CN1290604C - Process for preparing organic-inorganic hybrid nano microcapsule using polymer as core - Google Patents
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 53
- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 239000000839 emulsion Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 26
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 17
- 125000005401 siloxanyl group Chemical group 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 238000009396 hybridization Methods 0.000 claims description 14
- 239000006174 pH buffer Substances 0.000 claims description 13
- -1 substituted-phenyl Chemical group 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 8
- NGQVGVZIGBRWCI-UHFFFAOYSA-N C(CCCCCCCCCCC)N(C(CC)(C)C)S(=O)(=O)O Chemical compound C(CCCCCCCCCCC)N(C(CC)(C)C)S(=O)(=O)O NGQVGVZIGBRWCI-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
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- 230000000977 initiatory effect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000012875 nonionic emulsifier Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000012874 anionic emulsifier Substances 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
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- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 2
- 150000004028 organic sulfates Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 18
- 238000007334 copolymerization reaction Methods 0.000 abstract description 8
- 238000006482 condensation reaction Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 3
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 3
- 238000013270 controlled release Methods 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 8
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 238000002296 dynamic light scattering Methods 0.000 description 5
- 125000005395 methacrylic acid group Chemical group 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 235000019394 potassium persulphate Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 4
- 235000019799 monosodium phosphate Nutrition 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003973 paint Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- XURRMOXZJCIZJU-UHFFFAOYSA-N 2-methylprop-2-enoic acid;trimethoxysilicon Chemical compound CC(=C)C(O)=O.CO[Si](OC)OC XURRMOXZJCIZJU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001044369 Amphion Species 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
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- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
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- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
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Abstract
The present invention relates to a method for preparing an organic-inorganic hybridized nanometer microcapsule by using a polymer as a nucleus, which comprises the steps that the emulsion polymerization of vinyl monomers is used for synthesizing polymer seeds, the copolymerization of the vinyl monomers and siloxane monomers with double bonds is generated outside the seeds, and then the hydrolysis-condensation reaction of siloxane bases in the siloxane monomers with the double bonds is used for forming crosslinking shells so as to obtain organic-inorganic hybridized nuclear-shell emulsion particles; then, the moulding plate of the polymer seeds is dissolved by a solvent to obtain a hollow microcapsule. The present has a simple preparing process and can stably obtain a nanometer-grade hybridized microcapsule which has the advantages of controllable permeability and wider application range; moreover, the microcapsule obtained by the present invention can be widely used for occasions of catalyst loading, the controlled release of medicine and other substances, etc.
Description
Technical field
The present invention relates to a kind of novel method for preparing inorganic-organic hybridization nano microcapsule, a kind of specifically is the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer.
With vinyl monomer emulsion polymerisation synthetic polymer seed, outside seed, generate the siloxanyl monomers copolymerization of vinyl monomer and carbon-carbon double bonds again, utilize the hydrolysis-condensation reaction of siloxy group in the siloxanyl monomers of carbon-carbon double bonds, form crosslinked shell, obtain hybrid inorganic-organic type nucleocapsid emulsion particle.With solvent the polymer seeds template is dissolved then, can obtain hollow microcapsules.By the microcapsules that the present invention obtains, can be widely used in that catalyst is loaded with, the occasions such as control release of medicine and other material.
Background technology
Hollow microcapsules all has using value in a lot of fields with its special form.They have been widely used in the various occasions now, and white plastic pigment, uvioresistant additive and feel modifier etc. as paint and water paint are widely used in industries such as coating, paint, papermaking, leather, cosmetics; Another important use is an encapsulation function compound in it is hollow, make macromolecular material with slow-release function, be applied to pharmacy, medical diagnosis, biotechnology field, particularly successfully the material of biologically actives such as cell, DNA is coated wherein now, have breakthrough application and occur.And have nano level microcapsules because of its dimensional effect, and have bigger specific area, also therefore have bigger using value.
Hybrid inorganic-organic materials, the particularly research of inorganic-organic hybridization nano particle are emerging fields of polymer science.Because organic facies and inorganic alternate heterogeneity, the hybrid inorganic-organic particle has been for the colloidal solid that preparation has variform provides wide space, and the method that wherein is used for preparing the nano-hollow microcapsules has following several:
(1) alkoxyl ammonia initator in the grafting of inorganic silicon dioxide particle surface, then in its surperficial initiating activity radical polymerization, the monomer of its polymerization reaction take place contains crosslinkable functional group such as maleic anhydride, the crosslinking agent that adds two amines again makes it crosslinked, last silica core is removed by the method for chemical attack and is obtained hollow microcapsules (Mandal T K, Fleming M S, Walt D R.Chem Mater, 2000,12:3481-3487);
(2) utilization is adsorbed onto on the nano silicon colloidal particle in turn with the electrostatic attraction of the polyelectrolyte of different electric charges, remove template by the hydrofluoric acid corrosion then, obtain microcapsules (Donath E, Sukhorukov G B, Caruso F, et al.Angew Chem Int Ed, 1998,37:2201-2205);
(3) utilization is adsorbed onto the polystyrene moulding surface and the shell of formation multilayer in turn with the polyelectrolyte of different electric charges and the electrostatic attraction of nano grade inorganic particle, remove template by chemical extraction or calcining method then and form hollow microcapsules (Caruso F, Caruso R A, M hwald H.Science, 1998,282:1111-1114);
(4) by in the styrene emulsion polymerization, adding silane coupler, introduce the Si-OH group on the surface of polystyrene seed particle.Add tetraethoxysilane then, thereby sol gel reaction takes place on above-mentioned surface form the layer of silicon dioxide shell, under 600 ℃, calcine again, thereby form hollow microcapsules (Tissot I, Novat C, Lefebvre F, et al.Macromolecules, 2001,34:5737-5739);
(5) utilize the hydrophilic block copolymer of the hydrophobic end of an end to be self-assembled into micella, and on water-wet side, introduce the unit have siloxy group, utilize the hydrolysis-condensation effect of siloxy group again, form microcapsules (Kyoungmoo Koh, Kohji Ohno, Yoshinobu Tsujii, et al.Angew Chem Int Ed, 2003,42:4194-4197).
For method (1) and (2), need by the inorganic template of sour corrosion removal, condition is very harsh, and destroys shell structurre easily; For method (2) and (3), utilize the self assembly layer by layer of polyelectrolyte because the polyelectrolyte particulate easily flocculates, needs to carry out under extremely low concentration, can not stable dispersion in solvent, so its range of application also is restricted; For method (4), need be controlled on the nuclear template and carry out sol gel reaction, the parameter that control is more, and utilizes method for calcinating to remove the form that the nuclear template is destroyed microcapsules easily; For method (5), need to react first synthetic segmented copolymer, and then carry out self assembly with living radical, utilize the hydrolysis-condensation reaction to form inorganic phase again, remove hydrophobic polymer core again, step is more relatively, and has the limited problem of packaging efficiency.
Summary of the invention
The purpose of this invention is to provide a kind of easy be the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer.
In order to achieve the above object, at first carry out the seeded emulsion polymerization of vinyl monomer, and in shell, introduce the siloxanyl monomers and the vinyl monomer copolymerization of carbon-carbon double bonds, the capsule of nano that can obtain having the hybrid inorganic-organic structure then by solvent extraction.The present invention examines as template with the emulsion polymerisation process synthetic organic polymer earlier, select a kind of siloxanyl monomers and vinyl monomer copolymerization of carbon-carbon double bonds then, and generation hydrolysis-condensation reaction in copolymerization, form the inorganic network of Si-O-Si, obtain the hud typed emulsion particle of polymer core-hydridization shell.By solvent-extracted method, the organic polymer template is removed again, obtained having the microcapsules of hybrid structure.The pH value of used emulsifying agent, decentralized medium all has direct influence to the particle diameter of the emulsion of synthesizing stable, control emulsion particle and even microcapsules, and need the siloxanyl monomers of selected carbon-carbon double bonds that the hydrolysis-condensation speed that is complementary with radical copolymerization need be arranged under reaction condition, otherwise can cause the emulsion system instability, maybe can not form problems such as hybrid structure.
The present invention is dissolved in the water emulsifying agent, pH buffer earlier, and under the nitrogen bubble effect, according to the initiator system that is adopted, polymerization temperature is variable between 0～90 ℃.Add vinyl monomer then, initator carries out emulsion polymerisation, when the conversion ratio of vinyl monomer reaches 30%～100%, adds the siloxanyl monomers and/or the vinyl monomer of carbon-carbon double bonds, reaction is to fully.In radical copolymerization, the Si-OR group in the siloxanyl monomers of carbon-carbon double bonds is hydrolyzed-condensation reaction, has formed the Si-O-Si inorganic network, and obtaining with the organic polymer is that nuclear, organic-inorganic hybrid are the hud typed emulsion particle of shell.Can obtain microcapsules by two kinds of methods then: the one, with emulsion centrifugal after, the emulsion particle that precipitates is scattered in the good solvent of polymer core, nuclear is diffused out gradually, and then this dispersion liquid is centrifugal, disperse again, promptly get microcapsules after 2～12 times so repeatedly.The 2nd, the emulsion that polymerization obtains is put into permeable membrane, this permeable membrane can see through the macromolecule of polymer for nuclear, but can not see through emulsion particle, the outer good solvent that adds a large amount of polymer cores of permeable membrane, and regularly replace fresh solvent, like this, solvent constantly diffuses into permeable membrane, emulsion particle, and polymer template also gradually the dissolving diffuse out microcapsules and permeable membrane, be hybrid nano microcapsule after a period of time in the permeable membrane.
The method that the present invention adopts is: the total consumption of monomer is meant total consumption of the siloxanyl monomers of vinyl monomer and carbon-carbon double bonds, and total consumption of monomer and water ratio are 0.01: 1～2: 1;
This method comprises the following steps:
(1) emulsifying agent, pH buffer are dissolved in the water, obtain the pH value and be 5～10 emulsifier solution, the emulsifying agent consumption is 0.1%～5% of the total consumption of monomer, and pH buffer consumption is 0.1%～5% of a water consumption;
(2) fluid temperature that step (1) is obtained is adjusted to 0～90 ℃, under inert gas shielding, add vinyl monomer, chain-transferring agent, and then the adding initator carries out emulsion polymerisation, the vinyl monomer consumption is 30%～98% of the total consumption of monomer, the chain-transferring agent consumption is for adding 0%～10% of vinyl monomer consumption, and initiator amount is 0.05%～1% of the total consumption of monomer, reaction 30～300min;
(3) siloxanyl monomers of adding carbon-carbon double bonds in the emulsion that step (2) obtains, consumption is 2%～34% of the total consumption of monomer; And vinyl monomer, consumption is 0～68% of the total consumption of monomer, after continuing to react 30～300min, and is incubated 60min under 0～90 ℃ of temperature;
(4) get the emulsion that step (3) obtains and go in the centrifuge tube, centrifugal 5～45min under the rotating speed of 5000～40000rpm is scattered in ultra sonic bath in the good solvent of polymer core then, and cyclic washing 2～10 times obtains the hollow structure microcapsules;
Perhaps getting the emulsion that step (3) obtains joins in the permeable membrane, put into the container of the good solvent of the polymer core that 50～100 times of emulsion amounts are housed, container bottom carries out electromagnetic agitation, change good solvent one time every 1～3 day, change the dispersion liquid that is the hollow structure microcapsules behind 2～8 good solvents in the permeable membrane.
Vinyl monomer described in the invention has following several structure to form:
In the structural formula 1, R
1Be H, CH
3Perhaps C
2H
5, R
2Be phenyl, substituted-phenyl, Cl, CN, alkyl ether or OCOCH
3
In the structural formula 2, R
1Be H, CH
3Perhaps C
2H
5, X is C
1-C
8Aliphatic chain or the C of hydroxyl
1-C
8Aliphatic chain;
These vinyl monomers comprise: styrene, (methyl) acrylate, acrylonitrile, vinylacetate, vinyl chloride, vinyl ethers etc.
The siloxanyl monomers of described carbon-carbon double bonds has following several structure to form:
In the structural formula 3, R
1Be H, CH
3Perhaps C
2H
5, R
2Be C
1-C
4Aliphatic chain or phenyl ring;
In the structural formula 4, R
1Be H, CH
3Perhaps C
2H
5, R
2Be C
1-C
4Aliphatic chain or phenyl ring, Y is C
1-C
4Aliphatic chain, phenyl ring or-COOC
nH
2n-, n=1～4.
The siloxanyl monomers of these carbon-carbon double bonds comprises: vinyltrimethoxy silane, VTES, (methyl) acrylic acid trimethoxy silicon propyl ester etc.
Described emulsifying agent is anionic emulsifier organic carboxylate, organic sulfate, organic sulfonate, phosphate, or cationic emulsifier organic quaternary ammonium salt, or amphoteric ion type emulsifying agent dodecyl dimethyl Propylamino sulfonic acid, or nonionic emulsifier polyoxyethylene ester, APEO, polyoxyethylene amine, polyoxyethylate amide are wherein at least a.
Described initator is water soluble starter persulfate or water soluble oxidized reduction initiating system; Reducing substances in the described water soluble oxidized reduction initiating system is a sulphite.
Described pH buffer is 5～10 material for forming the pH value, is that sodium acetate, ammonium acetate, acetate, ammonium chloride, ammoniacal liquor, dihydric phosphate, phosphoric acid hydrogen disalt, borax, diphenate, carbonate, bicarbonate or trishydroxymethylaminomethane are wherein at least a.
Described chain-transferring agent is that butanethiol, lauryl mercaptan, octyl mercaptan, carbon tetrachloride, carbon tetrabromide or alkyl disulfide are wherein a kind of.
The good solvent of described polymer core is an oxolane, and described inert gas is a nitrogen.
The reactivity of considering 2 kinds of monomer radical polymerizations will be quite, and the hydrolysis-condensation speed of the siloxanyl monomers of carbon-carbon double bonds will with the rate-matched of free radical copolymerization, and the solubility of monomer in water of selecting need be as far as possible little, so the siloxanyl monomers of vinyl monomer and carbon-carbon double bonds is preferably styrene and methacrylic acid-3-trimethoxy silicon propyl ester respectively.Total consumption of 2 class monomers and water ratio are 0.01: 1～2: 1.
Consider in the emulsion system if there is a large amount of siloxy groups, its hydrolysis-condensation effect will make the emulsion system instability, the structure of shell copolymer is also uncontrollable, thus the used in amounts of the siloxanyl monomers of carbon-carbon double bonds be controlled at the vinyl monomer consumption 2%～50% between.
Emulsifying agent among the present invention can select for use ionic emulsifying agent (as anionic emulsifier lauryl sodium sulfate, dodecyl sodium sulfate etc., cationic emulsifier softex kw etc., amphion emulsifying agent dodecyl dimethyl Propylamino sulfonic acid etc.) or nonionic emulsifier (as TWEEN series, SPAN series, OP series etc.) or their mixture, consumption is 0.1%～5% of the total consumption of monomer.Initator then can be selected single water soluble starter (as potassium peroxydisulfate, ammonium persulfate etc.) or water soluble oxidized reduction initiating system (as hydrogen peroxide and ferrous sulfate system etc.) for use, and consumption is 0.05%～1% of the total consumption of monomer.
The present invention is in order to improve the stability of emulsion, control siloxy group hydrolysis-condensation speed, need in emulsion, to add pH buffer (as single or mixtures such as sodium dihydrogen phosphate, diammonium hydrogen phosphate, acetates), consumption is 0.1%～5% of a water consumption, and the pH value that is controlled at system in the course of reaction remains on 5～10.
Among the present invention, in order to remove the template of polymer better for nuclear, need reduce the molecular weight of polymer core, thus need chain-transferring agent (as lauryl mercaptan, butanethiol, carbon tetrabromide etc.) to reduce molecular weight, consumption be for the first time the vinyl monomer consumption 0～10%.
Preparation process of the present invention is simple, can stably obtain nano level hybridisation microcapsule, and the penetration property of microcapsules is controlled, and wider range of application is arranged.By the microcapsules that the present invention obtains, can be widely used in that catalyst is loaded with, the occasions such as control release of medicine and other material.
Description of drawings
Fig. 1 penetrates the ratio schematic diagram of permeable membrane for polystyrene core template among embodiment 1 and the embodiment 6.
Among the figure: mark No.1 curve is represented embodiment 1;
Mark No.6 curve is represented embodiment 6.
The specific embodiment
To describe the present invention in detail by specific embodiment below:
Embodiment 1:
Take by weighing emulsifying agent dodecyl dimethyl Propylamino sulfonic acid 0.2g, pH buffer sodium dihydrogen phosphate, each 1.5g of diammonium hydrogen phosphate; Add in the 1000g water, obtain the pH value and be 7 emulsifier solution.With aforesaid liquid adjustment to 80 ℃; under nitrogen protection; add styrene 50g, lauryl mercaptan 4g; and then adding potassium peroxydisulfate 1g initiated polymerization; behind the reaction 60min; in above-mentioned emulsion, add methacrylic acid-3-trimethoxy silicon propyl ester 15g, styrene 50g, after continuing to react 45min, and under this reaction temperature, be incubated 60min.Detecting its number average bead diameter with dynamic light scattering particle diameter instrument is 1.19 μ m.Use transmission electron microscope observation, find the product nucleus shell structure.
Get above-mentioned emulsion and go in the centrifuge tube, centrifugal 5min under the rotating speed of 5000rpm is dispersed in ultra sonic bath in the solvents tetrahydrofurane then, and centrifugal, dispersion cyclic washing can obtain microcapsules 3 times.With its form of transmission electron microscopy observation, be the hollow structure microcapsules.
Embodiment 2:
Take by weighing emulsifying agent dodecyl dimethyl Propylamino sulfonic acid 0.2g, pH buffer sodium dihydrogen phosphate, each 1.5g of diammonium hydrogen phosphate; Add in the 1000g water, obtain the pH value and be 7 emulsifier solution.With aforesaid liquid adjustment to 80 ℃; under nitrogen protection; add styrene 50g; and then adding potassium peroxydisulfate 1g initiated polymerization; behind the reaction 60min; in above-mentioned emulsion, add methacrylic acid-3-trimethoxy silicon propyl ester 15g, styrene 50g, after continuing to react 45min, and under this reaction temperature, be incubated 60min.Detecting its number average bead diameter with dynamic light scattering particle diameter instrument is 1.19 μ m.Use transmission electron microscope observation, find the product nucleus shell structure.
Get above-mentioned emulsion and go in the centrifuge tube, centrifugal 5min under the rotating speed of 5000rpm is dispersed in ultra sonic bath in the solvents tetrahydrofurane then, and centrifugal, dispersion cyclic washing needs 10 times, just obtains microcapsules.With its form of transmission electron microscopy observation, be the hollow structure microcapsules.
Embodiment 3:
The core-shell emulsion of example 1 is joined in the permeable membrane, put into the bottle of solvents tetrahydrofurane that 100 times of emulsion amounts are housed, electromagnetic agitation is carried out in the bottom of bottle, changes solvent every three days one time, changes the dispersion liquid that is microcapsules behind 4 solvents in the permeable membrane.With its form of transmission electron microscopy observation, be the hollow structure microcapsules, have only the nuclear template of few part particle not remove fully.
Embodiment 4:
Take by weighing emulsifying agent dodecyl dimethyl Propylamino sulfonic acid 3g, OP-10 nonionic emulsifier 4g, pH buffer borax 8g, Potassium Hydrogen Phthalate 7g; Add in the 1000g water, obtain the pH value and be 9 emulsifier solution.With aforesaid liquid adjustment to 50 ℃; under nitrogen protection; add methyl methacrylate 100g, butanethiol 0.2g; and then adding ammonium persulfate 0.5g initiated polymerization; behind the reaction 300min; in above-mentioned emulsion, add methacrylic acid-3-trimethoxy silicon propyl ester 55g, methyl methacrylate 15g, after continuing to react 300min, and under this reaction temperature, be incubated 60min.Detecting its number average bead diameter with dynamic light scattering particle diameter instrument is 95nm.Use transmission electron microscope observation, find the product nucleus shell structure, but have part not have the fine particle of nucleocapsid structure.
Get above-mentioned emulsion and go in the centrifuge tube, centrifugal 45min under the rotating speed of 40000rpm is dispersed in ultra sonic bath in the solvents tetrahydrofurane then, and centrifugal, dispersion cyclic washing can obtain microcapsules 4 times.With its form of transmission electron microscopy observation, be the hollow structure microcapsules, and fine particle disappears.
Embodiment 5:
Take by weighing emulsifying agent dodecyl dimethyl Propylamino sulfonic acid 0.5g, pH buffer sodium dihydrogen phosphate, each 1.5g of diammonium hydrogen phosphate; Add in the 1000g water, obtain the pH value and be 7 emulsifier solution.With aforesaid liquid adjustment to 80 ℃; under nitrogen protection; add styrene 100g, lauryl mercaptan 1g; and then adding potassium peroxydisulfate 1g initiated polymerization; behind the reaction 30min; in above-mentioned emulsion, add methacrylic acid-3-trimethoxy silicon propyl ester 10g, after continuing to react 300min, and under this reaction temperature, be incubated 60min.Detecting its number average bead diameter with dynamic light scattering particle diameter instrument is 98nm.Use transmission electron microscope observation, find the product nucleus shell structure.
Get above-mentioned emulsion and go in the centrifuge tube, centrifugal 30min under the rotating speed of 5000rpm is dispersed in ultra sonic bath in the solvents tetrahydrofurane then, and centrifugal, dispersion cyclic washing can obtain microcapsules 5 times.With its form of transmission electron microscopy observation, be the hollow structure microcapsules.
Embodiment 6:
Take by weighing emulsifier sodium lauryl sulfate 3g, pH buffer sodium acetate 40g, acetate 10g; Add in the 1000g water, obtain the pH value and be 5 emulsifier solution.With aforesaid liquid adjustment to 30 ℃; under nitrogen protection; add styrene 30g, carbon tetrabromide 1g; and then add potassium peroxydisulfate 0.07g, sodium hydrogensulfite 0.03g initator initiated polymerization; behind the reaction 240min; in above-mentioned emulsion, add vinyltrimethoxy silane 4g, styrene 70g, after continuing to react 180min, and under this reaction temperature, be incubated 60min.Detecting its number average bead diameter with dynamic light scattering particle diameter instrument is 265nm.Use transmission electron microscope observation, find the product nucleus shell structure.
Get above-mentioned emulsion and go in the centrifuge tube, centrifugal 30min under the rotating speed of 20000rpm is dispersed in ultra sonic bath in the solvents tetrahydrofurane then, and is centrifugal, disperse cyclic washing 6 times, can obtain microcapsules.With its form of transmission electron microscopy observation, be the hollow structure microcapsules.
Join the emulsion in 10g example 1 and the example 6 in the permeable membrane respectively, put into the bottle that 1000 milliliters of solvents tetrahydrofurane are housed, electromagnetic agitation is carried out in the bottom of bottle, follow the tracks of the polystyrene content that is penetrated into outside the permeable membrane with ultraviolet spectrometer, and calculating the ratio of its shared whole polystyrene mouldings, itself and time relation figure are as shown in Figure 1.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention and principal character.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only be thought can not limit the present invention to explanation of the present invention, claims have been pointed out scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, in implication suitable and any change in the scope, all should think to be included in the scope of claims with claims of the present invention.
Claims (8)
1, a kind of is the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer, it is characterized in that the total consumption of monomer is meant total consumption of the siloxanyl monomers of vinyl monomer and carbon-carbon double bonds, and total consumption of monomer and water ratio are 0.01: 1～2: 1; This method comprises the following steps:
(1) emulsifying agent, pH buffer are dissolved in the water, obtain the pH value and be 5～10 emulsifier solution, the emulsifying agent consumption is 0.1%～5% of the total consumption of monomer, and pH buffer consumption is 0.1%～5% of a water consumption;
(2) fluid temperature that step (1) is obtained is adjusted to 0～90 ℃, under inert gas shielding, add vinyl monomer, chain-transferring agent, and then the adding initator carries out emulsion polymerisation, the vinyl monomer consumption is 30%～98% of the total consumption of monomer, the chain-transferring agent consumption is for adding 0%～10% of vinyl monomer consumption, and initiator amount is 0.05%～1% of the total consumption of monomer, reaction 30～300mi n;
(3) siloxanyl monomers of adding carbon-carbon double bonds in the emulsion that step (2) obtains, consumption is 2%～34% of the total consumption of monomer; And vinyl monomer, consumption is 0～68% of the total consumption of monomer, after continuing to react 30～300min, and is incubated 60min under 0～90 ℃ of temperature;
(4) get the emulsion that step (3) obtains and go in the centrifuge tube, centrifugal 5～45min under the rotating speed of 5000～40000rpm is scattered in ultra sonic bath in the good solvent of polymer core then, and cyclic washing 2～10 times obtains the hollow structure microcapsules;
Perhaps getting the emulsion that step (3) obtains joins in the permeable membrane, put into the container of the good solvent of the polymer core that 50～100 times of emulsion amounts are housed, container bottom carries out electromagnetic agitation, change good solvent one time every 1～3 day, change the dispersion liquid that is the hollow structure microcapsules behind 2～8 good solvents in the permeable membrane.
2, according to claim 1 is the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer, it is characterized in that,
Described vinyl monomer structure be following one or more:
In the structural formula 1, R
1Be H, CH
3Perhaps C
2H
5, R
2Be phenyl, substituted-phenyl, Cl, CN, alkyl ether or OCOCH
3
In the structural formula 2, R
1Be H, CH
3Perhaps C
2H
5, X is C
1-C
8Aliphatic chain or the C of hydroxyl
1-C
8Aliphatic chain;
The siloxanyl monomers structure of described carbon-carbon double bonds be following one or more:
In the structural formula 3, R
1Be H, CH
3Perhaps C
2H
5, R
2Be C
1-C
4Aliphatic chain or phenyl ring;
In the structural formula 4, R
1Be H, CH
3Perhaps C
2H
5, R
2Be C
1-C
4Aliphatic chain or phenyl ring, Y is C
1-C
4Aliphatic chain, phenyl ring or-COOC
nH
2n-, n=1～4.
3, according to claim 1 or 2 described with the polymer be nuclear the method for preparing inorganic-organic hybridization nano microcapsule, it is characterized in that, described emulsifying agent is anionic emulsifier organic carboxylate, organic sulfate, organic sulfonate, phosphate, or cationic emulsifier organic quaternary ammonium salt, or amphoteric ion type emulsifying agent dodecyl dimethyl Propylamino sulfonic acid, or nonionic emulsifier polyoxyethylene ester, APEO, polyoxyethylene amine, polyoxyethylate amide are wherein at least a.
4, according to claim 3 is the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer, it is characterized in that described initator is water soluble starter persulfate or water soluble oxidized reduction initiating system; Reducing substances in the described water soluble oxidized reduction initiating system is a sulphite.
5, according to claim 3 is the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer, it is characterized in that, described pH buffer is 5～10 material for forming the pH value, is that sodium acetate, ammonium acetate, acetate, ammonium chloride, ammoniacal liquor, dihydric phosphate, phosphoric acid hydrogen disalt, borax, diphenate, carbonate, bicarbonate or trishydroxymethylaminomethane are wherein at least a.
6, according to claim 3 is the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer, it is characterized in that described chain-transferring agent is that butanethiol, lauryl mercaptan, octyl mercaptan, carbon tetrachloride, carbon tetrabromide or alkyl disulfide are wherein a kind of.
7, according to claim 3 is the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer, it is characterized in that the good solvent of described polymer core is an oxolane.
8, according to claim 3 is the method for preparing inorganic-organic hybridization nano microcapsule of nuclear with the polymer, it is characterized in that described inert gas is a nitrogen.
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| CN100423820C (en) * | 2006-06-23 | 2008-10-08 | 武汉大学 | Hollow inorganic oxide fibre, its synthesis and use |
| CN100512946C (en) * | 2007-06-15 | 2009-07-15 | 浙江大学 | Method of preparing temperature sensitive inorganic-organic hybridization nano microcapsule |
| CN100512945C (en) * | 2007-06-15 | 2009-07-15 | 浙江大学 | Method of preparing temperature sensitive nano microcapsule by using small molecule hydrocarbon as template |
| CN101519472B (en) * | 2009-03-27 | 2012-05-23 | 中山大学 | Composition for preparing capsule wall of hollow micro-capsule and preparation method thereof |
| CN104448088B (en) * | 2014-11-03 | 2017-02-15 | 西北工业大学 | Preparation method of temperature-sensitive anisotropic magnetic microcapsule |
| CN105712645B (en) * | 2015-12-31 | 2018-08-31 | 江苏苏博特新材料股份有限公司 | A kind of additive and preparation method thereof improving Mechanical Properties of Cement-based Materials |
| CN107159069B (en) * | 2017-06-15 | 2020-01-21 | 上海应用技术大学 | Osmanthus essence capsule for leather |
| CN109082120B (en) * | 2018-09-28 | 2021-06-01 | 华南协同创新研究院 | Elastic shell microcapsule phase change material and preparation method and application thereof |
| US20230090216A1 (en) * | 2020-01-29 | 2023-03-23 | Huntsman Advanced Materials Switzerland Gmbh | Functionalized particles |
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