer, after stirring, form disperse phase, monomer is selected from and is insoluble in water, has the composition of acrylic ester monomer, methyl acrylic ester monomer or esters of acrylic acid and the methyl acrylic ester of photocuring activity;
Step 2. is soluble in water together with colloid protective agent by emulsifying agent, after stirring, forms external phase;
Step 3. is mixed disperse phase with external phase, disperse to form stable emulsion under the effect of mulser;
Step 4. is placed in gained emulsion under ultraviolet lamp, carries out at ambient temperature polymerization, and UV light application time is less than 3 minutes, after being dried, obtains polymeric microball material.
2. light-initiated in-situ emulsion polymerization according to claim 1 is prepared the method for polymer microsphere, it is characterized in that the monomer described in step 1 is preferably from 2-phenoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, isobornyl methacrylic ester, ring TriMethylolPropane(TMP) methylal acrylate, benzyl acrylate, iso-bornyl acrylate, 1, one or more in 6-hexanediyl ester, 1,4 butanediol diacrylate, tristane dimethanol diacrylate or dioxane omega-diol diacrylate.
3. light-initiated in-situ emulsion polymerization according to claim 1 is prepared the method for polymer microsphere; it is characterized in that the oil soluble light trigger described in step 1 is selected from one or more in bitter almond oil camphor and derivative thereof, benzil derivative, a-hydroxyalkyl benzophenone, acyl group phosphorous oxides, or the composition of the composition of benzophenone and tertiary amine or thioxanthone and tertiary amine.
4. according to the light-initiated in-situ emulsion polymerization described in claim 1 or 3, prepare the method for polymer microsphere; it is characterized in that the preferred 2-methyl isophthalic acid of the oil soluble light trigger described in step 1-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone, dimethoxybenzoin, ethoxybenzoin or 2; 4; 6-trimethylbenzoyl-diphenyl phosphate oxidation, or preferred benzophenone and the composition of 4-dimethylin ethyl benzoate or the composition of isopropyl thioxanthone and 4-dimethylin ethyl benzoate.
5. light-initiated in-situ emulsion polymerization according to claim 1 is prepared the method for polymer microsphere, and the ratio that it is characterized in that the light trigger described in step 1 and monomer is 0.005 ~ 0.05g/ml; Described monomer and the volume ratio of water are 1:4 ~ 1:10.
6. light-initiated in-situ emulsion polymerization according to claim 1 is prepared the method for polymer microsphere; it is characterized in that the emulsifying agent described in step 2 is selected from one or more in fatty soap surfactant, sulfosalt surfactant, sulfate surfactant or polyoxyethylene nonionogenic tenside, colloid protective agent is selected from one or more in ether of cellulose, polyvinyl alcohol, block polyether or calcium salt.
7. according to the light-initiated in-situ emulsion polymerization described in claim 1 or 6, prepare the method for polymer microsphere; it is characterized in that the preferred Tween 80 of the emulsifying agent described in step 2, VH-50, NP-10, OP-10, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or sodium oleate, colloid protective agent preferably polyethylene alcohol, F68 type PDA polyethers, Natvosol or calcium phosphate powder.
8. light-initiated in-situ emulsion polymerization according to claim 1 is prepared the method for polymer microsphere, and the ratio that it is characterized in that the emulsifying agent described in step 2 and water is 0.0001 ~ 0.05g/ml; Described colloid protective agent and the ratio of water are 0.001 ~ 0.05g/ml.
9. light-initiated in-situ emulsion polymerization according to claim 1 is prepared the method for polymer microsphere, it is characterized in that the ultraviolet light wavelength described in step 4 is between 200 ~ 400nm, the light source using can be high voltage mercury lamp, Non-polarized lamp, LED lamp or halo lamp.
10. according to the light-initiated in-situ emulsion polymerization described in claim 1 or 9, prepare the method for polymer microsphere, it is characterized in that the high voltage mercury lamp of the preferred linear heat generation rate of the light source described in step 4 between 80 ~ 120W/cm.
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