CN1552760A - Carboxyl functional polymer/SiO2 composite nanometer particle and preparing method thereof - Google Patents
Carboxyl functional polymer/SiO2 composite nanometer particle and preparing method thereof Download PDFInfo
- Publication number
- CN1552760A CN1552760A CNA2003101217065A CN200310121706A CN1552760A CN 1552760 A CN1552760 A CN 1552760A CN A2003101217065 A CNA2003101217065 A CN A2003101217065A CN 200310121706 A CN200310121706 A CN 200310121706A CN 1552760 A CN1552760 A CN 1552760A
- Authority
- CN
- China
- Prior art keywords
- sio
- particle
- olefinic monomer
- functional group
- composite nano
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract 4
- 229910052681 coesite Inorganic materials 0.000 title abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 2
- 239000000377 silicon dioxide Substances 0.000 title abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 2
- 229910052682 stishovite Inorganic materials 0.000 title abstract 2
- 229910052905 tridymite Inorganic materials 0.000 title abstract 2
- 229920001002 functional polymer Polymers 0.000 title 1
- 239000002105 nanoparticle Substances 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 42
- -1 diene hydrocarbons Chemical class 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 31
- 125000000524 functional group Chemical group 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 239000000872 buffer Substances 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 102000004895 Lipoproteins Human genes 0.000 claims description 2
- 108090001030 Lipoproteins Proteins 0.000 claims description 2
- CBSOFSBFHDQRLV-UHFFFAOYSA-N N-methylbenzylamine hydrochloride Chemical compound [Cl-].C[NH2+]CC1=CC=CC=C1 CBSOFSBFHDQRLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- RCTOVWPTGOZSPJ-UHFFFAOYSA-N benzyl(ethyl)azanium;chloride Chemical compound Cl.CCNCC1=CC=CC=C1 RCTOVWPTGOZSPJ-UHFFFAOYSA-N 0.000 claims description 2
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 125000006178 methyl benzyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 150000003254 radicals 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
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 19
- 238000009826 distribution Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000005395 methacrylic acid group Chemical class 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical class [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- YTRIOKYQEVFKGU-UHFFFAOYSA-M benzyl(tripropyl)azanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 YTRIOKYQEVFKGU-UHFFFAOYSA-M 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
A composite nanoparticle is prepared from SiO2 nanoparticle, organic olefin monomer, the olefin monomer containing carboxyl function group, and coupling agent through polymerizing in the emulsion or suspension using water as medium. Its advantage is high chemical reaction activity and ionizing power.
Description
Technical field
The carboxyl function type polymer/SiO that the present invention relates to
2Composite nanoparticle and preparation method thereof belongs to macromolecular material
Technical field.
Background technology
Because nanoparticle can be widely used in numerous areas such as macromolecular material, chemical industry, biology, medical science, microelectronics, thereby has very important potentiality using value in Nano-technology Development.Wherein polymer/inorganic powder nano-complex particle has both inorganic nano-particle and organic macromolecule characteristic, so its exploitation and preparation become a focus direction in the research of current polymer novel material day by day.
The applicant is once in the patent of having applied for (China Patent No.: successfully epoxy-functional has been introduced polymer/SiO 03143111.9)
2Particle surface, the polymer/SiO of this surperficial epoxide functionization
2Nano-complex particle in the filled high polymer matrix time owing to have with matrix good interface consistency matrix properties is got a qualitative improvement.But epoxy-functional belongs to non-ionic type functional group, does not possess ionizing power, thereby has been subjected to bigger restriction in its application of the Ionized occasion of numerous needs; The group that can react with it simultaneously is comparatively limited, so the main application of this nano-complex particle is confined among the modification of a part of macromolecule matrix.
Summary of the invention
The purpose of this invention is to provide a kind of carboxyl function type polymer/SiO
2Composite nanoparticle and preparation method thereof, select for use have can and the inorganic particulate surface or can and importing at the polymkeric substance or the monomer of the lip-deep functional group reactions of inorganic particulate, by functional group reactions or by means such as polyreactions, make it at first to be grafted on the inorganic nano-particle sub-surface and form polymer covering layer, but introduce the more broad carboxyl functional group of the stronger reaction range of chemical reactivity at the polymer overmold laminar surface then.Guarantee to have between polymer layer and the inorganic particulate surface stronger chemical bond and connect, coating layer can not be come off; The introducing of carboxyl not only can be by reacting the interface compatibility that improves composite nanoparticle and matrix with the filling matrix, the more important thing is the reaction range of carboxyl broadness simultaneously and be easy to Ionized characteristic and given this nanoparticle very high reactive behavior, make it to be widely used in polymer modification agent, water conditioner, catalyzer, sensing agent and protein carrier, field such as microcapsule embedded.This method not only can solve the problem that coating layer that cladding nanometer particle in the past in use exists is easy to come off; Surperficial simultaneously carboxyl functional group can not only improve the interface compatibility with matrix greatly, and, make the use field of this composite nano particle and the raising that using value has obtained matter because it has broad chemical reaction scope, very high chemical reactivity and is easy to Ionized characteristic.
Polymer/inorganic composite type nanoparticle preparation method that the present invention adopts, the size that can not only keep its particle nanometer scale, simultaneously can make it to have both inorganic nano-particle and organic macromolecule characteristic, therefore aspects such as this external particle structure, size of particles, particle surface physical and chemical character have very high design freedom, are a kind of preparation methods of valuable composite nanoparticle.
The objective of the invention is to be achieved through the following technical solutions:
A kind of carboxyl function type polymer/SiO
2Composite nano particle is characterized in that: this composite nanoparticle has with inorganic nano SiO
2Particle is the structure that shell and carboxyl functional group are present in this particle case surface for nuclear with the olefinic organic hydrocarbon polymer, and its particle diameter is less than 100nm; It is a raw material with following material, by being that the letex polymerization carried out of medium or the method for suspension polymerization are prepared from water:
1) olefinic monomer: 100 parts by weight
2) contain the carboxyl functional group olefinic monomer: 0.1～40 part
3) SiO
2Particle: 0.1～40 part
4) coupling agent: account for SiO
21.5～30wt% of particle
5) emulsifying agent: 4.5～8 parts
6) initiator: 0.1～2 part
7) buffer reagent: account for 50～150% of carboxyl functional group olefinic monomer quality.
Olefinic monomer of the present invention is meant the monoolefine, the diene hydrocarbons that contain carbon carbon unsaturated double-bond (C=C) in molecular structure; Described olefinic monomer employing alpha-olefin is selected from one or more in vinylbenzene, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester; Described diene hydrocarbons employing diolefine is selected from one or more in suitable divinyl, isobutyl diene, the isoprene
Contain the carboxyl functional group olefinic monomer described in the present invention, be meant and in molecular structure, contain simultaneously with the represented carbon carbon unsaturated double-bond of chemical structure skeleton symbol (a) with the olefines material of the carboxyl functional group of (b) expression.
——COOH——(b)
Coupling agent described in the present invention, be meant in the molecular structure and should contain a carbon carbon unsaturated double-bond (C=C) at least, comprise in silane type, aluminic acid ester type, borate-type, titanic acid ester type, boron aluminic acid lipoprotein type, boron metatitanic acid fat type or the titanium aluminic acid ester type one or more.
Emulsifying agent described in the present invention can adopt one or more in the following material:
A. cationic: as to comprise three C
1～18Alkyl methyl ammonium chloride, three C
1～18Alkyl methyl brometo de amonio, three C
1～18Alkyl benzyl ammonium chloride, three C
1～18Alkyl benzyl brometo de amonio or three C
1～18Alkyl methyl benzyl ammonium chloride, three C
1～18Alkyl ethylbenzylammonium chloride, three C
1～18Alkyl methyl benzyl bromination; Three C
1～18Alkyl Ethylbenzyl brometo de amonio.
B. anionic: comprise C12～18 sodium alkyl sulfates, C12～18 alkylsurfuric acid potassium, C12～18 alkyl sodium sulfonates, C12～18 alkylsulphonic acid potassium, C12～18 sodium alkyl benzene sulfonates, C12～18 sodium alkyl benzene sulfonate potassium.
C. non-ionic type: comprise C3～10 alkyl phenol polyoxyethylenes (4～50) ether, C2～18 aliphatic alcohol polyethenoxies (4～50) ether, polyoxyethylene (4～50) sorbyl alcohol list C11～18 fatty acid esters or polyoxyethylene (4～50) sorbyl alcohol three C11～18 fatty acid esters.
Described initiator is meant can be under 40～95 ℃ of conditions, also can produce free radical causes olefinic monomer polymeric material to have 30～35kcal/mol ionic dissociation energy, comprises azo class, the peroxide material of persulfuric acid salt, hydroperoxide kind material or the organic type of inorganic type.For example adopt Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile), or the redox system formed with ferrous salt, sulphite, thiosulphate respectively of hydrogen peroxide, dibenzoyl peroxide.
The soluble substance of neutralization reaction can take place with acid for having certain alkalescence in described buffer reagent, comprises supercarbonate, carbonate, solubility bases material, as sodium bicarbonate, salt of wormwood, sodium hydroxide.
A kind of carboxyl function type polymer/SiO provided by the invention
2The preparation method of composite nano particle is characterized in that adopting emulsion polymerisation process, and this method comprises the steps:
(1) be raw material with following component and content:
1) olefinic monomer: 100 parts by weight;
2) contain the carboxyl functional group olefinic monomer: 0.1～40 part;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21.5～30wt% of particle;
5) emulsifying agent: 4.5～8 parts;
6) initiator: 0.1～2 part;
7) buffer reagent: account for 50～150% of carboxyl functional group olefinic monomer quality;
With SiO
2After the coupling agent treatment of particle with above-mentioned content, join institute and make it in the quantitative olefinic monomer to mix and be uniformly dispersed;
(2) described mixture is joined contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor, in reactor, add the part initiator, and make it to be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(3) add buffer reagent and the olefinic monomer that contains carboxyl functional group then, reacted 0.5～3 hour, add remaining initiator, continue reaction 0.5～2 hour;
(4) behind the cooling discharging, and after breakdown of emulsion, washing, drying and other steps are handled, can obtain carboxyl function type polymer/SiO that the present invention proposes
2Composite nano particle.
The present invention also provides another kind of carboxyl function type polymer/SiO
2The preparation method of composite nano particle is characterized in that adopting suspension polymerization to be prepared, and this method comprises the steps:
(1) be raw material with following component and content:
1) olefinic monomer: 100 parts by weight;
2) contain the carboxyl functional group olefinic monomer: 0.1～40 part;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21.5～30wt% of particle;
5) emulsifying agent: 4.5～8 parts;
6) initiator: 0.1～2 part;
7) buffer reagent: account for 50～150% of carboxyl functional group olefinic monomer quality;
With SiO
2After the coupling agent treatment of particle with above-mentioned content, join institute and make it in the quantitative olefinic monomer to mix and be uniformly dispersed;
(2) described mixture is joined contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor, and make it to be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(3) add buffer reagent and the olefinic monomer that contains carboxyl functional group then, reacted 0.5～3 hour, add remaining initiator, continue reaction 0.5～2 hour;
(4) behind the cooling discharging, and after breakdown of emulsion, washing, drying and other steps are handled, can obtain carboxyl function type polymer/SiO that the present invention proposes
2Composite nano particle.
Carboxyl function type polymer/SiO that the present invention proposes
2Composite nano particle and preparation method thereof is by at polymer/SiO
2The composite nano particle sub-surface is introduced carboxyl functional group, makes it to possess the ionizing power of good chemical reactivity and surface of good group, thereby has enlarged the Application Areas and the using value of this composite nano particle.Carboxyl function type polymer/SiO of the present invention
2Composite nanoparticle, all connect between its nucleocapsid with chemical bond, can not only solve the problem that coating layer that cladding nanometer particle in the past in use exists is easy to come off, and can solve low problem of percentage of grafting that the graft type nanoparticle exists and grafting efficiency and the problem that is difficult to realize functionalisation of surfaces in preparation, its overall yield of reaction is more than 90%, and percentage of grafting can be pressed monomer and SiO between tens thousand of percentage tens of
2The ratio adjustment, grafting efficiency is more than 80%.In addition, this carboxyl function type polymer/SiO
2The preparation manipulation of composite nanoparticle is simple, easily realizes suitability for industrialized production, and the product of making can stably remain on emulsion state, also can be dried to pulverulence, is easy to store and use.The more important thing is this carboxyl function type polymer/SiO
2The particle diameter of composite nano particle is all less than 100nm, and the carboxyl functional group on its particle surface have very high chemical reactivity, can ionization, these characteristics will make carboxyl function type polymer/SiO of the present invention
2Composite nano particle has purposes widely in from now on nanometer material science and technical development.
Description of drawings
Fig. 1: PMAA/PS/SiO
2Nano-complex particle (a), PS/SiO
2Nano-complex particle (b) and original SiO
2(c) infrared spectrum.
Fig. 2: original SiO
2(a) and PMAA/PS/SiO
2The electron micrograph of nano-complex particle (b).
Fig. 3: PMAA/PS/SiO
2The grain size distribution curve of nano-complex particle.
Embodiment
Following example will further specify the present invention.
Embodiment 1: with median size is 10 ± 5nm, and specific surface area is 640m
2The nanometer SiO of/g
2After 5wt%KH-570 silane type coupling agent treatment, take by weighing 4 parts and be added in 100 parts of styrene monomers, stirring and ultrasonic dispersing are even.In the four-hole bottle that mechanical stirring, reflux condensing tube, nitrogen protection and thermometer are housed, add 370 parts of deionized waters; 6 parts of sodium laurylsulfonates and 0.75 part of nonylphenol Soxylat A 25-7 (10); be warming up to 40 ℃ and make it stirring and dissolving after, add down monomers and SiO in 50 ℃
2Mixture.Then, add 70% of the initiator solution that is made into by 0.5 part of ammonium persulphate and 75 parts of deionized waters, temperature was risen to 82 ℃ of reactions after 1 hour, add 10 parts of sodium bicarbonates, dropwise add 10 parts of methacrylic acids (MAA) with 5 seconds 1 speed again.Dripped afterreaction 0.5 hour.Be warming up to 90 ℃, add the residue initiator solution, continue reaction postcooling discharging in 0.5 hour.Part emulsion after the discharging gets white powdery product after breakdown of emulsion, washing, drying, another part emulsion places test tube, finds to store after 6 months deposited phenomenon not occur.Overall yield of reaction 94.3% as calculated, uses the chloroform extracting after 12 hours on exsiccant composite nano particle, and recording its percentage of grafting is 2513%, and grafting efficiency is 91.4%.Its infrared spectra is seen Fig. 1 (SiO
2Nanoparticle and the PMAA/PS/SiO after extracting
2The infrared spectrum of composite nano particle), on spectrogram, show tangible PS, PMAA and SiO
2Characteristic peak, illustrate that PS and PMAA have been grafted on SiO fully
2On the surface.From Fig. 2 (SiO
2Nanoparticle and PMAA/PS/SiO
2The electron micrograph of composite nano particle.2a:SiO
2Nanoparticle; 2b, 2c:PMAA/PS/SiO
2The composite nano particle) and Fig. 3 (PMAA/PS/SiO
2The size distribution test result of composite nanoparticle) as can be seen, its size distribution is in 60～70nm scope.
Embodiment 2: with SiO
2Addition reduce to 0.1 part by 4 parts, the KH-570 consumption is 1.5wt%, changes the MAA addition into 0.1 part simultaneously, the buffer reagent consumption changes 0.1 part into, all the other prescriptions are identical with example 1.Monomer and SiO
2Mixture 50 ℃ of following adding systems, be reflected at and carry out dripping again in 8 hours MAA under 60 ℃.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 97.4%, 98325% and 98.3%, and size distribution is 60～70nm.
Embodiment 3: with SiO
2Addition be increased to 40 parts by 4 parts, the KH-570 consumption is 30wt%, buffer reagent changes 5 parts of sodium hydroxide into, all the other prescriptions are identical with example 1.MAA drips and finishes afterreaction 3 hours.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 89.7%, 254% and 92.1%, and size distribution is 60～70nm.
Embodiment 4: emulsifying agent SDS consumption is increased to 8 parts, and the olefinic monomer that has carboxyl changes vinylformic acid (AA) consumption into and increases to 40 parts, and the APS consumption is kept to 0.1 part, and the buffer reagent consumption changes 30 parts into, and all the other prescriptions are identical with example 1.Be reflected at and carry out dripping again in 0.5 hour AA under 95 ℃.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 89.7%, 3124% and 83.3%, and size distribution is 60～70nm.
Embodiment 5: emulsifying agent SDS consumption is reduced to 4.5 parts, and the APS consumption increases to 2 parts, and buffer reagent changes 15 parts of salt of wormwood into, and all the other prescriptions are identical with example 1.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 92.5%, 2436% and 88.6%, and size distribution is 60～70nm.
Embodiment 6: the preparation method is with example 1, sodium laurylsulfonate is changed into the Sodium dodecylbenzene sulfonate of measuring, and changing 0.75 part nonylphenol Soxylat A 25-7 into 2 parts 12 fatty alcohol-polyoxyethylene ether (20), initiator adopts the mixture of 0.5 part of dibenzoyl peroxide and 0.5 part of S-WAT.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 87.9%, 2494% and 90.7%, and size distribution is 60～70nm.
Embodiment 7: the preparation method is with example 1, changes vinylbenzene the vinylbenzene and the methyl methacrylate mixture (half and half) of equivalent into, and emulsifying agent adopts the tripropyl benzyl ammonium chloride of equivalent, changes ammonium persulphate into amount Diisopropyl azodicarboxylate.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 93.2%, 2516% and 91.5%, and size distribution is 60～70nm.
Embodiment 8: the preparation method changes vinylbenzene into the methyl methacrylate of equivalent and the mixture of isobutyl diene with example 1, and coupling agent adopts oleic acid base aluminic acid ester type coupling agent, adds remaining initiator afterreaction and finishes in 2 hours.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 94.2%, 2467% and 89.7%, and size distribution is 60～70nm.
Embodiment 9: the preparation method changes vinylbenzene with vinylbenzene and the butyl acrylate mixture (half and half) measured into example 1, and emulsifying agent adopts the tripropyl methyl brometo de amonio of equivalent, and initiator adopts dibenzoyl peroxide.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 92.4%, 2492% and 90.6%, and size distribution is 60～70nm.
Embodiment 10: the preparation method changes KH-570 silane type coupling agent into boron aluminic acid ester type coupling agent with example 1, and the olefinic monomer that contains carboxyl functional group changes oleic acid into.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 87.1%, 2327% and 84.6%, and size distribution is 60～70nm.
Comparative example 1: the preparation method is with example 1, but SiO
2Do not use coupling agent treatment, the discovery system precipitates in reaction process.
Comparative example 2: the preparation method is with example 1, but do not add sodium laurylsulfonate and nonylphenol Soxylat A 25-7 (10), and breakdown of emulsion and precipitation take place in reaction process system.
Comparative example 3: preparation is filled a prescription with example 1, but with 4 parts of SiO that handle through KH-570
2, 100 parts of vinylbenzene and 10 parts of methacrylic acids are mixed in disposable together adding, system generation breakdown of emulsion.
In above each example, example 1,2,3,4,5,6,8,10 belongs to method of emulsion polymerization, and example 7,9 belongs to the method for suspension polymerization.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or 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, therefore, suitable with claims of the present invention contain with scope in any change, all should think to be included in the scope of claims.
Claims (11)
1. carboxyl function type polymer/SiO
2Composite nano particle is characterized in that: this composite nanoparticle has with inorganic nano SiO
2Particle is the structure that shell and carboxyl functional group are present in this particle case surface for nuclear with the olefinic organic hydrocarbon polymer, and its particle diameter is less than 100nm; It is a raw material with following material, by being that the letex polymerization carried out of medium or the method for suspension polymerization are prepared from water:
1) olefinic monomer: 100 parts by weight;
2) contain the carboxyl functional group olefinic monomer: 0.1～40 part;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21.5～30wt% of particle;
5) emulsifying agent: 4.5～8 parts;
6) initiator: 0.1～2 part;
7) buffer reagent: the 50～150wt% that accounts for the carboxyl functional group olefinic monomer.
2. according to described composite nano particle of claim 1, it is characterized in that: described olefinic monomer is meant monoolefine, the diene hydrocarbons that contains carbon carbon unsaturated double-bond (C=C) in molecular structure.
3. according to described composite nano particle of claim 2, it is characterized in that: described olefinic monomer adopts alpha-olefin, as in vinylbenzene, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester one or more; Described diene hydrocarbons adopts diolefine, as along in divinyl, isobutyl diene, the isoprene one or more.
4. according to described composite nano particle of claim 1, it is characterized in that: the described carboxyl functional group olefinic monomer that contains is meant and contains simultaneously in molecular structure with the represented carbon carbon unsaturated double-bond of chemical structure skeleton symbol (a) with the olefines material of the carboxyl functional group of formula (b) expression.
-COOH-(b)
5. according to described composite nano particle of claim 1, it is characterized in that: described coupling agent, be meant in the molecular structure and should contain a carbon carbon unsaturated double-bond (C=C) at least, as in silane type, aluminic acid ester type, borate-type, titanic acid ester type, boron aluminic acid lipoprotein type, boron metatitanic acid fat type or the titanium aluminic acid ester type one or more.
6. according to described composite nano particle of claim 1, it is characterized in that: described emulsifying agent adopts one or more in the following material:
A. cationic: as to comprise three C
1～18Alkyl methyl ammonium chloride, three C
1～18Alkyl methyl brometo de amonio, three C
1～18Alkyl benzyl ammonium chloride, three C
1～18Alkyl benzyl brometo de amonio or three C
1～18Alkyl methyl benzyl ammonium chloride, three C
1～18Alkyl ethylbenzylammonium chloride, three C
1～18Alkyl methyl benzyl bromination; Three C
1～18Alkyl Ethylbenzyl brometo de amonio;
B. anionic: comprise C12～18 sodium alkyl sulfates, C12～18 alkylsurfuric acid potassium, C12～18 alkyl sodium sulfonates, C12～18 alkylsulphonic acid potassium, C12～18 sodium alkyl benzene sulfonates, C12～18 sodium alkyl benzene sulfonate potassium;
C. non-ionic type: comprise C3～10 alkyl phenol polyoxyethylenes (4～50) ether, C2～18 aliphatic alcohol polyethenoxies (4～50) ether, polyoxyethylene (4～50) sorbyl alcohol list C11～18 fatty acid esters or polyoxyethylene (4～50) sorbyl alcohol three C11～18 fatty acid esters.
7. according to described composite nano particle of claim 1, it is characterized in that: described initiator is meant can be under 40～95 ℃ of conditions, also can produce free radical causes olefinic monomer polymeric material to have 30～35kcal/mol ionic dissociation energy, comprises azo class, the peroxide material of persulfuric acid salt, hydroperoxide kind material or the organic type of inorganic type.
8. according to the described composite nano particle of claim 7, it is characterized in that: described initiator is selected for use in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or the 2,2'-Azobis(2,4-dimethylvaleronitrile) a kind of; The redox system of perhaps selecting for use hydrogen peroxide, dibenzoyl peroxide to form with ferrous salt, sulphite, thiosulphate respectively.
9. according to the described composite nanoparticle of claim 1, it is characterized in that: the soluble substance of neutralization reaction can take place with acid for having certain alkalescence in described buffer reagent, is selected from supercarbonate, carbonate or solubility bases material.
10. one kind prepares carboxyl function type polymer/SiO as claimed in claim 1
2Composite nano particle is characterized in that adopting emulsion polymerisation process, and this method comprises the steps:
(1) be raw material with following component and content:
1) olefinic monomer: 100 parts by weight;
2) contain the carboxyl functional group olefinic monomer: 0.1～40 part;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21.5～30wt% of particle;
5) emulsifying agent: 4.5～8 parts;
6) initiator: 0.1～2 part;
7) buffer reagent: account for 50～150% of carboxyl functional group olefinic monomer quality; With SiO
2After the coupling agent treatment of particle with above-mentioned content, join institute and make it in the quantitative olefinic monomer to mix and be uniformly dispersed;
(2) described mixture is joined contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor and in reactor, add the part initiator, and make it to be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(3) add buffer reagent and the olefinic monomer that contains carboxyl functional group then, reacted 0.5～3 hour, add remaining initiator, continue reaction 0.5～2 hour;
(4) behind the cooling discharging, and after breakdown of emulsion, washing, drying and other steps are handled, can obtain carboxyl function type polymer/SiO that the present invention proposes
2Composite nano particle.
11. one kind prepares carboxyl function type polymer/SiO according to claim 1
2The method of composite nano particle is characterized in that adopting suspension polymerization to be prepared, and specifically comprises the steps:
(1) be raw material with following component and content:
1) olefinic monomer: 100 parts by weight;
2) contain the carboxyl functional group olefinic monomer: 0.1～40 part;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21.5～30wt% of particle;
5) emulsifying agent: 4.5～8 parts;
6) initiator: 0.1～2 part;
7) buffer reagent: account for 50～150% of carboxyl functional group olefinic monomer quality;
With SiO
2After the coupling agent treatment of particle with above-mentioned content, itself and part initiator are joined in the quantitative olefinic monomer of institute, make it to mix and be uniformly dispersed;
(2) described mixture is joined contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor, and make it to be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(3) add buffer reagent and the olefinic monomer that contains carboxyl functional group then, reacted 0.5～3 hour, add remaining initiator, continue reaction 0.5～2 hour;
(4) behind the cooling discharging, and after breakdown of emulsion, washing, drying and other steps are handled, can obtain carboxyl function type polymer/SiO that the present invention proposes
2Composite nano particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101217065A CN1298778C (en) | 2003-12-19 | 2003-12-19 | Carboxyl functional polymer/SiO2 composite nanometer particle and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101217065A CN1298778C (en) | 2003-12-19 | 2003-12-19 | Carboxyl functional polymer/SiO2 composite nanometer particle and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1552760A true CN1552760A (en) | 2004-12-08 |
| CN1298778C CN1298778C (en) | 2007-02-07 |
Family
ID=34338520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101217065A Expired - Fee Related CN1298778C (en) | 2003-12-19 | 2003-12-19 | Carboxyl functional polymer/SiO2 composite nanometer particle and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1298778C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341781C (en) * | 2004-03-12 | 2007-10-10 | 河南大学 | Reactive nanometer particle of silica dioxide |
| CN117777904A (en) * | 2024-02-27 | 2024-03-29 | 湖南高瑞电源材料有限公司 | Positive electrode fluorine-free binder material, and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6243445A (en) * | 1985-08-20 | 1987-02-25 | Sumitomo Chem Co Ltd | Vulcanized rubber composition |
| KR20010032104A (en) * | 1997-12-15 | 2001-04-16 | 엑손 케미칼 패턴츠 인코포레이티드 | Transparent and colorable elastomeric compositions |
-
2003
- 2003-12-19 CN CNB2003101217065A patent/CN1298778C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341781C (en) * | 2004-03-12 | 2007-10-10 | 河南大学 | Reactive nanometer particle of silica dioxide |
| CN117777904A (en) * | 2024-02-27 | 2024-03-29 | 湖南高瑞电源材料有限公司 | Positive electrode fluorine-free binder material, and preparation method and application thereof |
| CN117777904B (en) * | 2024-02-27 | 2024-05-28 | 湖南高瑞电源材料有限公司 | Positive electrode fluorine-free binder material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1298778C (en) | 2007-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1417249A (en) | Composite polyolefin/sio2 nano particle and its prepn | |
| CN1304436C (en) | Process for preparing reaction functional macromolecule/Al2O3 nano composite particles | |
| CN1289535C (en) | Polymerizable compounds and uses thereof | |
| CN106634089B (en) | A kind of ultraviolet-curing paint and preparation method thereof based on carbon nanotube | |
| CN1662590A (en) | Carbon nanotube-filled composites | |
| CN102241866B (en) | Transparent acrylic acid silicone resin nano composite material and preparation method thereof | |
| CN1276930C (en) | Method for preparing high solid ingredient for polymer nano particle | |
| CN101050258A (en) | An amphipathic polymer, preparation method and application | |
| CN1757668A (en) | High molecule/calcium carbonate nanometer particles, functional particles and prepn. method thereof | |
| CN1660917A (en) | Modification method for graft polymerization of acrylic ester of silicane coupled to Nano SiO2 | |
| CN1246351C (en) | Nano macromolecule microball of epoxy function type cross-linked nucleocapsid structure and preparation process thereof | |
| CN100336834C (en) | Process for preparing micro capsule of imitating active fine emulsion polymerizing by oil-soluble initiating agent | |
| CN102140217A (en) | Preparation method and use of polyacrylate/silica solution composite material | |
| CN1298778C (en) | Carboxyl functional polymer/SiO2 composite nanometer particle and preparing method thereof | |
| CN1693317A (en) | Process for preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent | |
| CN1258540C (en) | Macromolecule/A12O3 nano complex particle preparation method | |
| CN1258570C (en) | Sulfonic acid functional macromolecular/SiO2 composite nano-particles and process for preparing same | |
| CN1775819A (en) | Method for preparing nano silicon dioxide-acrylate polymeric microball material | |
| CN1218969C (en) | Composite nano epoxy functional polymer/SiO2 particle and its prepn process | |
| CN1246352C (en) | Nano macromolecule microball of carboxy function type cross-linked nucleocapsid structure and preparation process thereof | |
| CN1258544C (en) | Nano macromolecule microball of carboxy function type cross-linked nucleocapsid structure and preparation process thereof | |
| CN1246346C (en) | Process for preparing carboxyl functional macromolecular/SiO2 composite nano-particles | |
| CN1279068C (en) | Crosslinked core-shell structure nano-polymer microsphere and its preparation method | |
| CN1257924C (en) | C9 maleic anhydride copolymer and its preparation method | |
| CN1202148C (en) | Process for preparing acrylic latex with agglomeration |
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: 20070207 Termination date: 20101219 |