CN1246346C - Process for preparing carboxyl functional macromolecular/SiO2 composite nano-particles - Google Patents
Process for preparing carboxyl functional macromolecular/SiO2 composite nano-particles Download PDFInfo
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- CN1246346C CN1246346C CN 200410000746 CN200410000746A CN1246346C CN 1246346 C CN1246346 C CN 1246346C CN 200410000746 CN200410000746 CN 200410000746 CN 200410000746 A CN200410000746 A CN 200410000746A CN 1246346 C CN1246346 C CN 1246346C
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Abstract
The present invention relates to a method for preparing carboxyl functional macromolecule / SiO2 composite nanometer particles, which belongs to the technical field of polymer materials. The carboxyl functional macromolecule / SiO2 composite nanometer particle is prepared by in the way that nanometer SiO2 particles, resin acceptor, organic alkene monomers, and olefin monomers with carboxyl or carboxylate functional groups are used as raw materials; the raw materials are prepared into the carboxyl functional macromolecule / SiO2 composite nanometer particles through soap-free emulsion with water as media, or soap-free suspension polymerization. The composite nanometer particle has the structural characteristics that inorganic nanometer SiO2 is used as a kernel, an organic olefin polymer is a casing and carboxyl is a spheroidal particle of a surface functional group; the particle diameter is uniform and is smaller than 100 nanometers. The composite nanometer particle has the advantages of high chemical reaction activity, high application value and wide application area. The composite nanometer particle can be easily purified because of non soap polymerization. The preparing method is suitable for various fields with high purity requirements, greatly reduces the production cost and has a profound application prospect in the development of nanotechnology.
Description
Technical field
The soap-free polymerization method that the present invention relates to prepares carboxyl function type polymer/SiO
2Composite nanoparticle 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 (application number: 200310121706.5) successfully carboxyl functional group has been introduced polymer/SiO in the patent of application on December 19th, 2003
2Particle surface, the polymer/SiO of this carboxyl-functional
2The nano-complex particle surface has the very high and ionogenic carboxyl functional group of chemical reactivity, has very high using value in reactive blending or association area.But, the synthetic employing of this nano-complex particle be conventional letex polymerization or suspension polymerization, using to product separation purification and purification of emulsifying agent or dispersion agent brought big difficulty, makes it to be subjected to bigger restriction in the Application for Field that product purity is had relatively high expectations.Simultaneously, increased the difficulty of purifying and meaned and improved production cost, and the use of emulsifying agent or dispersion agent itself makes that promptly production cost increases greatly.
Summary of the invention
The objective of the invention is to adopt the synthetic a kind of carboxyl function type polymer/SiO of method of soap-free polymerization
2Composite nanoparticle, 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, be introduced in the reactive blending carboxyl functional group that can react with multiple macromolecule matrix at the polymer overmold laminar surface then.Soap-free polymerization method of the present invention is not additionally used emulsifying agent, serve as emulsifying agent but choose the monomer that has carboxyl functional group that to participate in polyreaction, final this monomer has saved the step of washing emulsifying agent by being reacted into the part for composite particles.So both 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, and make product can be competent at the Application Areas very high purity requirement; Can solve the problem that coating layer that cladding nanometer particle in the past in use exists is easy to come off again, guarantee to have between polymer layer and the inorganic particulate surface stronger chemical bond and connected; Simultaneously, particle surface have can with the carboxyl functional group of multiple substance reaction, improved its using value greatly.The soap-free polymerization method that the present invention adopts prepares polymer/inorganic composite type nanoparticle, 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
2The emulsifier-free emulsion polymerization method of composite nanoparticle is characterized in that: this method is a raw material with following material,
Olefinic monomer: 100 parts by weight;
Contain carboxyl or carboxylate group functional group olefinic monomer: 2～50 parts;
SiO
2Particle: 0.1～40 part;
Coupling agent: account for SiO
21～30wt% of particle;
Water soluble starter: 0.1～3 part;
Its concrete processing step is as follows:
(1) presses proportioning in the above-mentioned raw materials with SiO
2Particle uses coupling agent after dry method or wet processing, joins to make it in the olefinic monomer to mix and be uniformly dispersed;
With quality is that 50～150% water-soluble alkalis for the olefinic monomer quality that contains carboxyl functional group add and to contain carboxyl
(2) be that the water-soluble alkali adding that contains the olefinic monomer 50～150% of carboxyl functional group contains in the olefinic monomer of carboxyl functional group with quality; If what adopt is the olefinic monomer that contains carboxylate group, then do not need to add alkali;
(3) add 20～80% of the total material that obtains by step (2) in 40 ℃～50 ℃ the reactor to containing deionized water and being warming up to, add the mixture that step (1) obtains then and form uniform milk sap;
(4) in same reactor, add 50～80% of whole water soluble starters, and be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(5) in same reactor, add the remaining material that obtains by step (2), continue reaction 0.5～8 hour;
(6) add remaining water soluble starter, reacted 0.5～2 hour;
(7) behind the cooling discharging, adding quality is the water soluble acid that contains the olefinic monomer quality 50～150% of carboxyl functional group, after breakdown of emulsion, washing, drying etc. are handled, can obtain carboxyl function type polymer/SiO that the present invention proposes then
2Composite nano particle.
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.
Carboxyl or the carboxylate group 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 carboxyl functional group 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 carboxylate group functional group of formula (c) expression.
-COOH -(b)
-COO
M
-(c) M
=Li
Or Na
Or K
Or NH
4
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.
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.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.
Another kind of preparation carboxyl function type polymer/SiO provided by the invention
2The composite nano particle submethod is characterized in that it being to adopt no soap suspension polymerization, and this method is a raw material with following material,
Olefinic monomer: 100 parts by weight;
Contain carboxyl or carboxylate group functional group olefinic monomer: 2～50 parts;
SiO
2Particle: 0.1～40 part.
Coupling agent: account for SiO
21～30wt% of particle;
Oil-soluble initiator: 0.1～3 part;
Its processing step is as follows:
(1) presses proportioning in the above-mentioned raw materials with SiO
2Particle, joins in the described olefinic monomer with 50～80% of whole oil-soluble initiators after dry method or wet processing with coupling agent, makes it to mix and be uniformly dispersed;
(2) be that the water-soluble alkali adding that contains the olefinic monomer 50～150% of carboxyl functional group contains in the olefinic monomer of carboxyl functional group with quality; If what adopt is the olefinic monomer that contains carboxylate group, then do not need to add alkali;
(3) add 20～80% of the total material that obtains by step (2) in 40 ℃～50 ℃ the reactor to containing deionized water and being warming up to, add the mixture that step (1) obtains then and form uniform milk sap;
(4) emulsion system that step (3) is obtained is warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(5) in same reactor, add the remaining material that obtains by step (2), continue reaction 0.5～8 hour;
(6) add remaining oil-soluble initiator, reacted 0.5～2 hour;
(7) behind the cooling discharging, add quantitative water soluble acid.After breakdown of emulsion, washing, drying etc. are handled, can obtain carboxyl function type polymer/SiO that the present invention proposes then
2Composite nano particle.
Carboxyl function type polymer/SiO that the present invention proposes
2Composite nano particle and preparation method thereof, additionally do not use emulsifying agent, significantly reduced production cost, play a part that becomes particle after the olefinic monomer reaction that has carboxyl functional group of emulsifying effect simultaneously, saved the step of washing emulsifying agent, be easy to product separation and purify purification, improved production efficiency, and made product can be widely used in the field very high purity requirement; Pass through at polymer/SiO simultaneously
2The composite nano particle sub-surface is introduced carboxyl functional group, makes it to have good reactive behavior in macromolecular material filling-modified.Carboxyl function type polymer/SiO that the present invention is prepared
2Composite nanoparticle has with inorganic nano SiO
2Be nuclear, the olefinic organic hydrocarbon polymer is a shell, carboxyl is the spheroidal particle constitutional features of surface functional group, 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 carboxyl function type polymer/SiO
2The particle diameter of composite nano particle is less than 100nm, and the carboxyl functional group on its particle surface has very high chemical reactivity; 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 steady in a long-termly be preserved, and also can be dried to pulverulence, is easy to store and use.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: the poly-oleic acid (POA) that obtains under the different oleic acid additions/polystyrene (PS)/SiO
2Nano-complex particle and original SiO
2Infrared spectrum: (a), 50 parts of oleic acid (is 100 parts in vinylbenzene, down with); (b), 30 parts; (c), 10 parts; (d), 2 parts; (e), PS/SiO
2Nano-complex particle.
Fig. 2 (a): original SiO
2Electron micrograph.
Fig. 2 (b): POA/PS/SiO
2The electron micrograph of nano-complex particle.
Fig. 3: POA/PS/SiO
2The grain size distribution curve of nano-complex particle.
The following examples 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 is also even with ultrasonic dispersing.The solution that is made into 50 parts of oleic acid with by 25 parts of sodium hydroxide and 100 parts of deionized waters is evenly mixed.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 370 parts of deionized waters, be warming up to 40 ℃, add the mixture of 1/5th above-mentioned oleic acid and sodium hydroxide then.Add above-mentioned monomer 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 hour.In system, dropwise add remaining 4/5ths the oleic acid and the mixture of sodium hydroxide, dripped afterreaction 1 hour.Be warming up to 90 ℃, add remaining initiator solution, continue reaction postcooling discharging in 0.5 hour, add 75 parts of concentrated hydrochloric acids then.The part emulsion is got 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 90.4% as calculated, uses the chloroform extracting after 12 hours on exsiccant composite nano particle, and recording its percentage of grafting is 3328%, and grafting efficiency is 84.3%.Its infrared spectra is seen Fig. 1 (a), shows tangible PS, SiO on spectrogram
2With the characteristic peak of POA, illustrate that PS and POA have been grafted on SiO fully
2On the surface.As can be seen from Figures 2 and 3, its size distribution is in 50～60nm scope.
Embodiment 2: 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 is also even with ultrasonic dispersing.10 parts of sodium acrylates are dissolved in 30 parts of deionized waters.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 370 parts of deionized waters, be warming up to 40 ℃, add 80% sodium acrylate solution, add above-mentioned monomer and SiO down in 50 ℃ again
2Mixture.Then, add 50% 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 2 hours.Add remaining vinylformic acid again and receive solution, reacted 1 hour.Be warming up to 90 ℃, add remaining initiator solution, continue reaction postcooling discharging in 2 hours, add 25 part 20% sulphuric acid soln again.Part emulsion after the discharging also obtains the white powder product after breakdown of emulsion, washing, drying, another part emulsion places test tube, also finds to store after 6 months deposited phenomenon not occur.Product total recovery 92.1%, percentage of grafting 2626%, grafting efficiency 90.7%, size distribution is in 50～60nm scope.
Embodiment 3: the butyl acrylate that the vinylbenzene among the embodiment 1 is changed into equivalent, reaction was carried out under 60 ℃ 8 hours earlier, continue to react 8 hours after dripping residue 4/5ths oleic acid and sodium hydroxide mixing solutions, be warming up to 95 ℃, add residue initiator afterreaction and finished in 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 89.2%, 3478% and 88.1%, and size distribution is 50～60nm.
Embodiment 4: change the vinylbenzene among the embodiment 1 into the isobutyl diene of identical gross weight and the mixture of methyl methacrylate (half and half), each step was all carried out under 95 ℃ 0.5 hour in the reaction, and 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 86.4%, 3639% and 92.2%, and size distribution is 50～60nm.
Embodiment 5: with the SiO among the embodiment 2
2Addition reduce to 0.1 part by 4 parts, the KH-570 consumption is 1wt%, adopts 2 parts of 1-lauroleic acid sodium to replace sodium acrylates, the total consumption of initiator ammonium persulfate is 0.1 part, 50 ℃ of 0.05 parts of adding down wherein add remaining 0.05 part in the time of 90 ℃, all the other prescriptions are identical with example 2.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 94.7%, 111389% and 96.2%, and size distribution is 40～50nm.
Embodiment 6: 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 ammonium persulphate is 3 parts, 50 ℃ add 2.4 parts down, 90 ℃ add remaining 0.6 part down, 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 87.1%, 354% and 89.8%, and size distribution is 60～70nm.
Embodiment 7: with SiO
2, take by weighing 0.1 part and be added in 100 parts of styrene monomers after dry process with 1wt% boron aluminic acid ester type coupling agent, add 0.08 part of oil-soluble initiator Diisopropyl azodicarboxylate, stirring is also even with ultrasonic dispersing.The solution that is made into 2 parts of oleic acid with by 3 parts of sodium hydroxide and 10 parts of deionized waters is evenly mixed.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 370 parts of deionized waters, be warming up to 40 ℃, add then above-mentioned oleic acid and sodium hydroxide mixture 80%.Add above-mentioned monomer and SiO down in 50 ℃
2Mixture.Then temperature is risen to 60 ℃ of reactions 8 hours.The mixture that dropwise adds remaining oleic acid and sodium hydroxide in system dripped afterreaction 8 hours.Be warming up to 90 ℃, add 0.02 part of Diisopropyl azodicarboxylate, continue reaction postcooling discharging in 0.5 hour, add 3 parts of concentrated hydrochloric acids then.Emulsion is got the white powder product after breakdown of emulsion, washing, drying, the productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 94.5%, 3612% and 91.5%, and size distribution is 50～60nm.
Embodiment 8: with SiO
2, take by weighing 40 parts and be added in 100 parts of styrene monomers after wet processing with 30wt% oleic acid base aluminic acid ester type coupling agent, add 1.5 parts of oil-soluble initiator dibenzoyl peroxide, stirring is also even with ultrasonic dispersing.The solution that is made into 50 parts of oleic acid with by 25 parts of sodium hydroxide and 100 parts of deionized waters is evenly mixed.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 370 parts of deionized waters, be warming up to 40 ℃, add then above-mentioned oleic acid and sodium hydroxide mixture 20%.Add above-mentioned monomer and SiO down in 50 ℃
2Mixture.Then temperature is risen to 95 ℃ of reactions 0.5 hour.In system, add the mixture of remaining oleic acid and sodium hydroxide, reacted then 0.5 hour.Add 1.5 parts of dibenzoyl peroxide, continue reaction postcooling discharging in 0.5 hour, add 25 parts of concentrated hydrochloric acids then.Emulsion is got the white powder product after breakdown of emulsion, washing, drying, the productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 90.6%, 3489% and 88.4%, and size distribution is 50～60nm.
Embodiment 9: with SiO
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, add 0.4 part of oil-soluble initiator dibenzoyl peroxide, stirring is also even with ultrasonic dispersing.10 parts of sodium acrylates are dissolved in 30 parts of deionized waters.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 370 parts of deionized waters, be warming up to 40 ℃, add 80% sodium acrylate solution, add above-mentioned monomer and SiO down in 50 ℃ again
2Mixture.Then, temperature is risen to 82 ℃ of reactions 2 hours.Add remaining vinylformic acid again and receive solution, reacted 1 hour.Be warming up to 90 ℃, add 0.1 part of dibenzoyl peroxide, continue reaction postcooling discharging in 2 hours, add 15 part 20% sulphuric acid soln again.Part emulsion after the discharging also obtains 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%, 3628% and 91.9%, and size distribution is 50～60nm.
Comparative example 1: the preparation method is with embodiment 1, but with the disposable whole adding systems of the mixing solutions of oleic acid and sodium hydroxide, the slight breakdown of emulsion of system, the productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 64.1% (very low), 462% and 11.7% (very low), and size distribution is 30～120nm (it is very wide to distribute).
Comparative example 2: the preparation method is with embodiment 1, but do not add sodium hydroxide in the oleic acid, and serious breakdown of emulsion and precipitation take place in reaction process system.
Comparative example 3: the preparation method is with example 2, but SiO
2Do not use coupling agent treatment, the discovery system precipitates in reaction process.
In above each embodiment, embodiment 1,2,3,4,5,6 belongs to the method for emulsifier-free emulsion polymerization, and embodiment 7,8,9 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 (6)
1. carboxyl function type polymer/SiO
2The emulsifier-free emulsion polymerization method of composite nanoparticle is characterized in that: this method is a raw material with following material,
Olefinic monomer: 100 parts by weight;
Contain carboxyl or carboxylate group functional group olefinic monomer: 2～50 parts;
SiO
2Particle: 0.1～40 part;
Coupling agent: account for SiO
21～30wt% of particle;
Water soluble starter: 0.1～3 part;
Described olefinic monomer is meant monoolefine, the diene hydrocarbons that contains carbon carbon unsaturated double-bond in molecular structure; Described monoolefine adopts one or more in alpha-olefin, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester; Described diene hydrocarbons adopts diolefine; Described diolefine adopts one or more in suitable divinyl, isobutyl diene, the isoprene;
Its concrete processing step is as follows:
(1) presses proportioning in the above-mentioned raw materials with SiO
2Particle uses coupling agent after dry method or wet processing, joins to make it in the olefinic monomer to mix and be uniformly dispersed;
(2) be that the water-soluble alkali adding that contains the olefinic monomer 50～150% of carboxyl functional group contains in the olefinic monomer of carboxyl functional group with quality; If what adopt is the olefinic monomer that contains carboxylate group, then do not need to add alkali;
(3) add 20～80% of the total material that obtains by step (2) in 40 ℃～50 ℃ the reactor to containing deionized water and being warming up to, add the mixture that step (1) obtains then and form uniform milk sap;
(4) in same reactor, add 50～80% of whole water soluble starters, and be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(5) in same reactor, add the remaining material that obtains by step (2), continue reaction 0.5～8 hour;
(6) add remaining water soluble starter, reacted 0.5～2 hour;
(7) behind the cooling discharging, adding quality is the water soluble acid that contains the olefinic monomer quality 50～150% of carboxyl functional group, after breakdown of emulsion, washing, drying treatment, promptly obtains carboxyl function type polymer/SiO then
2Composite nanoparticle.
2. according to the described carboxyl function type of claim 1 polymer/SiO
2The emulsifier-free emulsion polymerization method of composite nanoparticle, it is characterized in that: described carboxyl or the carboxylate group 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 carboxylate group 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 carboxyl functional group of formula (b) expression.
-COOH -(b)
-COO
M
-(c) M
=Li
Or Na
Or K
Or NH
4
3. according to the described carboxyl function type of claim 1 polymer/SiO
2The emulsifier-free emulsion polymerization method of composite nanoparticle is characterized in that: described coupling agent adopts one or more 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.
4. according to the described carboxyl function type of claim 1 polymer/SiO
2The emulsifier-free emulsion polymerization method of composite nanoparticle, 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.
5. according to the described carboxyl function type of claim 4 polymer/SiO
2The emulsifier-free emulsion polymerization method of composite nanoparticle is characterized in that: described initiator is a kind of in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or the 2,2'-Azobis(2,4-dimethylvaleronitrile); The perhaps redox system of forming with ferrous salt, sulphite, thiosulphate respectively for hydrogen peroxide, dibenzoyl peroxide.
6. carboxyl function type polymer/SiO
2The no soap suspension polymerization of composite nanoparticle is characterized in that: this method is a raw material with following material,
Olefinic monomer: 100 parts by weight
Contain carboxyl or carboxylate group functional group olefinic monomer: 2～50 parts
SiO
2Particle: 0.1～40 part
Coupling agent: account for SiO
21～30wt% of particle
Oil-soluble initiator: 0.1～3 part
Described olefinic monomer is meant monoolefine, the diene hydrocarbons that contains carbon carbon unsaturated double-bond in molecular structure; Described monoolefine adopts one or more in alpha-olefin, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester; Described diene hydrocarbons adopts diolefine; Described diolefine adopts one or more in suitable divinyl, isobutyl diene, the isoprene;
Its processing step is as follows:
(1) presses proportioning in the above-mentioned raw materials with SiO
2Particle, joins in the described olefinic monomer with 50～80% of whole oil-soluble initiators after dry method or wet processing with coupling agent, makes it to mix and be uniformly dispersed;
(2) be that the water-soluble alkali adding that contains the olefinic monomer 50～150% of carboxyl functional group contains in the olefinic monomer of carboxyl functional group with quality; If what adopt is the olefinic monomer that contains carboxylate group, then do not need to add alkali;
(3) add 20～80% of the total material that obtains by step (2) in 40 ℃～50 ℃ the reactor to containing deionized water and being warming up to, add the mixture that step (1) obtains then and form uniform milk sap;
(4) emulsion system that step (3) is obtained is warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～8 hour;
(5) in same reactor, add the remaining material that obtains by step (2), continue reaction 0.5～8 hour;
(6) add remaining oil-soluble initiator, reacted 0.5～2 hour;
(7) behind the cooling discharging, add water soluble acid and make system be adjusted to slightly acidic, after breakdown of emulsion, washing, drying treatment, promptly obtain carboxyl function type polymer/SiO then
2Composite nanoparticle.
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