CN101085423A - Method of preparing temperature sensitive inorganic-organic hybridization nano microcapsule - Google Patents
Method of preparing temperature sensitive inorganic-organic hybridization nano microcapsule Download PDFInfo
- Publication number
- CN101085423A CN101085423A CN 200710069317 CN200710069317A CN101085423A CN 101085423 A CN101085423 A CN 101085423A CN 200710069317 CN200710069317 CN 200710069317 CN 200710069317 A CN200710069317 A CN 200710069317A CN 101085423 A CN101085423 A CN 101085423A
- Authority
- CN
- China
- Prior art keywords
- monomer
- temperature sensitive
- consumption
- structural formula
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 36
- 239000003094 microcapsule Substances 0.000 title claims description 26
- 238000009396 hybridization Methods 0.000 title claims description 19
- 239000000178 monomer Substances 0.000 claims abstract description 127
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 3
- -1 small molecule hydrocarbon Chemical class 0.000 claims description 38
- 239000003995 emulsifying agent Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 125000005401 siloxanyl group Chemical group 0.000 claims description 24
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000006174 pH buffer Substances 0.000 claims description 13
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen 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
- 239000000243 solution Substances 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000012875 nonionic emulsifier Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 230000009467 reduction Effects 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
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000012874 anionic emulsifier Substances 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 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
- 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
- 239000004971 Cross linker Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 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
- 150000001412 amines Chemical class 0.000 claims description 2
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000004028 organic sulfates Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 239000007858 starting material Substances 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
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002775 capsule Substances 0.000 abstract description 27
- 150000003254 radicals Chemical class 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 238000006482 condensation reaction Methods 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 4
- 239000011147 inorganic material Substances 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000006210 lotion Substances 0.000 abstract 1
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 40
- 239000011324 bead Substances 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002088 nanocapsule Substances 0.000 description 13
- 239000011257 shell material Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000002296 dynamic light scattering Methods 0.000 description 12
- 238000004627 transmission electron microscopy Methods 0.000 description 12
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 9
- 235000019394 potassium persulphate Nutrition 0.000 description 9
- 238000009833 condensation Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 6
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000007334 copolymerization reaction Methods 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
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 4
- 235000019799 monosodium phosphate Nutrition 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 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 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011557 critical solution Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- ZJDNTSGQAOAXNR-UHFFFAOYSA-N n-ethenyl-2-methylpropanamide Chemical compound CC(C)C(=O)NC=C ZJDNTSGQAOAXNR-UHFFFAOYSA-N 0.000 description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000010900 secondary nucleation Methods 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001044369 Amphion Species 0.000 description 1
- PUWFWMBEPHFKRT-UHFFFAOYSA-N C(=O)(C=C)NC(=O)C=C.C(C(O)C(O)C(=O)O)(=O)O Chemical compound C(=O)(C=C)NC(=O)C=C.C(C(O)C(O)C(=O)O)(=O)O PUWFWMBEPHFKRT-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 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
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229960005181 morphine Drugs 0.000 description 1
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Natural products O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to the making of a nanometer capsule. It uses organic small mole hydrocarbon drop as the template, using fine lotion polymer, polymerizing temperature sensitive monomer, vinyl monomer, oxosilane with carbon-to-carbon double bond that participate with the polymerization with the free radical, Si-O-R going through hydrolysis and condensation reaction, through dropping with extra monomers of the above to form into temperature sensitive nanometer capsule. It has features of the high polymer material and inorganic material, being able to control loading and release feature through adjusting the environment temperature, with potential application in nanometer reaction field.
Description
Technical field
The present invention relates to a kind of method for preparing capsule of nano, be specifically related to a kind of method for preparing temperature sensitive inorganic-organic hybridization nano microcapsule.
Background technology
Temperature sensing polymer is to environmental change, and variations in temperature especially can intelligent and reversibly response.Therefore, (Heskins M, Guillet J E.J Macromol Sci Chem, 1969 after finding the responsive to temperature characteristic of linear poly N-isopropyl acrylamide in 1969,2:1441-1455), the research for this base polymer is one of the focus in polymer science field always.Temperature sensing polymer can show the phase transition phenomenon near minimum critical solution temperature (LCST), generally believe that reason that the phase transition phenomenon appears in temperature sensing polymer is because the hydrogen bond that forms between the hydrophilic radical on the temperature sensing polymer macromolecular chain and the water is destroyed when being higher than minimum critical phase transition temperature, make the dehydration of temperature sensing polymer molecule, thereby make complete dissolved state (the become random coil structure) dehydration of temperature sensing polymer when being lower than minimum critical solution temperature be shrunk to graininess.
The characteristics combination of scholar with the environment-responsive characteristics and the inorganic material of temperature sensing polymer arranged at present, prepare structurized temperature sensitive inorganic-organic hybridization material.On hydrophobic adjusted silicon nuclear, coat one deck poly-N-isopropyl acrylamide by emulsion polymerization, obtain core-shell material (Karg M, the Pastoriza-Santos I of temperature sensitive property, Liz-Marzan L M, et al.ChemPhysChem, 2006,7:2298-2301).Be purpose to obtain hud typed temperature sensitive inorganic-organic nano particle equally, people such as Liu are the combined polymerization in tetrahydrofuran solvent with N-N-isopropylacrylamide and 3-methacrylic acid trimethoxy silicon propyl ester earlier then, copolymer is connected to nm-class core-and-shell particles (the Liu J that obtains temperature sensitive inorganic-organic hybridization on the nano silicon particles by graft reaction again, Pelton R, Hrymak A N.J Colloid Interf Sci, 2000,227:408-411).But the method that up to the present, prepares temperature sensitive inorganic-organic hybridization nano microcapsule does not also have report.
In order to prepare capsule of nano, patent and document reported than multi-method, as sacrificing template, big molecule self-assembly method, directly polymerization and self-assembly method layer by layer.They also have been widely used in various occasions, as the industries such as coating, paint, papermaking, leather, cosmetics such as white plastic pigment, uvioresistant additive and feel modifier as paint and water paint; Another important use is an encapsulation function compound therein, makes the macromolecular material with slow-release function, is applied to occasions such as pharmacy, medical diagnosis, biotechnology.Especially now successfully the material of biologically actives such as cell, DNA is coated wherein, have breakthrough application and occur.
The method for preparing capsule of nano, having of having proposed is following several:
(1) 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 siloxanes, utilize the hydrolysis-condensation effect of siloxanes again, form capsule of nano (the Kyougmoo Koh of hydridization, Kohji Ohno, Yoshinobu Tsujii, et al.Angew Chem Int Ed, 2003,42:4194-4197).
(2) utilize polystyrene to be template, outside template, utilize the method for self assembly layer by layer, connect multi-layer polyelectrolyte and inorganic nano-particle, remove template by chemical extraction or calcining method then, obtain Nano capsule (Caruso F, Caruso R A, Mohwald H.Sci ence, 1998,282:1111-1114); As the expansion of self-assembling method layer by layer, it is template with silicon nuclear that report is arranged recently, utilize intermolecular Van der Waals force will be complete with and with the self assembly of polymethyl methacrylate layers layer outside template, obtain polymethyl methacrylate microcapsules (Kida T with chemical method after with the silicon karyolysis then, Mouri M, Akashi M.AngewChem Int Ed, 2006,45:7534-7536).
(3) utilize emulsion polymerisation, outside polymer template, form the shell that one deck is formed by styrene and double bond containing siloxanyl monomers copolymerization, wherein in emulsion polymerization process siloxy group also hydrolysis-condensation become inorganic network, get rid of the nuclear template then, obtain Nano capsule (Tissot I, Novat C, Lefebvre F, et al.Macromolecules, 2001,34:5737-5739).
(4) make its volumetric expansion by the toluene swell polystyrene nanoparticle, make its volume contraction with the granules of polystyrene after the cooled with liquid nitrogen swelling again, because toluene changes into solid-state from liquid state, volume contraction and in the inner hole that forms of granules of polystyrene, making the toluene volatilization below 0 ℃, obtain pipe/polyhenylethylene nano capsule (Im S H, Jeong U at last, Xia Y.Nature Mater.2005,4:671-675).
(5) utilize the New Emulsion polymerization, original position encapsulation small molecule hydrocarbon, synthetic microcapsules (US4,973,670,1990; McDonald C J, Bouck K J, Chaput A B, et al.Macromolecules, 2000,33:1593-1605); With the hexadecane be template mini-emulsion polymerization styrene one-step method prepare Nano capsule (Tiarks, F, Landfester K, Antonietti M.Langmuir, 2001,17:908-918); With the normal octane is template, styrene and the combined polymerization of 3-methacryl trimethoxy silicon propyl ester miniemulsion prepare the inorganic-organic hybridization nano capsule (Ni K F, Shan G R, Weng Z X.Macromolecules, 2006,39:2529-2535).
For method (1), need block polymer synthesis with active free radical polymerization elder generation, carry out self assembly then, utilize the hydrolysis-condensation reaction to form inorganic phase, remove hydrophobic polymer core again, step is more relatively, and has the limited problem of packaging efficiency; For method (2), utilize the self assembly layer by layer of polyelectrolyte, also need to remove the step of template, and 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 (3), though synthetic easier, relatively very difficult for the removal of polymer template, and the polymer of removing is also cumbersome with separating of microcapsules; For method (4), preparation condition is harsh relatively; For method (5), preparation process is the easiest, only needs single step reaction just can obtain microcapsules, and the removal of small molecule hydrocarbon class template is convenient, is the good method of preparation microcapsules.The present invention will be on the basis of the method, and the capsule of nano of preparation temperature sensitive inorganic-organic hybridization does not have the report that utilizes the synthetic temperature sensitive inorganic-organic capsule of nano of this method at present as yet.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of method for preparing novel temperature sensitive inorganic-organic hybridization nano microcapsule is provided, this preparation process is simple, can stably obtain the capsule of nanoscale temperature sensitive inorganic-organic hybridization, this capsule possesses the common feature of macromolecular material and inorganic material simultaneously, and can produce intelligence and reversible response to the variation of environment temperature, have wide practical use.
For achieving the above object, the inventor finds through further investigation, adopt the mini-emulsion polymerization method, polymerization is preceding with temperature sensitive monomer, vinyl monomer, the siloxanyl monomers and the small molecule hydrocarbon of carbon-carbon double bonds are mixed together, be dispersed into miniemulsion, with the small molecule hydrocarbon is template, directly polymerization obtains the capsule of nano of hybrid inorganic-organic, the siloxanyl monomers of carbon-carbon double bonds also is hydrolyzed-condensation reaction except that participating in radical copolymerization simultaneously in the polymerization process, and the inorganic network structure of Si-O-Si that hydrogen bond action between the silicon hydroxyl that hydrolysis forms or condensation form can both play the effect of stablizing shell; By continuing to drip the mixed aqueous solution of adding temperature sensitive monomer and water-soluble cross-linked monomer, on capsule of nano, form the shell of the crosslinked temperature sensing polymer of one deck then, finally obtain the capsule of nano of temperature sensitive inorganic-organic hybridization.In the process of synthesis of nano microcapsules, by control prescription and polymerizing condition, the shell that contains the temperature sensitive monomer unit is coated on the small molecule hydrocarbon drop interface, form capsule of nano.This method need not to remove the step of template, greatly simplifies the preparation process of microcapsules.
The present invention is dissolved in the water emulsifying agent, pH buffer earlier, siloxanyl monomers, small molecule hydrocarbon and the co-stabilizer of temperature sensitive monomer, vinyl monomer, carbon-carbon double bonds are mixed, join in the above-mentioned aqueous solution, above-mentioned mixed liquor is disperseed, obtain stable miniemulsion with ultrasonic wave; Above-mentioned miniemulsion is heated to 40～80 ℃, adds the initator initiated polymerization.Initator is decomposed into elementary free radical in water, according to the difference of initiator type, and elementary free radical positively chargeable, negative electrical charge or big molecule hydrophilic chain.Temperature sensitive monomer is a hydrophilic monomer, so has the more oligomer free radical that is formed by temperature sensitive monomer in the polymerization system.Polymerization temperature is generally greater than LCST, and therefore temperature sensitive property oligomer free radical reaches after the critical chain length and can separate out and dripped by monomer liquid and to catch from water.Although temperature sensing polymer shows hydrophobicity more than LCST, but the polymer that its hydrophobicity still forms less than the siloxanyl monomers of small molecule hydrocarbon and vinyl monomer and carbon-carbon double bonds, so the temperature sensing polymer free radical tends to be distributed on the drop outer surface.Thermodynamics motive force, electrostatic interaction or (with) under the acting in conjunction of steric effect, the oligomer free radical of aqueous phase and dead polymers can be adsorbed by drop, the drop surface becomes main polymerization place, monomer is constantly replenished from drop inside.Because polymer is mutually incompatible with monomer droplet, carry out with reaction, the new polymer that forms is separated out on the drop surface rapidly.Interfacial tension between polymer phase and the water is less than the interfacial tension of small molecule hydrocarbon and water, form polymer although still have a small amount of free radical to enter the inner initiated polymerization of drop, but this part polymer can be coated on the surface of small molecule hydrocarbon drop from the drop diffusion inside to the drop surface under the effect of thermodynamics motive force.The siloxanyl monomers of carbon-carbon double bonds is when participating in radical copolymerization, hydrolysis will take place in siloxanes in its molecule simultaneously, generate the silicon hydroxyl, and then form the inorganic network structure that constitutes by the Si-O-Si key by condensation reaction, finally obtain the stable inorganic-organic hybridization nano microcapsule that shell contains the temperature sensitive monomer unit.It should be noted that degree, even but under the very low situation of condensation level, the hydrogen bond action of silicon hydroxyl also can make shell stable according to the different controllable silicon oxygen alkane hydrolysis-condensations of prescription.In addition, the silicon hydroxyl that forms after the hydrolysis of siloxanes can increase the hydrophily of polymer, from the thermodynamics angle, will help the formation of Nano capsule.Therefore, the adding of the siloxanyl monomers of carbon-carbon double bonds not only can make material have the performance of inorganic material, makes the Nano capsule of formation have stable shell structurre, but also helps the formation of Nano capsule.
After the system conversion ratio reaches 90%, add initator, and begin to drip the mixed aqueous solution of adding temperature sensitive monomer and water-soluble cross-linked monomer.The homopolymers of the temperature sensitive monomer that forms in the former miniemulsion system and copolymer can improve the compatibility between temperature sensing polymer and Nano capsule shell, so the oligomer that the second stage temperature sensitive monomer forms tends to be adsorbed by Nano capsule and coat in the Nano capsule outside; Polymer generation graft reaction on part temperature sensitive monomer and the Nano capsule, above-mentioned two processes finally all can obtain temperature sensitive nano microcapsule.
The method that the present invention adopts is: the monomer that participates in reaction comprises the siloxanyl monomers of at least a temperature sensitive monomer, at least a vinyl monomer and at least a carbon-carbon double bonds, the total consumption of monomer is meant the gross mass of the siloxanyl monomers of temperature sensitive monomer, vinyl monomer and carbon-carbon double bonds, but does not comprise and add temperature sensitive monomer and water-soluble cross-linked monomer;
This method comprises the following steps:
(1) emulsifying agent, pH buffer are dissolved in the water, obtain the pH value and be 5～10 the emulsifying agent and the mixed solution of buffer, the ratio of total consumption of monomer and water is 0.0025: 1～0.5: 1, the emulsifying agent consumption is 3%～20% of the total consumption of monomer, and pH value buffer consumption is 0.1%～5% of a water consumption;
(2) siloxanyl monomers of temperature sensitive monomer with small molecule hydrocarbon, co-stabilizer, vinyl monomer, carbon-carbon double bonds mixed, join in the mixed solution that step (1) obtains, above-mentioned mixed liquor is disperseed, obtain stable miniemulsion with ultrasonic wave;
Wherein, the small molecule hydrocarbon consumption is 40%～360% of the total consumption of monomer, the consumption of co-stabilizer is 3%～25% of a small molecule hydrocarbon consumption, the temperature sensitive monomer consumption is 2.5%～20% of the total consumption of monomer in this step, the vinyl monomer consumption is 50%～80% of the total consumption of monomer, and the siloxanyl monomers consumption of carbon-carbon double bonds is 7.5%～40% of the total consumption of monomer;
(3) adjustment to 40～80 of the emulsion that step (2) is obtained ℃, under inert gas shielding, add initator and carry out mini-emulsion polymerization, initiator amount is 3%～25% of the total consumption of monomer, react after 120～600 minutes, can obtain the hybrid nano microcapsule that the shell polymer contains the temperature sensitive monomer unit;
(4) after the system conversion ratio reaches more than 90%, add initator and drip the mixed aqueous solution add temperature sensitive monomer and water-soluble cross-linked monomer, the dropping time was controlled in 30～240 minutes, after adding monomer solution and dripping, was incubated 3～20 hours;
Wherein, the consumption of adding temperature sensitive monomer is 2～15 times of the middle temperature sensitive monomer of step (2), water-soluble cross-linked monomer consumption is to add 10%～50% of temperature sensitive monomer, the ratio of adding total consumption of monomer and water is 0.01: 1～0.5: 1, add the total consumption of monomer and be meant the gross mass of adding temperature sensitive monomer, water-soluble cross-linked monomer, adding initiator amount is to add 3%～20% of the total consumption of monomer;
Described temperature sensitive monomer is at least a in caprolactam or the following structural formula with adding temperature sensitive monomer:
R in the structural formula (1)
1, R
2Be H, C
2～C
5Aliphatic chain, and R
1, R
2Can not be H simultaneously, R
3Be H, CH
3
R in the structural formula (2)
1Be C
1～C
5Aliphatic chain, R
2, R
3Be H, CH
3
Described vinyl monomer structure is at least a in the following structural formula:
In the structural formula (3), R
1Be H, CH
3Perhaps C
2H
5, R
2Be phenyl, substituted-phenyl, Cl, CN, alkyl ether or OCOCH
3
In the structural formula (4), R
1Be H, CH
3Perhaps C
2H
5, X is C
1～C
12Aliphatic chain or the C of hydroxyl
1～C
12Aliphatic chain;
The structure of the siloxanyl monomers of described carbon-carbon double bonds is at least a in the following structural formula:
In the structural formula (5), R
1Be H, CH
3, C
2H
5, R
2Be C
1～C
4Aliphatic chain or phenyl ring;
In the structural formula (6), R
1Be H, CH
3, 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 structure of described water-soluble cross-linker is at least a in the following structural formula:
Described water-soluble cross-linked monomer is at least a in structural formula (7), formula (8), the formula (9).
Among the present invention, described small molecule hydrocarbon is at least a in the alkane of cycloalkane, aromatic hydrocarbon or 5～14 carbon.
Among the present invention, described co-stabilizer is C
12～C
18Aliphatic hydrocarbon, C
12～C
18Fatty alcohol, structural formula (10) or structural formula (11) at least a:
In the structural formula (10), R
1Be H, CH
3, C
2H
5, X is C
12～C
18Aliphatic chain;
In the structural formula (11), R
1Be H, CH
3, CF
3, m=0～17, R
fBe C
nH
jF
2n+1-jFluoro fat (n=1～18, j=0～34), and m+n=12～18.
Among the present invention, described emulsifying agent is organic carboxylate, organic sulfate, organic sulfonate, organic phosphate anionic emulsifier, the organic quaternary ammonium salt cationic emulsifier, the amphoteric ion type emulsifying agent, at least a in polyoxyethylene ester, APEO or the polyoxyethylene amine nonionic emulsifier.
Among the present invention, described water soluble starter is at least a in hydrogen peroxide, persulfate, cationic diazo salt, polyethylene glycol azo macromole evocating agent or the water soluble oxidized reduction initiating system; The reducing substances that is added in the described water soluble oxidized reduction initiating system is at least a in primary amine, secondary amine, tertiary amine alcohol, sulphite, thiosulfate or the ferrous salt.
Among the present invention, described pH buffer is 5～10 material for forming the pH value, at least a in sodium acetate, ammonium acetate, acetate, ammonium chloride, ammoniacal liquor, dihydric phosphate, phosphoric acid hydrogen disalt, borax, diphenate, carbonate, bicarbonate or the trishydroxymethylaminomethane.
Considering that the monomer hydrophily is excessive causes secondary nucleation easily, is difficult to obtain capsule of nano, so consumption that must the control temperature sensitive monomer in the prescription of mini-emulsion polymerization, reduces the quantity of secondary nucleation.Temperature sensitive monomer consumption in the system should be controlled in 2.5%～20% scope of the total consumption of monomer.
The shell of considering capsule of nano must possess enough mechanical strengths to keep certain form, and therefore the consumption of the siloxanyl monomers of the carbon-carbon double bonds that adds must be controlled at 7.5%～40%.The amount of siloxanyl monomers that adds carbon-carbon double bonds is very few, and silicon hydroxyl that shell forms and Si-O-Si key are very few and can't obtain stable shell; When the amount of the siloxanyl monomers of adding carbon-carbon double bonds was too much, the compliance of segment was too high, causes subsiding of microcapsules easily.
Consider the stability of system, the hydrolysis-condensation speed of the siloxanyl monomers of carbon-carbon double bonds will be complementary with free radical copolymerization speed, the therefore preferential 3-methacrylic acid trimethoxy silicon propyl ester of selecting.
Total consumption of monomer and water ratio are 0.0025: 1～0.5: 1.
Small molecule hydrocarbon is at least a in alkane (as pentane, octane, dodecane etc.), cycloalkane (as cyclohexane) or the aromatic hydrocarbon (benzene, toluene etc.) of 5～14 carbon among the present invention, and consumption is 40%～360% of the total consumption of monomer.
Co-stabilizer is at least a in the alcohol (as hexadecanol etc.), structural formula (10) (as lauryl methacrylate etc.), structural formula (11) (as methacrylic acid perfluoro capryl ethyl ester etc.) of the alkane (as hexadecane etc.) of 12～18 carbon, 12～18 carbon among the present invention, and consumption is 3%～25% of a small molecule hydrocarbon consumption.
Emulsifying agent among the present invention can select for use ionic emulsifying agent (as anionic emulsifier lauryl sodium sulfate, dodecyl sodium sulfate, 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 3%～20% of the total consumption of monomer.
Water-soluble peroxide initiator of the optional usefulness of initator (as potassium peroxydisulfate, Ammonium Persulfate 98.5 etc.) or water soluble oxidized reduction initiating system are (as systems such as persulfate and triethanolamine, tetramethyl two ethylenediamines, morphine quinolines, hydrogen peroxide and ferrous sulfate system) or the water-soluble cationic azo-initiator (as 2,2 '-azo (2-amidine propane) dichloride hydrogen etc.) at least a in, consumption is 3% ~ 25% of the total consumption of monomer.
Consider that system stability and elementary free radical and oligomer free radical are trapped within the ratio on the drop interface, emulsifying agent of selecting for use and initator must couplings, cationic initator can with cationic or (with) nonionic emulsifier uses simultaneously; The nonionic initator then can use with single ionic or nonionic emulsifier, also can with ionic and the composite use of nonionic emulsifier; The anionic initator can with anionic or (with) nonionic emulsifier uses simultaneously.
System pH has material impact to the hydrolysis-condensation reaction of the siloxanyl monomers of carbon-carbon double bonds, and hydrolysis-condensation speed can have material impact to the stability of emulsion system and the structure control of shell polymer, so should select different pH buffers with the performance of kind and target product according to the siloxanyl monomers content of carbon-carbon double bonds in the system, the hydrolysis-condensation speed of the siloxanyl monomers of control carbon-carbon double bonds.
The invention has the beneficial effects as follows:
Preparation process of the present invention is simple, can stably obtain the Nano capsule of temperature sensitive inorganic-organic hybridization, and the penetration property of capsule can have wider range of application by the reversible adjusting of variation of environment temperature.The hollow capsules that the present invention obtains can be widely used in catalyst and load with; The control of medicine, protein and other bioactivator discharges; Also can load the particle of nanoscale; Fields such as the loading of other reagent and control release.In nanometer microreactor field potential using value is also arranged.
The specific embodiment
Describe the present invention in detail below by specific embodiment, wherein the data of embodiment 1～3 are as shown in table 1, and the data of embodiment 4～6 are shown in Table 2.
Embodiment 1:
Take by weighing emulsifier sodium lauryl sulfate 0.54g, pH buffer sodium dihydrogen phosphate, each 1g of diammonium hydrogen phosphate add in the 1000g water, and obtaining the pH value is 7 emulsifier solutions.Octane 10.5g, hexadecane 0.42g, N-N-isopropylacrylamide 0.1g, styrene 2g, 3-methacrylic acid trimethoxy silicon propyl ester 0.9g are mixed, join in the mentioned emulsifier aqueous solution, above-mentioned mixed liquor is disperseed, obtain stable emulsion with ultrasonic wave; Adjustment to 80 ℃ under nitrogen protection, adds potassium peroxydisulfate 0.25g and causes, reaction 120min.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 38.7nm under 25 ℃ of conditions; Its number average bead diameter is 38.0nm under 40 ℃ of conditions, and particle does not have temperature sensitive property.With its form of transmission electron microscopy observation, be the capsule of hollow structure.Add potassium peroxydisulfate 0.05g, drip 1.5gN-N-isopropylacrylamide, 0.15g diallylamine and the formulated aqueous solution of 95g water, dripped off in 0.5 hour, drip off back insulation 18 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 96.1nm under 25 ℃ of conditions; Its number average bead diameter is 47.7nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, particle is a hollow capsules.
Embodiment 2:
Take by weighing emulsifying agent softex kw 37.5g, pH buffer sodium dihydrogen phosphate, each 1g of diammonium hydrogen phosphate add in the 1000g water, obtain the pH value and be 7 emulsifier solution.Octane 500g, hexadecane 50g, caprolactam 45g, methyl methacrylate 137.5g, 3-methacrylic acid trimethoxy silicon propyl ester 67.5g are mixed, join in the mixed aqueous solution of mentioned emulsifier and pH buffer, with ultrasonic wave above-mentioned mixed liquor is disperseed, obtain stable emulsion; Adjustment to 60 ℃ under nitrogen protection, adds 2, and 2 '-azo (2-amidine propane) dihydrochloride 25g causes, reaction 180min.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 86.3nm under 25 ℃ of conditions; Its number average bead diameter is 65.8nm under 40 ℃ of conditions, and particle shows certain temperature sensitive property.With its form of transmission electron microscopy observation, be the capsule of hollow structure.Add potassium peroxydisulfate 7.4g, drip 100g caprolactam, 48g tartaric acid diacrylamine and the formulated aqueous solution of 300g water, dripped off in 2 hours, drip off back insulation 10 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 189.9nm under 25 ℃ of conditions; Its number average bead diameter is 93.4nm under 40 ℃ of conditions, and particle shows temperature sensitive property.With its form of transmission electron microscopy observation, particle is a hollow capsules.
Embodiment 3:
Take by weighing dodecyl dimethyl Propylamino sulfonic acid 14.4g, pH buffer sodium dihydrogen phosphate, each 1g of diammonium hydrogen phosphate add in the 1000g water, obtain emulsifier solution.Pentane 216g, hexadecanol 52g, vinyl isobutyramide 48g, butyl acrylate 240g, VTES 192g are mixed, join in the above-mentioned aqueous solution that contains emulsifying agent, above-mentioned mixed liquor is disperseed, obtain stable emulsion with ultrasonic wave; Adjustment to 50 ℃ under nitrogen protection, adds potassium peroxydisulfate 9.6g, and sodium sulfite 4.8g causes, reaction 300min.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 95.8nm under 25 ℃ of conditions; Its number average bead diameter is 94.7nm under 40 ℃ of conditions, and particle does not have temperature sensitive property substantially.With its form of transmission electron microscopy observation, be the capsule of hollow structure.Add potassium peroxydisulfate 28g, ethamine 28g drips 240g vinyl isobutyramide, 60gN, and the N '-methylene diacrylamine and the formulated aqueous solution of 800g water dripped off in 3 hours, drips off back insulation 3 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 287.4nm under 25 ℃ of conditions; Its number average bead diameter is 135.3nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, particle is a hollow capsules.
Embodiment 4:
Take by weighing emulsifier op-10 11.4g, pH buffer sodium acetate 40g, acetate 6g; Add in the 1000g water, obtain the pH value and be 5 emulsifier solution.With cyclohexane 100g, methacrylic acid perfluoro capryl ethyl ester 10g, N-N-isopropylacrylamide 8g, styrene 50g, (methyl) acrylic acid triethoxysilicane methyl esters 5g mixes, join in the above-mentioned aqueous solution that contains emulsifying agent, above-mentioned mixed liquor is disperseed, obtain stable emulsion with ultrasonic wave; Adjustment to 40 ℃ under nitrogen protection, adds potassium peroxydisulfate 10g, and triethanolamine 5g causes, reaction 600min.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is for being 99.3nm under 25 ℃ of conditions; Its number average bead diameter is 98.4nm under 40 ℃ of conditions, and particle does not have temperature sensitive property.With its form of transmission electron microscopy observation, be the microcapsules of hollow structure.Add potassium peroxydisulfate 1g, diethylamine 0.5g drips 32gN-N-isopropylacrylamide, 8gN, and the N '-methylene diacrylamine and the formulated aqueous solution of 200g water dripped off in 2 hours, drips off back insulation 10 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 254.6nm under 25 ℃ of conditions; Its number average bead diameter is 119.5nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, be the capsule of hollow.
Embodiment 5:
Take by weighing emulsifier sodium lauryl sulfate 5g, OP-10 5g, pH buffer borax 3.81g add in the 1000g water, obtain the pH value and be 9 emulsifier solution.With toluene 200g, lauryl methacrylate 15g, N-N-isopropylacrylamide 8g, acrylonitrile 77g, 3-methacrylic acid trimethoxy silicon propyl ester 15g mixes, join in the above-mentioned aqueous solution that contains emulsifying agent, above-mentioned mixed liquor is disperseed, obtain stable emulsion with ultrasonic wave; Adjustment to 50 ℃ under nitrogen protection, adds hydrogen peroxide 15g, and sodium thiosulfate 7.5g causes, reaction 180min.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 64.3nm under 25 ℃ of conditions; Its number average bead diameter is 62.7nm under 40 ℃ of conditions, and particle does not have temperature sensitive property substantially.With its form of transmission electron microscopy observation, be the microcapsules of hollow structure.Add potassium peroxydisulfate 3g, ferrous sulfate 1.5g Dropwise 5 0gN-N-isopropylacrylamide, 7.5gN, the N '-methylene diacrylamine and the formulated aqueous solution of 300g water dripped off in 2 hours, dripped off back insulation 15 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 167.9nm under 25 ℃ of conditions; Its number average bead diameter is 88.2nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, be the capsule of hollow.
Embodiment 6:
Take by weighing emulsifier op-10 25g, pH buffer sodium dihydrogen phosphate, each 1g of diammonium hydrogen phosphate add in the 1000g water, obtain emulsifier solution.With octane 300g, hexadecane 50g, caprolactam 25g, styrene 100g, VTES 25g mixes, and joins in the above-mentioned aqueous solution that contains emulsifying agent, with ultrasonic wave above-mentioned mixed liquor is disperseed, and obtains stable emulsion; Adjustment to 75 ℃ under nitrogen protection, adds polyethylene glycol 800 azo macromole evocating agent 35g and causes, reaction 240min.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 94.2nm under 25 ℃ of conditions; Its number average bead diameter is 92.7nm under 40 ℃ of conditions, and particle does not have temperature sensitive property.With its form of transmission electron microscopy observation, be the microcapsules of hollow structure.Add polyethylene glycol 800 azo macromole evocating agent 8g, drip 70g caprolactam, 14gN, the N '-methylene diacrylamine and the formulated aqueous solution of 400g water dripped off in 4 hours, dripped off back insulation 20 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its number average bead diameter is 212.3nm under 25 ℃ of conditions; Its number average bead diameter is 114.2nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, be the capsule of hollow.
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 experimental program of the present invention all can only be thought can not limit the present invention to explanation of the present invention, claim has 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 variation in the scope, all should think to be included in the scope of claims with claims of the present invention.
Claims (6)
1, a kind of method for preparing temperature sensitive inorganic-organic hybridization nano microcapsule, it is characterized in that, the monomer that participates in reaction comprises the siloxanyl monomers of at least a temperature sensitive monomer, at least a vinyl monomer and at least a carbon-carbon double bonds, the total consumption of monomer is meant the gross mass of the siloxanyl monomers of temperature sensitive monomer, vinyl monomer and carbon-carbon double bonds, but does not comprise and add temperature sensitive monomer and water-soluble cross-linked monomer;
This method comprises the following steps:
(1) emulsifying agent, pH buffer are dissolved in the water, obtain the pH value and be 5～10 the emulsifying agent and the mixed solution of buffer, the ratio of total consumption of monomer and water is 0.0025: 1～0.5: 1, the emulsifying agent consumption is 3%～20% of the total consumption of monomer, and pH value buffer consumption is 0.1%～5% of a water consumption;
(2) siloxanyl monomers of temperature sensitive monomer with small molecule hydrocarbon, co-stabilizer, vinyl monomer, carbon-carbon double bonds mixed, join in the mixed solution that step (1) obtains, above-mentioned mixed liquor is disperseed, obtain stable miniemulsion with ultrasonic wave;
Wherein, the small molecule hydrocarbon consumption is 40%～360% of the total consumption of monomer, the consumption of co-stabilizer is 3%～25% of a small molecule hydrocarbon consumption, the temperature sensitive monomer consumption is 2.5%～20% of the total consumption of monomer in this step, the vinyl monomer consumption is 50%～80% of the total consumption of monomer, and the siloxanyl monomers consumption of carbon-carbon double bonds is 7.5%～40% of the total consumption of monomer;
(3) adjustment to 40～80 of the emulsion that step (2) is obtained ℃, under inert gas shielding, add initator and carry out mini-emulsion polymerization, initiator amount is 3%～25% of the total consumption of monomer, react after 120～600 minutes, obtain the hybrid nano microcapsule that the shell polymer contains the temperature sensitive monomer unit;
(4) after the system conversion ratio reaches more than 90%, add initator and drip the mixed aqueous solution add temperature sensitive monomer and water-soluble cross-linked monomer, the dropping time was controlled in 30～240 minutes, after adding monomer solution and dripping, was incubated 3～20 hours;
Wherein, the consumption of adding temperature sensitive monomer is 2～15 times of the middle temperature sensitive monomer of step (2), water-soluble cross-linked monomer consumption is to add 10%～50% of temperature sensitive monomer, the ratio of adding total consumption of monomer and water is 0.01: 1～0.5: 1, add the total consumption of monomer and be meant the gross mass of adding temperature sensitive monomer, water-soluble cross-linked monomer, adding initiator amount is to add 3%～20% of the total consumption of monomer;
Described temperature sensitive monomer is at least a in caprolactam or the following structural formula with adding temperature sensitive monomer:
R in the structural formula (1)
1, R
2Be H, C
2～C
5Aliphatic chain, and R
1, R
2Can not be H simultaneously, R
3Be H, CH
3
R in the structural formula (2)
1Be C
1～C
5Aliphatic chain, R
2, R
3Be H, CH
3
Described vinyl monomer structure is at least a in the following structural formula:
In the structural formula (3), R
1Be H, CH
3Perhaps C
2H
5, R
2Be phenyl, substituted-phenyl, Cl, CN, alkyl ether or OCOCH
3
In the structural formula (4), R
1Be H, CH
3Perhaps C
2H
5, X is C
1～C
12Aliphatic chain or the C of hydroxyl
1～C
12Aliphatic chain;
The structure of the siloxanyl monomers of described carbon-carbon double bonds is at least a in the following structural formula:
In the structural formula (5), R
1Be H, CH
3, C
2H
5, R
2Be C
1～C
4Aliphatic chain or phenyl ring;
In the structural formula (6), R
1Be H, CH
3, 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 structure of described water-soluble cross-linker is at least a in the following structural formula:
Described water-soluble cross-linked monomer is at least a in structural formula (7), formula (8), the formula (9).
According to the described method for preparing temperature sensitive inorganic-organic hybridization nano microcapsule of claim 1, it is characterized in that 2, described small molecule hydrocarbon is at least a in the alkane of cycloalkane, aromatic hydrocarbon or 5～14 carbon.
According to the described method for preparing temperature sensitive inorganic-organic hybridization nano microcapsule of claim 1, it is characterized in that 3, described co-stabilizer is C
12～C
18Aliphatic hydrocarbon, C
12～C
18Fatty alcohol, structural formula (10) or structural formula (11) at least a:
In the structural formula (10), R
1Be H, CH
3, C
2H
5, X is C
12～C
18Aliphatic chain;
In the structural formula (11), R
1Be H, CH
3, CF
3, m=0～17, R
fBe C
nH
jF
2n+1-jFluoro fat (n=1～18, j=0～34), and m+n=12～18.
4, according to the described method for preparing temperature sensitive inorganic-organic hybridization nano microcapsule of claim 1, it is characterized in that, described emulsifying agent is organic carboxylate, organic sulfate, organic sulfonate, organic phosphate anionic emulsifier, the organic quaternary ammonium salt cationic emulsifier, the amphoteric ion type emulsifying agent, at least a in polyoxyethylene ester, APEO or the polyoxyethylene amine nonionic emulsifier.
5, according to the described method for preparing temperature sensitive inorganic-organic hybridization nano microcapsule of claim 1, it is characterized in that described water soluble starter is at least a in hydrogen peroxide, persulfate, cationic diazo salt, polyethylene glycol azo macromole evocating agent or the water soluble oxidized reduction initiating system; The reducing substances that is added in the described water soluble oxidized reduction initiating system is at least a in primary amine, secondary amine, tertiary amine alcohol, sulphite, thiosulfate or the ferrous salt.
6, according to the described method for preparing temperature sensitive inorganic-organic hybridization nano microcapsule of claim 1, it is characterized in that, described pH buffer is 5～10 material for forming the pH value, at least a in sodium acetate, ammonium acetate, acetate, ammonium chloride, ammoniacal liquor, dihydric phosphate, phosphoric acid hydrogen disalt, borax, diphenate, carbonate, bicarbonate or the trishydroxymethylaminomethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100693170A CN100512946C (en) | 2007-06-15 | 2007-06-15 | Method of preparing temperature sensitive inorganic-organic hybridization nano microcapsule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100693170A CN100512946C (en) | 2007-06-15 | 2007-06-15 | Method of preparing temperature sensitive inorganic-organic hybridization nano microcapsule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101085423A true CN101085423A (en) | 2007-12-12 |
| CN100512946C CN100512946C (en) | 2009-07-15 |
Family
ID=38936698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100693170A Expired - Fee Related CN100512946C (en) | 2007-06-15 | 2007-06-15 | Method of preparing temperature sensitive inorganic-organic hybridization nano microcapsule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100512946C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580636A (en) * | 2012-02-09 | 2012-07-18 | 杭州师范大学 | Preparation method of inorganic submicron capsule |
| CN105712645A (en) * | 2015-12-31 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Admixture for improving mechanical properties of cement-based materials and preparation method of admixture |
| CN109913177A (en) * | 2019-03-04 | 2019-06-21 | 河北工业大学 | Double phase-change accumulation energy automatically cleaning materials for walls and its application |
| CN114673016A (en) * | 2022-03-15 | 2022-06-28 | 连云港鹰游新立成纺织科技有限公司 | Preparation method of nano disperse dye capsule for textile printing |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1344070A (en) * | 1969-06-27 | 1974-01-16 | Piron J G J | Dry transfer materials |
| CN1290604C (en) * | 2004-12-29 | 2006-12-20 | 浙江大学 | Process for preparing organic-inorganic hybrid nano microcapsule using polymer as core |
| CN100354039C (en) * | 2005-01-26 | 2007-12-12 | 浙江大学 | Preparation of organic-inorganic hybridized nanometer microcapsule with organic micromolecular hydrocarbon as model plate |
-
2007
- 2007-06-15 CN CNB2007100693170A patent/CN100512946C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580636A (en) * | 2012-02-09 | 2012-07-18 | 杭州师范大学 | Preparation method of inorganic submicron capsule |
| CN105712645A (en) * | 2015-12-31 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Admixture for improving mechanical properties of cement-based materials and preparation method of admixture |
| CN109913177A (en) * | 2019-03-04 | 2019-06-21 | 河北工业大学 | Double phase-change accumulation energy automatically cleaning materials for walls and its application |
| CN114673016A (en) * | 2022-03-15 | 2022-06-28 | 连云港鹰游新立成纺织科技有限公司 | Preparation method of nano disperse dye capsule for textile printing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100512946C (en) | 2009-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100512945C (en) | Method of preparing temperature sensitive nano microcapsule by using small molecule hydrocarbon as template | |
| JP2614707B2 (en) | Method for producing emulsion polymer having hollow structure | |
| JP5484673B2 (en) | Thermally foamable microspheres and their production methods and applications | |
| CA1237223A (en) | Sequential heteropolymer dispersion and a particulate material obtainable therefrom, useful in coating compositions as an opacifying agent | |
| Zhang et al. | Silica-PMMA core-shell and hollow nanospheres | |
| US7741378B2 (en) | Porous monodispersed particles and method for production thereof, and use thereof | |
| CN100512946C (en) | Method of preparing temperature sensitive inorganic-organic hybridization nano microcapsule | |
| Fallahi-Samberan et al. | Investigating Janus morphology development of poly (acrylic acid)/poly (2‑(dimethylamino) ethyl methacrylate) composite particles: An experimental study and mathematical modeling of DOX release | |
| CN104628923A (en) | Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by oil-soluble initiator | |
| CN100354039C (en) | Preparation of organic-inorganic hybridized nanometer microcapsule with organic micromolecular hydrocarbon as model plate | |
| CN111944191B (en) | Quantum dot fluorescent microsphere and preparation method thereof | |
| Eldin et al. | Poly (acrylonitrile-co-methyl methacrylate) nanoparticles: I. Preparation and characterization | |
| Li et al. | Clustering of asymmetric dumbbell-shaped silica/polystyrene nanoparticles by solvent-induced self-assembly | |
| CN103965421A (en) | Preparation method and product of thermo-sensitive amphipathic block copolymer with nucleocapsid structure | |
| Wang et al. | One-pot synthesis of mushroom-shaped polymeric Janus particles by soap-free emulsion copolymerization | |
| CN101381435B (en) | Preparation method of spherical polyelectrolyte brush and use thereof | |
| CN103772598B (en) | A kind of regulate and control method of single dispersing functional polymer microsphere surfaceness | |
| JP2006257139A (en) | Core-shell type polymer particulate and method for producing the same | |
| CN110590982A (en) | Quantum dot fluorescent microsphere and preparation method thereof | |
| CN1331590C (en) | Hollow microcapsule preparing process | |
| Cao et al. | A versatile technique to fabricate capsules: miniemulsion | |
| CN105777967A (en) | Preparation method of two-sided polymer particulates with controllable shapes | |
| CN107880218B (en) | Polymer hollow nano-microsphere and preparation method and application thereof | |
| CN102660022A (en) | Preparation method of novel conductive particulate emulsifier | |
| Vasilaki et al. | Non-cross-linked hollow polymer nanocapsules of controlled size and shell thickness |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090715 Termination date: 20130615 |