CN1557876A - Sulfonic acid functional macromolecular/SiO2 composite nano-particles and process for preparing same - Google Patents
Sulfonic acid functional macromolecular/SiO2 composite nano-particles and process for preparing same Download PDFInfo
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- CN1557876A CN1557876A CNA2004100007473A CN200410000747A CN1557876A CN 1557876 A CN1557876 A CN 1557876A CN A2004100007473 A CNA2004100007473 A CN A2004100007473A CN 200410000747 A CN200410000747 A CN 200410000747A CN 1557876 A CN1557876 A CN 1557876A
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Abstract
The present invention belongs to the field of polymer material technology. Nano silica grain, coupling agent, organic olefin monomer and olefin monomer containing sulfonic radical or sulfonate radical as materials are polymerized in soap-free emulsion with water as medium or soap-free suspension polymerized to prepare the composite functional nano sulfonic polymer/SiO2 particle. The product is spherical particle with inorganic nano SiO2 as core, organic polyolefin as shell and sulfonic radical as surface functional group, and has particle size smaller than 100 nm. The present invention has lowered production cost and easy purification of product, and may meet high purity requirement. The introduction of sulfonic radical results in high chemical reaction activity and ionizing capacity and thus raised application value.
Description
Technical field
The present invention relates to a kind of sulfonate functional type polymer/SiO
2Composite nanoparticle and preparation method thereof belongs to technical field of polymer materials.
Background technology
Polymer/inorganic powder nano-complex particle is owing to have inorganic nano-particle and organic macromolecule characteristic concurrently, thereby can be widely used in numerous areas such as macromolecular material, chemical industry, biology, medical science, microelectronics, in Nano-technology Development, have very important potentiality using value.Conventional letex polymerization or suspension polymerization are the important means of synthetic this class nano-complex particle.
The applicant is once at the patent of having applied for (application number: 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, the synthetic employing of this nano-complex particle be conventional letex polymerization or suspension polymerization, the use of emulsifying agent or dispersion agent has greatly improved production cost on the one hand, and the more important thing is and make it to be subjected to bigger restriction in the Application for Field that product purity is had relatively high expectations for product separation purifies and purification has brought big difficulty.Epoxy-functional belongs to non-ionic type functional group simultaneously, does not possess ionizing power, thereby also has been subjected to bigger restriction in its application of the Ionized occasion of numerous needs.
Summary of the invention
The purpose of this invention is to provide a kind of sulfonate functional type polymer/SiO
2Composite nanoparticle and preparation method thereof, this method intend selecting for use have can and the inorganic particulate surface or can and importing at SiO
2The monomer of the functional group reactions on the particle surface, by soap-free polymerization reaction means, make it at first to be grafted on the inorganic nano-particle sub-surface and form polymer covering layer, introduce at the polymer overmold laminar surface then and have the very sulfonate functional groups of extensive chemical reactive behavior and broad reaction range, and the formation of the former coating layer and latter sulfonic acid functional group's introducing are finished simultaneously, have improved production efficiency greatly.Soap-free polymerization method of the present invention is not owing to additionally use emulsifying agent, can solve in the production technique in the past because the cost that the use of emulsifying agent brings improves, product separation purifies problems such as purification difficult is bigger, make product can be competent at the Application Areas very high purity requirement; And guarantee to have between polymer layer and the inorganic particulate surface stronger chemical bond and connect, can solve the problem that coating layer that cladding nanometer particle in the past in use exists is easy to come off; Simultaneously, the introducing of sulfonic acid surfactant base 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 while sulfonic group broadness and being easy to Ionized characteristic has 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, make its using value obtain the raising of matter.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 sulfonate functional 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 sulfonate functional groups 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 emulsifier-free emulsion polymerization that carries out of medium or the method for not having soap suspension polymerization are prepared from water:
1) olefinic monomer: 100 parts by weight;
2) contain sulfonic group or sulphonate-base functional group olefinic monomer: 3～30 parts;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21～30wt% of particle:
5) initiator: 0.1～3 part.
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; In described olefinic monomer employing alpha-olefin such as 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.
Sulfonic group or the sulphonate-base functional group olefinic monomer of containing of the present invention 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 sulfonate functional groups of formula (b) expression; Perhaps 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 sulphonate-base functional group of formula (c) expression.
M
=Li
Or Na
Or K
Or NH
4
Should contain a carbon carbon unsaturated double-bond (C=C) at least in the coupling agent molecule structure described in the present invention, 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.
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 water miscible persulfuric acid salt, hydroperoxide kind material or oil-soluble azo class, peroxide material.Can adopt Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or dibenzoyl peroxide, or the redox system formed with ferrous salt, sulphite, thiosulphate respectively of hydrogen peroxide, dibenzoyl peroxide.
A kind of sulfonate functional type polymer/SiO provided by the invention
2The sub-emulsifier-free emulsion polymerization method of composite nano particle is characterized in that, this method is a raw material with following material:
1) olefinic monomer: 100 parts by weight;
2) contain sulfonic group or sulphonate-base functional group olefinic monomer: 3～30 parts;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21～30wt% of particle;
5) water soluble starter: 0.1～3 part;
Concrete processing step is as follows:
(1), adopt dry method or wet method with SiO by the proportioning in the described raw material
2Particle with coupling agent treatment after, join and make it in the described olefinic monomer to mix and be uniformly dispersed;
(2) described mixture is joined the olefinic monomer that contains deionized water and contain sulfonic group or sulphonate-base functional group and be warming up in advance and form uniform milk sap in 40 ℃～50 ℃ the reactor, in same reactor, add 50～80% of whole water soluble starters, and make it to be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(3) add remaining water soluble starter, 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 sulfonate functional type polymer/SiO that the present invention proposes
2Composite nano particle.
The present invention also provides a kind of preparation sulfonate functional type polymer/SiO
2The no soap suspension polymerization of composite nano particle is characterized in that, this method is a raw material with following material:
1) olefinic monomer: 100 parts by weight;
2) contain sulfonic group or sulphonate-base functional group olefinic monomer: 3～30 parts;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21～30wt% of particle;
5) oil-soluble initiator: 0.1～3 part;
Concrete processing step is as follows:
(1) by the proportioning in the described raw material, with SiO
2Particle joins it in olefinic monomer with 50～80% of whole oil-soluble initiators after adopting dry method or wet processing with coupling agent, makes it to mix and be uniformly dispersed;
(2) described mixture is joined the olefinic monomer that contains deionized water and contain sulfonic group or sulphonate-base functional group and be warming up in advance and form uniform milk sap 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 remaining oil-soluble 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 sulfonate functional type polymer/SiO that the present invention proposes
2Composite nano particle.
Sulfonate functional type polymer/SiO that the present invention proposes
2Composite nano particle and preparation method thereof does not additionally use emulsifying agent, has significantly reduced production cost, is easy to product separation simultaneously and purifies purification, makes product can be widely used in the field very high to purity requirement; Pass through at polymer/SiO simultaneously
2The composite nano particle sub-surface is introduced sulfonate functional groups, 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.Sulfonic group functional macromolecule/SiO of the present invention
2Composite nanoparticle, all connect between its nucleocapsid with chemical bond, solved the problem that coating layer that cladding nanometer particle in the past in use exists is easy to come off, and 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 have been solved in preparation, its overall yield of reaction is generally more than 90%, and percentage of grafting can be pressed monomer and SiO between hundreds thousand of percentage tens of
2The ratio adjustment, grafting efficiency is general all more than 90%.What is more important, this sulfonic group functional macromolecule/SiO
2The particle diameter of composite nano particle is less than 100nm, and the sulfonate functional groups on its particle surface have very high chemical reactivity, can ionization; In addition, this sulfonic group functional macromolecule/SiO
2The preparation manipulation of composite nanoparticle is simple, easily realizes suitability for industrialized production, and the product of making is stable existence for a long time, also can be dried to pulverulence, is easy to store and use.These characteristics will make sulfonic group functional macromolecule/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: original SiO
2(a), PS/SiO
2Nano-complex particle (b) and poly-(1-tetradecylene base sulfonic acid)/polystyrene/SiO
2The infrared spectrum of nano-complex particle (c).
Fig. 2 (a): original SiO
2Electron micrograph.
Fig. 2 (b): poly-(1-tetradecylene base sulfonic acid)/polystyrene/SiO
2The electron micrograph of nano-complex particle.
Fig. 3: poly-(1-tetradecylene base sulfonic acid)/polystyrene/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
2, take by weighing 4 parts and be added in 100 parts of styrene monomers after dry process with 5wt%KH-570 silane type coupling agent, stirring and ultrasonic dispersing are even.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 370 parts of deionized waters, 7 parts of 1-tetradecylene base sodium sulfonates, be warming up to 40 ℃ and make it stirring and dissolving after, add monomers and SiO down in 50 ℃
2Mixture.Then, add 80% of the initiator solution that is made into by 0.5 part of water soluble starter ammonium persulphate and 75 parts of deionized waters, temperature is risen to 82 ℃ of reactions 1.5 hours.Be warming up to 90 ℃, add the residue water soluble initiator solution, continue reaction postcooling discharging in 0.5 hour.Part emulsion after the discharging gets the white powder 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 97.1% as calculated, uses the chloroform extracting after 12 hours on exsiccant composite nano particle, and recording its percentage of grafting is 2765%, and grafting efficiency is 98.2%.Its infrared spectra is seen Fig. 1 (SiO
2Nanoparticle and poly-(the 1-tetradecylene base sulfonic acid)/polystyrene/SiO after extracting
2The infrared spectrum of nano-complex particle), on spectrogram, show tangible PS, SiO
2With the characteristic peak of poly-(1-tetradecylene base sulfonic acid), illustrate that PS and poly-(1-tetradecylene base sulfonic acid) have been grafted on SiO fully
2On the surface.As can be seen from Figures 2 and 3, its size distribution is in 60～70nm scope.
Embodiment 2: change the vinylbenzene among the embodiment 1 butyl acrylate of equivalent into, be reflected at and carried out under 60 ℃ 8 hours, add residue water soluble starter afterreaction and finished in 2 hours, all the other prescriptions are identical with embodiment 1 with step.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 94.6%, 2723% and 96.7%, and size distribution is 60～70nm.
Embodiment 3: change the vinylbenzene among the embodiment 1 into the isobutyl diene of identical gross weight and the mixture of methyl methacrylate (half and half), 50 ℃ add 50% of whole initiators down, be reflected at and carried out under 95 ℃ 0.5 hour, all the other prescriptions are identical with embodiment 1 with step.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 93.8%, 2579% and 91.6%, and size distribution is 60～70nm.
Embodiment 4: with the SiO among the embodiment 1
2Addition be increased to 40 parts by 4 parts, the KH-570 consumption is 30wt%, and adopts wet processing; The total consumption of initiator ammonium persulfate is 0.1 part, and 50 ℃ of 0.08 parts of adding down wherein, adds remaining 0.02 part in the time of 90 ℃, and all the other are filled a prescription with identical with embodiment 1.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 90.5%, 341% and 89.3%, and size distribution is 70～80nm.
Embodiment 5: with the SiO among the embodiment 1
2Addition reduce to 0.1 part by 4 parts, the KH-570 consumption is 1wt%, the total consumption of initiator ammonium persulfate is 3 parts, and 50 ℃ of 1.5 parts of adding down wherein, adds remaining 1.5 parts in the time of 90 ℃, all the other prescriptions are identical with example 1.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 98.5%, 106783% and 98.8%, and size distribution is 60～70nm.
Embodiment 6: change the sulfonic olefinic monomer that has among the embodiment 1 into 1-laurylene base Phenylsulfonic acid, consumption is kept to 3 parts, and all the other prescriptions are identical with embodiment 1.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 90.4%, 2402% and 88.6%, and size distribution is 70～80nm.
Embodiment 7: change the sulfonic olefinic monomer that has among the embodiment 1 into 1-octadecylene base potassium sulfonate, consumption increases to 30 parts, and KH-570 type coupling agent is changed into the boron aluminic acid ester type coupling agent of measuring, and all the other prescriptions are identical with embodiment 1.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 97.8%, 2966% and 86.7%, and size distribution is 40～50nm.
Embodiment 8: with SiO
2, after dry process, take by weighing 0.1 part and be added in 100 parts of styrene monomers with the oleic acid base aluminic acid ester type coupling agent of 1wt%, add 1.5 parts of oil-soluble initiator Diisopropyl azodicarboxylates again, stir and ultrasonic dispersing even.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 370 parts of deionized waters, 3 parts of 1-tetradecylene base sodium sulfonates, be warming up to 40 ℃ and make it stirring and dissolving after, add vinylbenzene, SiO down in 50 ℃
2Mixture with Diisopropyl azodicarboxylate.Temperature is risen to 60 ℃ of reactions 8 hours.Be warming up to 90 ℃, add 1.5 parts of Diisopropyl azodicarboxylates again, continue reaction postcooling discharging in 2 hours.Emulsion after the discharging gets the white powder product after breakdown of emulsion, washing, drying, the productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 91.7%, 2593% and 92.1%, and size distribution is 60～70nm.
Embodiment 9: with SiO
2, after wet processing, take by weighing 40 parts and be added in 100 parts of styrene monomers with the KH-570 type coupling agent of 30wt%, add 0.08 part of oil-soluble initiator dibenzoyl peroxide again, stir and ultrasonic dispersing even.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 370 parts of deionized waters, 30 parts of 1-tetradecylene base sodium sulfonates, be warming up to 40 ℃ and make it stirring and dissolving after, add vinylbenzene, SiO down in 50 ℃
2Mixture with dibenzoyl peroxide.Temperature is risen to 95 ℃ of reactions 0.5 hour.And then add 0.02 part of dibenzoyl peroxide, continue reaction postcooling discharging in 2 hours.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 93.2%, 2658% and 94.4%, 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 adds excessive 1-tetradecylene base sodium sulfonate (50 parts), and the productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 89.7%, 584% and 14.8% (very low), and size distribution is 40～70nm (it is wide to distribute).
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 1-tetradecylene base sodium sulfonates are mixed in disposable together adding, system generation breakdown of emulsion.
In above each example, example 1,2,3,4,5,6,7 belongs to the method for emulsifier-free emulsion polymerization, and example 8,9 belongs to the method for no soap 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 (9)
1. sulfonate functional 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 sulfonate functional groups 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 emulsifier-free emulsion polymerization that carries out of medium or the method for not having soap suspension polymerization are prepared from water:
1) olefinic monomer: 100 parts by weight;
2) contain sulfonic group or sulphonate-base functional group olefinic monomer: 3～30 parts;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21～30wt% of particle;
5) initiator: 0.1～3 part.
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 in molecular structure.
3. according to described composite nano particle of claim 2, it is characterized in that: described olefinic monomer adopts alpha-olefin, is selected from vinylbenzene, vinylchlorid, vinyl cyanide, acrylate or the methacrylic ester one or more; Described diene hydrocarbons adopts diolefine, is selected from suitable divinyl, isobutyl diene, the isoprene one or more.
4. according to described composite nano particle of claim 1, it is characterized in that: described sulfonic group or the sulphonate-base functional group olefinic monomer of containing, be meant and in molecular structure, contain simultaneously, perhaps 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 sulphonate-base functional group of formula (c) expression with the represented carbon carbon unsaturated double-bond of chemical structure skeleton symbol (a) with the olefines material of the sulfonate functional groups of formula (b) expression.
5. according to described composite nano particle of claim 1, it is characterized in that: described coupling agent, be meant and contain a carbon carbon unsaturated double-bond in the molecular structure at least, one or more in employing 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.
6. according to described composite nano particle of claim 1, it is characterized in that: described initiator is meant under 40～95 ℃ of conditions, also can produce free radical causes olefinic monomer polymeric material to have 30～35kcal/mol ionic dissociation energy, comprises water miscible persulfuric acid salt, hydroperoxide kind material or oil-soluble azo class, peroxide material.
7. according to the described composite nano particle of claim 6, it is characterized in that: described water soluble starter is Potassium Persulphate, ammonium persulphate; Described oil-soluble initiator is a kind of in Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) or the dibenzoyl peroxide; The perhaps redox system of forming with ferrous salt, sulphite, thiosulphate respectively for hydrogen peroxide, dibenzoyl peroxide.
8. emulsifier-free emulsion polymerization method for preparing composite nanoparticle as claimed in claim 1 is characterized in that this method is a raw material with following material:
1) olefinic monomer: 100 parts by weight;
2) contain sulfonic group or sulphonate-base functional group olefinic monomer: 3～30 parts;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21～30wt% of particle;
5) water soluble starter: 0.1～3 part;
Concrete processing step is as follows:
(1), adopt dry method or wet method with SiO by the proportioning in the described raw material
2Particle with coupling agent treatment after, join and make it in the described olefinic monomer to mix and be uniformly dispersed;
(2) described mixture is joined the olefinic monomer that contains deionized water and contain sulfonic group or sulphonate-base functional group and be warming up in advance and form uniform milk sap in 40 ℃～50 ℃ the reactor, in same reactor, add 50～80% of whole water soluble starters, and make it to be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(3) add remaining water soluble starter, 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 sulfonate functional type polymer/SiO that the present invention proposes
2Composite nano particle.
9. one kind prepares sulfonate functional type polymer/SiO as claimed in claim 1
2The no soap suspension polymerization of composite nano particle is characterized in that, this method is a raw material with following material:
1) olefinic monomer: 100 parts by weight;
2) contain sulfonic group or sulphonate-base functional group olefinic monomer: 3～30 parts;
3) SiO
2Particle: 0.1～40 part;
4) coupling agent: account for SiO
21～30wt% of particle;
5) oil-soluble initiator: 0.1～3 part;
Concrete processing step is as follows:
(1) by the proportioning in the described raw material, with SiO
2Particle joins it in olefinic monomer with 50～80% of whole oil-soluble initiators after adopting dry method or wet processing with coupling agent, makes it to mix and be uniformly dispersed;
(2) described mixture is joined the olefinic monomer that contains deionized water and contain sulfonic group or sulphonate-base functional group and be warming up in advance and form uniform milk sap 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 remaining oil-soluble 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 sulfonate functional type polymer/SiO that the present invention proposes
2Composite nano particle.
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|---|---|---|---|
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|---|---|---|---|
| CN 200410000747 CN1258570C (en) | 2004-01-16 | 2004-01-16 | Sulfonic acid functional macromolecular/SiO2 composite nano-particles and process for preparing same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013533342A (en) * | 2010-06-24 | 2013-08-22 | スリーエム イノベイティブ プロパティズ カンパニー | Polymerizable composition not containing organic emulsifier, polymer and production method thereof |
| CN106902870A (en) * | 2017-02-21 | 2017-06-30 | 湖北硒诺唯新功能化硅胶材料有限公司 | Functionalization material and its production technology with use |
-
2004
- 2004-01-16 CN CN 200410000747 patent/CN1258570C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013533342A (en) * | 2010-06-24 | 2013-08-22 | スリーエム イノベイティブ プロパティズ カンパニー | Polymerizable composition not containing organic emulsifier, polymer and production method thereof |
| US10954318B2 (en) | 2010-06-24 | 2021-03-23 | 3M Innovative Properties Company | Polymerizable compositions free of organic emulsifier and polymers and methods of making thereof |
| CN106902870A (en) * | 2017-02-21 | 2017-06-30 | 湖北硒诺唯新功能化硅胶材料有限公司 | Functionalization material and its production technology with use |
| CN106902870B (en) * | 2017-02-21 | 2018-08-21 | 湖北硒诺唯新功能化硅胶材料有限公司 | Functionalization material and its production technology and use |
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| Publication number | Publication date |
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| CN1258570C (en) | 2006-06-07 |
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