CN1246351C - Nano macromolecule microball of epoxy function type cross-linked nucleocapsid structure and preparation process thereof - Google Patents
Nano macromolecule microball of epoxy function type cross-linked nucleocapsid structure and preparation process thereof Download PDFInfo
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Abstract
The present invention relates to nanometer macromolecule microspheres with epoxy function type cross-linked core-shell structures and a preparation method thereof, which belong to the technical field of macromolecule materials. The present invention uses a plurality of alkene monomers and alkene monomers with epoxy functional groups as raw materials, under the condition of the existence of emulsifying agents and initiating agents, the nanometer macromolecule microsphere with an epoxy function type cross-linked core-shell structure is prepared by emulsion using water as media or suspension polymerization. Inner parts of cores and shells of the production are in cross-linked structures, the cores and the shells are connected by a chemical bond, the epoxy functional groups are grafted on surfaces of the microspheres, and grain diameter is less than 100 nm. The present invention obtains a plurality of epoxy function type nanometer macromolecule microspheres with different physical and chemical characteristics by changing the composite of the cores and the shells, and the present invention has very high freedom on the selection of structural design. The present invention solves problems that in past, core-shell macromolecule microspheres have no nanometer sizes, and the cores and the shells are linear polymer; simultaneously, the present invention enhances the interface compatibility of the microspheres in the process of filling with macromolecule matrix by introducing the epoxy functional groups on surfaces, and widens application fields.
Description
Technical field
The present invention relates to nano polymer microspheres of a kind of cross-linked core-shell structure and preparation method thereof, belong to technical field of polymer materials.
Background technology
Preparation with nano polymer microspheres of nucleocapsid structure has received numerous investigators' concern in recent years.In preparation, application need according to different field, composition that can be by changing microballoon nuclear and shell and proportioning synthesize have different structure, the nano polymer microspheres of different physicochemical properties, have very high design freedom, thereby have wide prospect in the research of nanometer novel material with in using.
The inventor is at the Chinese patent (application number: successfully synthesized cross-linked core-shell structure nano polymer microsphere 200410000745.4) of application on January 16th, 2004.This invention has solved forefathers do not possess nanoscale about the nucleocapsid polymer microsphere problem, also solve forefathers' synthetic nucleocapsid polymer microsphere general kernel or shell and be linear macromolecule, microballoon swelling ratio in solvent is very low, the problem that good solubility-resistence energy and oil absorptiveness are also relatively poor has also been simplified technology simultaneously, has been improved productive rate.But, this Nano microsphere is when the filled high polymer matrix, only exist the interface interaction based on physical compatibility on the interface between microballoon and the macromolecule matrix, this interface interaction is very weak, make microballoon in matrix dispersion and be subjected to bigger influence with the effect that combines of matrix.
Thereby, the present invention plans to have the epoxy-functional of very high chemical reactivity and introduces cross-linked core-shell nano polymer microspheres surface by the method for chemical graft, make it when the filled high polymer matrix, can and then form chemical bond, thereby greatly strengthen interfacial interaction and the dispersiveness of microballoon in matrix by surface functional group and matrix generation chemical reaction.
Summary of the invention
The purpose of this invention is to provide a kind of epoxide function type cross-linked core-shell structure nano polymer microsphere and preparation method thereof, this method is incited somebody to action in the past on the one hand, and the yardstick of polymer core-shell particles is reduced in the nanoscale scope, make the nuclear and the shell inside of product all form crosslinking structure simultaneously, and introduce the epoxy-functional that can react with multiple macromolecule matrix at microsphere surface, thereby not only solved preparation and had the problem of nanoscale nucleocapsid latex particle, nucleocapsid latex particle good solubility-resistence and the relatively poor problem of oil absorbency have in the past also been solved, the more important thing is introducing by surperficial epoxy-functional make this microballoon when the filled high polymer matrix and the interfacial interaction between the matrix obtained the raising of matter, finally can show various good properties in actual applications.The present invention can design nuclear and the composition of shell and structure, yardstick as required, thereby obtain various the have soft nuclear duricrust of different physicochemical properties and application value or the nanoparticles of stone soft shell type, on form and structure Design, have very high degree of freedom, greatly widened its Application Areas and application prospect.
The objective of the invention is to be achieved through the following technical solutions:
Epoxide function type cross-linked core-shell structure nano polymer microsphere, it is characterized in that: this microballoon has nucleocapsid structure, and the connection structure is all presented in the inner and shell inside of nuclear, examine with shell between be connected by chemical bond, and epoxy-functional grafts on microsphere surface, and its particle diameter is less than 100nm; It is a raw material with following material, by being that medium adopts the method for letex polymerization or suspension polymerization to be prepared from water:
1) monoolefine monomer: count 100 parts (other each components are carried out quantitatively as benchmark) with the total mass of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
2) multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
3) have the olefinic monomer of epoxy-functional: 0.1～50 part;
3) emulsifying agent: 2～7 parts;
4) initiator: 0.5～2 part.
Monoolefine of the present invention is meant one or more in the alpha-olefin that contains a carbon-carbon double bond (C=C) in the molecule, vinylbenzene, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester, and should guarantee that stratum nucleare monoolefine monomer and shell monoolefine monomer are incomplete same; Described Polyene Hydrocarbons material is meant the material that contains two or more carbon-carbon double bonds in the molecule, is selected from suitable divinyl, isobutyl diene, isoprene, Vinylstyrene, the trihydroxy methyl propane trimethyl acrylate one or more.
The olefinic monomer that has epoxy-functional of the present invention is meant the olefinic monomer that contains simultaneously in the molecule with the represented epoxy-functional of the represented carbon-carbon double bond of chemical structure skeleton symbol (a) and chemical structure skeleton symbol (b), can select in propenyl glycidyl ether, butenyl glycidyl ether, glycidyl acrylate, the glycidyl methacrylate one or more for use.
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 brometo de amonio, 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 alkyl benzene sulphonate (ABS) potassium.
C. non-ionic type: comprise C3～10 polyoxyethylene alkylphenol ethers, C2～18 fatty alcohol-polyoxyethylene ether, the single C11 of polyoxyethylene sorbitol～18 fatty acid esters or polyoxyethylene sorbitol three C11～18 fatty acid esters; Described polyoxyethylated ethylene oxide number of repeat unit is 4～50.
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 be selected from 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 preparation method of a kind of epoxide function type cross-linked core-shell structure nano polymer microsphere provided by the invention is characterized in that adopting emulsion polymerisation process, and this method is a raw material with following material:
Monoolefine monomer: count 100 parts (other each components are carried out quantitatively as benchmark) with the total mass of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
Multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
The olefinic monomer that has epoxy-functional: 0.1～50 part;
Emulsifying agent: 2～7 parts;
Water soluble starter: 0.5～2 part;
The concrete processing step of this method is as follows:
(1) preparation of stratum nucleare:
(a) by the above-mentioned raw materials proportioning with the stratum nucleare multi-olefin monomer of the stratum nucleare monoolefine monomer of 30-70% and 30-70% mixed evenly put into to contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor form uniform emulsion, in this reactor, add and account for the water soluble starter of total amount 20～80%, and make it to be warming up to 70 ℃～95 ℃ temperature range internal reaction 0.5～2 hour;
(b) evenly add in the above-mentioned system remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer are mixed, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(2) preparation of shell:
Select for use the monoolefine monomer different as in shell monoolefine monomer and the reacted system of the mixed evenly adding step (b) of shell multi-olefin monomer according to described proportion of raw materials with the stratum nucleare monoolefine monomer, add the residue water soluble starter then, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(3) grafting of epoxy-functional:
According to evenly adding the olefinic monomer that has epoxy-functional in the system of described proportioning raw materials after step (2) reaction finishes, continue reaction 0.5～3 hour then.Behind the cooling discharging, and after breakdown of emulsion, washing and drying step are handled, can obtain the epoxide function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes.
The present invention also provides the preparation method of another kind of epoxide function type cross-linked core-shell structure nano polymer microsphere, it is characterized in that adopting suspension polymerization to be prepared, and this method is a raw material with following material:
Monoolefine monomer: count 100 parts (other each components are carried out quantitatively as benchmark) with the total mass of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
Multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
The olefinic monomer that has epoxy-functional: 0.1～50 part;
Emulsifying agent: 2～7 parts;
Oil-soluble initiator: 0.5～2 part;
The concrete processing step of this method is as follows:
(1) preparation of stratum nucleare:
(a) by the proportioning in the described raw material with the oil-soluble initiator of the stratum nucleare multi-olefin monomer of the stratum nucleare monoolefine monomer of 30-70%, 30-70% and 20-80% mixed evenly put into to contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor form uniform milk sap, and make it to be warming up to 70 ℃～95 ℃ temperature range internal reaction 0.5～2 hour;
(b) evenly add in the above-mentioned system remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer are mixed, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(2) preparation of shell:
Select for use the monoolefine monomer different as shell monoolefine monomer and shell multi-olefin monomer with remaining oil-soluble initiator is mixed evenly adds in the reacted system of step (b) by the proportioning in the described raw material, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour with the stratum nucleare monoolefine monomer;
(3) grafting of epoxy-functional:
According to evenly adding the olefinic monomer that has epoxy-functional in the system of described proportioning raw materials after step (2) reaction finishes, continue reaction 0.5～3 hour then.Behind the cooling discharging, and after breakdown of emulsion, washing and drying step are handled, can obtain the epoxide function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes.
Epoxide function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes and preparation method thereof, under the condition that emulsifying agent and initiator exist by the polymer microsphere that with water is that the emulsion or the suspension polymerization of medium has obtained having nucleocapsid structure, nanoscale, surface have epoxy-functional.Be connected with chemical bond between the epoxide function type cross-linked core-shell structure nano polymer microsphere of the present invention, stratum nucleare and shell, have very strong interface interaction; Nuclear all is crosslinked form with shell inside; Epoxy-functional is connected microsphere surface by chemical graft.Not only solve preparation and had the problem of nanoscale nucleocapsid latex particle, nucleocapsid latex particle good solubility-resistence and the relatively poor problem of oil absorbency have in the past also been solved, the more important thing is introducing by surperficial epoxy-functional make this microballoon when the filled high polymer matrix and the interfacial interaction between the matrix obtained the raising of matter, finally can show various good properties in actual applications.Can design simultaneously the composition of nuclear and shell and structure, yardstick as required, thereby obtain various epoxide function type nano polymer microspheres with different physicochemical properties and application value, and place nucleocapsid structure for a long time and can not reverse, on form and structure Design, have very high degree of freedom.Overall yield of reaction and gel fraction are generally all more than 90%.In addition, preparation technology is simple to operate, easily realizes suitability for industrialized production, and the epoxide function type nano polymer microspheres of making can be preserved for a long time, also can be dried to pulverulence, is easy to store and use.The particle diameter of this epoxide function type cross-linked core-shell structure nano polymer microsphere has the property that nanoscale and nanoparticle possess all less than 100nm.These characteristics will make cross-linked core-shell structure nano polymer microsphere of the present invention have purposes widely in from now on nanometer material science and technical development.
Description of drawings
Fig. 1 is the electron micrograph of epoxide function type cross-linked core-shell nano-high molecule PBA/PMMA/PGMA microballoon.
Fig. 2 is the grain size distribution curve figure of epoxide function type cross-linked core-shell nano-high molecule PBA/PMMA/PGMA microballoon.
Embodiment
The invention will be further described below by embodiment, understands the present invention with further.
Embodiment 1: 70 parts of butyl acrylates (BA) are evenly mixed as the stratum nucleare multi-olefin monomer, stand-by as stratum nucleare monoolefine monomer and 7 parts of trihydroxy methyl propane trimethyl acrylates (TM).In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 360 parts of deionized waters, 4 parts of sodium laurylsulfonates (SDS) and 0.5 part of nonylphenol Soxylat A 25-7, be warming up to 50 ℃, add the uniform emulsion of 30% formation of the miscellany for preparing previously.Add 80% of the initiator solution that is made into by 0.5 part of water soluble starter ammonium persulphate and 72 parts of deionized waters then, temperature is risen to 82 ℃ of reactions 1.5 hours.In system, drip the remaining mixture for preparing previously then, waited to drip afterreaction 1.5 hours.Add remaining initiator solution again, in system, drip mixture, dripped afterreaction 1.5 hours by 30 parts of methyl methacrylates (MMA) (as the shell monoolefine monomer) and 3 parts of trihydroxy methyl propane trimethyl acrylates (TM) (as the shell multi-olefin monomer).In this system, drip 10 parts of glycidyl methacrylate then, reacted again after dripping 1 hour.Be warming up to 90 ℃, 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, find that storage deposited phenomenon do not occur after 6 months, and electron microscopic observation finds that down the nucleocapsid structure of microsphere particles still keeps better, and reversal development does not take place.Reaction yield 92.1% as calculated, uses the chloroform extracting after 12 hours exsiccant cross-linked core-shell structure nano polymer microsphere, and recording gel fraction is 94.2%, illustrates that nucleocapsid all exists with crosslinked form.Can be clear that the nucleocapsid structure of expection from Fig. 1 (electromicroscopic photograph of PBA/PMMA/PGMA), as can be seen, its median size is in 40～50nm scope for Fig. 2 (the size distribution test of PBA/PMMA/PGMA) simultaneously, and size distribution is very narrow.
Embodiment 2: 30 parts of vinylbenzene (St) are evenly mixed as the stratum nucleare multi-olefin monomer, stand-by as stratum nucleare monoolefine monomer and 3 parts of Vinylstyrenes (DVB).In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 360 parts of deionized waters, 6.5 parts of sodium laurylsulfonates (SDS) and 0.5 part of nonylphenol Soxylat A 25-7, be warming up to 50 ℃, add the uniform emulsion of 70% formation of the miscellany for preparing previously.Add 20% of the initiator solution that is made into by 0.5 part of water soluble starter ammonium persulphate and 72 parts of deionized waters then, temperature is risen to 82 ℃ of reactions 40 minutes.In system, add the remaining mixture for preparing previously then, continue reaction 1 hour.Add whole remaining initiator solutions again, in system, add mixture, reacted then 2 hours by 70 parts of butyl acrylates (BA) (as the shell monoolefine monomer) and 7 parts of Vinylstyrenes (DVB) (as the shell multi-olefin monomer).Add 10 parts of butenyl glycidyl ethers then, reacted 1 hour.Be warming up to 90 ℃, 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, also find to store after 6 months deposited phenomenon not occur, and electron microscopic observation finds that down the nucleocapsid structure of microsphere particles still keeps better, and reversal development does not take place.Reaction yield 90.9% as calculated, uses the chloroform extracting after 12 hours exsiccant cross-linked core-shell structure nano polymer microsphere, and recording gel fraction is 91.2%, also illustrates that nucleocapsid all exists with crosslinked form.The size distribution test shows that its median size is 40～50nm, and size distribution is very narrow.
Embodiment 3: with the butyl acrylate of quality such as the stratum nucleare monoolefine monomer among the embodiment 1 becomes and the mixture of methyl acrylate, the shell monoolefine monomer is become the mixture of St and MMA, wherein MMA and St mass ratio are 2: 1, and changing the consumption of glycidyl methacrylate into 0.1 part, all the other prescriptions are identical with example 1.Products therefrom productive rate 94.1%, gel fraction 90.6%, size distribution 40～50nm.
Embodiment 4: the stratum nucleare monoolefine monomer among the embodiment 1 is become with the methyl acrylate of measuring, initiator amount increases to 2 parts, change the consumption of glycidyl methacrylate into 50 parts, speed with 3 seconds/dropwise adds, system temperature is 70 ℃, each following reaction times of step is respectively 2 hours, 3 hours, 3 hours, 3 hours, and saves at last and be warming up to 90 ℃ and react 0.5 hour this step, and all the other prescriptions are identical with embodiment 1.Products therefrom productive rate 92.5%, gel fraction 91.6%, size distribution 40～50nm.
Embodiment 5: stratum nucleare multi-olefin monomer among the embodiment 2 and shell multi-olefin monomer are all become 1 part of N, the N-methylene diacrylamine, emulsifying agent adopts 2 parts of sodium lauryl sulphate, system temperature is 95 ℃, and each following reaction times of step was respectively 0.5 hour, 1 hour, 1 hour, 0.5 hour.All the other prescriptions are identical with embodiment 2.Products therefrom productive rate 93.4%, gel fraction 89.7%, size distribution 40～50nm.
Embodiment 6: 30 parts of vinylbenzene are evenly mixed as the stratum nucleare multi-olefin monomer, stand-by as stratum nucleare monoolefine monomer and 20 parts of isoprene.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 360 parts of deionized waters, 2 parts of tripropyl ammonio methacrylates, be warming up to 50 ℃, the 70% and 0.1 part of oil-soluble initiator Diisopropyl azodicarboxylate that adds the miscellany for preparing previously forms uniform milk sap.Temperature is risen to 70 ℃ of reactions 2 hours.In system, add the mixture of remaining vinylbenzene and isoprene then, continue reaction 3 hours.In system, add mixture again, reacted then 3 hours by whole remaining initiators, 70 parts of butyl acrylates (BA) (as the shell monoolefine monomer) and 30 parts of low polyhutadiene (as the shell multi-olefin monomer).Add 0.1 part of propenyl glycidyl ether again, reacted 3 hours, be warming up to 90 ℃, continue reaction postcooling discharging in 0.5 hour.Products therefrom productive rate 89.4%, gel fraction 92.3%, size distribution 40～50nm.
Embodiment 7: the mixture that the emulsifying agent among the embodiment 6 is adopted 6 parts of tripropyl benzyl ammonium chlorides and 1 part of 12 fatty alcohol-polyoxyethylene ether, Diisopropyl azodicarboxylate is changed into the oil-soluble initiator dibenzoyl peroxide of measuring, and change propenyl glycidyl ether consumption into 50 parts, speed with 3 seconds/dropwise adds, system temperature is 95 ℃, each step time was respectively 0.5 hour, 1 hour, 1 hour, 0.5 hour, and save and be warming up to 0.5 hour this step of 90 ℃ of afterreactions, all the other prescriptions are identical with embodiment 6.Products therefrom productive rate 92.6%, gel fraction 91.8%, size distribution 40～50nm.
Embodiment 8: change the tripropyl ammonio methacrylate among the embodiment 6 into Sodium dodecylbenzene sulfonate, the stratum nucleare monoolefine monomer changes 70 parts of BA into, the shell monoolefine monomer changes 30 parts of MMA into, and initiator is that all the other prescriptions are identical with embodiment 1 with the oil-soluble initiator Diisopropyl azodicarboxylate of amount.Products therefrom productive rate 95.8%, gel fraction 91.5%, size distribution 40～50nm.
Embodiment 9: the emulsifying agent among the embodiment 6 is changed into the tripropyl methyl brometo de amonio of measuring, and initiator is 2 parts of oil-soluble initiator BPO, and all the other prescriptions are identical with embodiment 1.Products therefrom productive rate 90.6%, gel fraction 94.0%, size distribution 40～50nm.
Comparative example 1: the preparation method is with example 1, but all do not add multi-olefin monomer among BA and the MMA, and products therefrom productive rate 82.1%, gel fraction are 0, size distribution 30～60nm.The product microballoon is shaped as irregular sphere simultaneously, and size distribution is wide.
Comparative example 2: the preparation method does not add emulsifying agent with example 2, system water oil content layer, and polymerization begins the back and block precipitation occurs.
In above each embodiment, embodiment 1,2,3,4,5 belongs to method of emulsion polymerization, and embodiment 6,7,8,9 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, any change in claims scope of the present invention all should be thought to be included in the scope of claims.
Claims (8)
1. epoxide function type cross-linked core-shell structure nano polymer microsphere, it is characterized in that: this microballoon has nucleocapsid structure, and the connection structure is all presented in the inner and shell inside of nuclear, examine with shell between be connected by chemical bond, and epoxy-functional grafts on microsphere surface, and its particle diameter is less than 100nm; It is a raw material with following material, by being that medium adopts the method for letex polymerization or suspension polymerization to be prepared from water:
1) monoolefine monomer: 100 parts of the total mass meters of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
2) multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
3) have the olefinic monomer of epoxy-functional: 0.1～50 part;
4) emulsifying agent: 2～7 parts;
5) initiator: 0.5～2 part;
Described monoolefine monomer is meant one or more in the alpha-olefin that only contains a carbon-carbon double bond in the molecule, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester, and should guarantee that stratum nucleare monoolefine monomer and shell monoolefine monomer are incomplete same; Described multi-olefin monomer is meant the material that contains two or more carbon-carbon double bonds in the molecule.
2. according to the described epoxide function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: the described material that contains two or more carbon-carbon double bonds is selected from along in the divinyl, isobutyl diene, isoprene, Vinylstyrene, trihydroxy methyl propane trimethyl acrylate one or more.
3. according to the described epoxide function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: the described olefinic monomer that has epoxy-functional is meant the olefinic monomer that contains simultaneously in the molecule with the represented epoxy-functional of the represented carbon-carbon double bond of chemical structure skeleton symbol (a) and chemical structure skeleton symbol (b), is selected from propenyl glycidyl ether, butenyl glycidyl ether, glycidyl acrylate, the glycidyl methacrylate one or more.
4. according to the described epoxide function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: described emulsifying agent adopts one or more in the following material:
A. cationic: as to comprise three C
11～18Alkyl 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 brometo de amonio, 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 alkyl benzene sulphonate (ABS) potassium;
C. non-ionic type: comprise C3～10 polyoxyethylene alkylphenol ethers, C2～18 fatty alcohol-polyoxyethylene ether, the single C11 of polyoxyethylene sorbitol～18 fatty acid esters or polyoxyethylene sorbitol three C11～18 fatty acid esters; Described polyoxyethylated ethylene oxide number of repeat unit is 4～50.
5. according to the described epoxide function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: described initiator is meant can be under 40～95 ℃ of conditions, have 30～35kcal/mol ionic dissociation energy and can produce free radical to cause olefinic monomer polymeric water-soluble persulfuric acid salt material or oil-soluble azo class, peroxide material.
6. according to the described epoxide function type of claim 5 cross-linked core-shell structure nano polymer microsphere, it 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.
7. emulsion polymerisation process for preparing epoxide function type cross-linked core-shell structure nano polymer microsphere as claimed in claim 1, it is characterized in that: this method is a raw material with monoolefine monomer, multi-olefin monomer, the olefinic monomer that has epoxy-functional, emulsifying agent and initiator, and wherein the content of each composition is:
Monoolefine monomer: 100 parts of the total mass meters of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
Multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
The olefinic monomer that has epoxy-functional: 0.1～50 part;
Emulsifying agent: 2～7 parts;
Water soluble starter: 0.5～2 part;
The processing step of this method is as follows:
(1) preparation of stratum nucleare:
(a) by the above-mentioned raw materials proportioning with the stratum nucleare multi-olefin monomer of the stratum nucleare monoolefine monomer of 30-70% and 30-70% mixed evenly put into to contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor form uniform emulsion, in this reactor, add and account for the water soluble starter of total amount 20～80%, and make it to be warming up to 70 ℃～95 ℃ temperature range internal reaction 0.5～2 hour;
(b) evenly add in the above-mentioned system remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer are mixed, said temperature scope internal reaction 1～3 hour;
(2) preparation of shell:
Select for use the monoolefine monomer different as in shell monoolefine monomer and the reacted system of the mixed evenly adding step (b) of shell multi-olefin monomer according to described proportion of raw materials with the stratum nucleare monoolefine monomer, add the residue water soluble starter then, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(3) grafting of epoxy-functional:
According to evenly adding the olefinic monomer that has epoxy-functional in the system of described proportioning raw materials after step (2) reaction finishes, continue reaction 0.5～3 hour then.Behind the cooling discharging, and after breakdown of emulsion, washing and drying step are handled, can obtain the epoxide function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes.
8. one kind prepares the suspension polymerization of epoxide function type cross-linked core-shell structure nano polymer microsphere according to claim 1, it is characterized in that: this method is a raw material with monoolefine monomer, multi-olefin monomer, the olefinic monomer that has epoxy-functional, emulsifying agent and initiator, and wherein the content of each composition is:
Monoolefine monomer: 100 parts of the total mass meters of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
Multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
The olefinic monomer that has epoxy-functional: 0.1～50 part;
Emulsifying agent: 2～7 parts;
Oil-soluble initiator: 0.5～2 part;
The processing step of this method is as follows:
(1) preparation of stratum nucleare:
(a) by the proportioning in the described raw material with the oil-soluble initiator of the stratum nucleare multi-olefin monomer of the stratum nucleare monoolefine monomer of 30-70%, 30-70% and 20-80% mixed evenly put into to contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor form uniform milk sap, and make it to be warming up to 70 ℃～95 ℃ temperature range internal reaction 0.5～2 hour;
(b) with in the mixed reaction system that evenly adds above-mentioned steps (a) of remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(2) preparation of shell:
Select for use the monoolefine monomer different as shell monoolefine monomer and shell multi-olefin monomer with remaining oil-soluble initiator is mixed evenly joins in the reacted system of step (b) by the proportioning in the described raw material, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour with the stratum nucleare monoolefine monomer;
(3) grafting of epoxy-functional:
According to evenly adding the olefinic monomer that has epoxy-functional in the system of described proportioning raw materials after step (2) reaction finishes, continue reaction 0.5～3 hour then.Behind the cooling discharging, and after breakdown of emulsion, washing and drying step are handled, can obtain the epoxide function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes.
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| US9061900B2 (en) | 2005-12-16 | 2015-06-23 | Bridgestone Corporation | Combined use of liquid polymer and polymeric nanoparticles for rubber applications |
| US8288473B2 (en) | 2005-12-19 | 2012-10-16 | Bridgestone Corporation | Disk-like nanoparticles |
| US8697775B2 (en) | 2005-12-20 | 2014-04-15 | Bridgestone Corporation | Vulcanizable nanoparticles having a core with a high glass transition temperature |
| US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
| WO2008014464A2 (en) | 2006-07-28 | 2008-01-31 | Bridgestone Corporation | Polymeric core-shell nanoparticles with interphase region |
| US7597959B2 (en) | 2006-12-19 | 2009-10-06 | Bridgestone Corporation | Core-shell fluorescent nanoparticles |
| US8846819B2 (en) | 2008-12-31 | 2014-09-30 | Bridgestone Corporation | Core-first nanoparticle formation process, nanoparticle, and composition |
| US9062144B2 (en) | 2009-04-03 | 2015-06-23 | Bridgestone Corporation | Hairy polymeric nanoparticles with first and second shell block polymer arms |
| US9115222B2 (en) | 2009-12-29 | 2015-08-25 | Bridgestone Corporation | Well defined, highly crosslinked nanoparticles and method for making same |
| US9428604B1 (en) | 2011-12-30 | 2016-08-30 | Bridgestone Corporation | Nanoparticle fillers and methods of mixing into elastomers |
| CN104341546B (en) * | 2013-07-25 | 2016-06-08 | 中国石油天然气股份有限公司 | A kind of preparation method of shelly oil absorbing polymer microsphere |
| CN115322707B (en) * | 2022-09-14 | 2023-09-05 | 武汉弘毅共聚新材料科技有限公司 | Water-based VC glue for medicine packaging and preparation method thereof |
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