CN101585898B - Resin microparticle in multilayered structure, dispersion liquid and preparation method thereof - Google Patents
Resin microparticle in multilayered structure, dispersion liquid and preparation method thereof Download PDFInfo
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- CN101585898B CN101585898B CN2008100249926A CN200810024992A CN101585898B CN 101585898 B CN101585898 B CN 101585898B CN 2008100249926 A CN2008100249926 A CN 2008100249926A CN 200810024992 A CN200810024992 A CN 200810024992A CN 101585898 B CN101585898 B CN 101585898B
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Abstract
The invention discloses a resin microparticle in a multilayered structure. Thermoplastic resin is arranged at the outermost layer of the resin microparticle, and thermosetting resin is arranged at theinnermost layer of the resin microparticle. The resin microparticle has an average grain diameter of 0.01-50 microns and a specific surface area of 5-50 m<2>/g, and a mass ratio of the thermoplasticresin to the thermosetting resin is from 0.1/99.9 to 50/50. The resin microparticle in the multilayered structure not only has the advantages of common thermosetting resin microparticles, but also canbe dispersed in organic solvent and an aqueous solution containing a surface active agent because of the thermoplastic resin covered on the outer layer.
Description
Technical field
The invention belongs to technical field of macromolecules, be specifically related to resin microparticle, its dispersion liquid of a kind of multilayered structure and preparation method thereof.
Background technology
High molecular particle is claimed polymeric microball material again, be meant diameter in nanometer to micron order, be shaped as sphere or type spheroidal macromolecular material or polymer composite.Because its special size and pattern, specific surface area are big, monodispersity, be easy to preparation and modification and to characteristics such as biocompatibility are adjustable, play special and crucial effect in many important fields, thereby receive People more and more concern how.Polymeric microball material is mainly used in high-technology fields such as engineering in medicine, biotechnology, electronic information.But for the superfine particle, also exist surface energy greatly, very easily reunite, be difficult for being dispersed in matrix or the medium problem of solvent.The method that solves particle aggregation and bad dispersibility is that it is carried out modification.Thereby become one of main direction of studying of micropartical preparation through the resin microparticle that surface-treated obtains multilayered structure.
The method that with the monomer is feedstock production high molecular polymer microballoon mainly is divided into letex polymerization, no saponification letex polymerization, dispersion polymerization, precipitation polymerization, suspension polymerization, micro emulsion polymerization, mini-emulsion polymerization and seeding polymerization.Diverse ways can prepare the microballoon of different size.Each preparing method's polymerization process all can be divided into nucleation process and nuclear developmental process, and these two processes are important factors of control microballoon size, distribution of sizes and polymeric constituent.We know that its molecular structure of thermosetting resin is the build crosslinking structure in addition, and it comprises most condensation resins.The advantage of thermosetting resin is that thermotolerance is high, and pressurized is not yielding etc.Thermosetting resin mainly contains phenolic, epoxy type, amino-type, unsaturated polyester type and silicon ether type etc.Advantages such as the thermosetting resin micropartical has had thermosetting resin and atomic advantage concurrently, has sticking power high like epoxy resin micro-particle, and the high and wear resistance of hardness is good.The corresponding emulsion of thermosetting resin micropartical general using obtains through particle is carried out aftertreatment.Patent CN101117390A has reported a kind of method for preparation of waterborne epoxy emulsion, and the aqueous epoxy resin emulsion that this invention proposes, is prepared through phase inversion technique through reactive emulsifier and cationic surfactant emulsification by epoxy resin.The aqueous epoxy emulsion that this patent obtains is hydrophilic, and does not pass through surface-treated, can not be dispersed in the organic solvent well.Patent CN1911920A has reported 2-aminoethyl sulfonic acid modified aqueous epoxy resin and preparation method thereof and by the aqueous epoxy emulsion of this aqueous epoxy resins preparation; It is thinner that the aqueous epoxy emulsion of this invention preparation has a particle; Stability of emulsion is high, technical characterstics such as cured product hardness and resistance to impact shock excellent property.Though the epoxy emulsion that this patent prepares through modification, because the emulsion after the modification still is a wetting ability, can not improve its dispersiveness in organic solvent.
Summary of the invention
The purpose of this invention is to provide a kind of resin microparticle that can be dispersed in organic solvent or contain the multilayered structure in the aqueous solution of tensio-active agent.
Another object of the present invention provides a kind of resin microparticle with multilayered structure and is dispersed in organic solvent or contains the dispersion liquid in the aqueous solution of tensio-active agent.
A further object of the invention provides a kind of resin microparticle preparation method of above-mentioned multilayered structure.
The object of the invention can reach through following measure:
A kind of resin microparticle of multilayered structure, the outermost layer of this resin microparticle are thermoplastic resin, and innermost layer is a thermosetting resin, and the mass ratio of wherein said thermoplastic resin and thermosetting resin is 0.1/99.9～50/50, is preferably 0.1/99.9～20/80.This micropartical also contains solidifying agent; Wherein solidifying agent is piperazine, hydrazine, adipic dihydrazide, diethylenetriamine, triethylene tetramine or two aliphatic amides such as (the amino ring of 4-ethyls) or is aromatic amines such as diamino-diphenyl maple or diaminodiphenyl-methane; The content of solidifying agent is 5%～35%, and this atomic median size is 0.01～50 μ m.Micropartical reality of the present invention comprises the structure of thermosetting resin for thermoplastic resin; Outermost layer is a thermoplastic resin; Innermost layer is a thermosetting resin, is the structure that thermoplastic resin and thermosetting resin are entwined each other between the two, also comprises other components in this micropartical; Like solidifying agent etc., its specific surface area is 5～50m
2/ g.
Thermoplastic resin of the present invention is the resin that contains conjugated double bond, is meant that specifically acrylic ester resin, acrylic resin, methacrylic acid ester are that resin, methylacrylic acid are resin, phenylethylene resin series or cyanic acid vinylite.Thermosetting resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin or brominated epoxy resin.
A kind of resin microparticle dispersion liquid of multilayered structure; The resin microparticle that is about to multilayered structure is dispersed in the solvent, and its solvent is one or more in aromatic hydrocarbon solvent, fat hydrocarbon solvent, halogenated hydrocarbon solvent, alcoholic solvent, ether solvent, crassitude ketones solvent or the aqueous solution that contains tensio-active agent.Atomic content is 0.5～5% (weight part per-cent) in the dispersion liquid, and wherein preferred solvent is halogenated hydrocarbon solvent and crassitude ketones solvent.
A kind of preparation method of resin microparticle of multilayered structure; Thermoset micropartical emulsion 50～200 weight parts are joined in the deionized water of 50～200 weight parts, then add the resin monomer that contains conjugated double bond (being olefin(e) acid class ester) of 0.5～2 weight part and the initiator of 0.01～0.05 weight part.The resin monomer that wherein contains conjugated double bond is meant propenoate, methacrylic acid ester, vinylbenzene or cyanic acid ethene etc., and initiator is meant Diisopropyl azodicarboxylate class such as (AIBN) azo or BPO peroxo-two acyl class initiators such as (BPO).Under nitrogen protection, mix, under elevated temperature to 40～100 ℃ (preferred 80～100 ℃) take place polymerization send out should, react after 3～6 hours, filtration, drying obtains the resin microparticle of multilayered structure.Wherein thermoset micropartical emulsion adopts the preparation of phase reversion emulsion process; Specifically be in reaction vessel, to add the emulsifying agent of 80～120 parts by weight of epoxy resin (this epoxy resin can be bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin or brominated epoxy resin) and 16 weight parts (wherein emulsifying agent is a non-ionics; The HLB value is 12～26, mainly comprises polyoxyethylene nonylphenol, T 46155 (4) sorbitan mono-laurate (Tween 21), T 46155 (20) anhydrous sorbitol list hard fatty acid ester (Tween60), T 46155 (20) sorbitan monooleate (Tween 80) or polyethers P65 (PlurnoicP65) etc.).Stir after being warmed up to 60 ℃, stirring velocity be 320rpm (rpm).React after 20 minutes adjustment stirring velocity to 400～700rpm, the deionized water of adding 10～40 weight parts.React after 10～20 minutes, add 10～40 parts by weight of deionized water again; React after 10～20 minutes, add 10～40 parts by weight of deionized water for the third time; React after 10～20 minutes, add aqueous solution of curing agent by the deionized water formation of the solidifying agent (like piperazine, hydrazine, adipic dihydrazide, diethylenetriamine, triethylene tetramine, two (the amino ring of 4-ethyls), diamino-diphenyl maple or diaminodiphenyl-methane etc.) of 10～20 weight parts and 100～120 weight parts.Under 20～30 ℃, 300～350rpm stirs to solidify and promptly obtained the epoxy resin micro-particle emulsion in 20～48 hours.
Surface-treated can change the physicochemical property of particle.It not only can improve dispersiveness and the consistency of superfine particle in matrix or solvent, and can make atomic surface-functionalized, thereby improve the over-all properties of material.For example pigment dyestuff is in surface treatment process; For making its particle surface polarity have good consistency or matching with employed dispersion medium (as being connected material, vehicles, organic solvent etc.); Need when adding surface treatment agent or coating; Usually at first add surface-modifying agent, it be adsorbed on the particle surface with specified substituent (like sulfonic group, amino etc.), add then can with surface-modifying agent with mode bonded surface treatment agents such as chemical bond, pair ion or hydrogen bonds; Make surface treatment agent be adsorbed in surface of pigments more securely, reach the modification purpose of pigment particles.
The resin microparticle that the invention has the beneficial effects as follows this multilayered structure has not only possessed the atomic advantage of ordinary hot thermosetting resin; And because its skin is coated with thermoplastic resin; Can be as the filler of other thermoplastic resins, thus the consistency between the matrix material increased.And this multi-layer resinous particle has covered thermoplastic resin because of skin, thereby can be dispersed in organic solvent and contain in the aqueous solution of tensio-active agent.Can be applicable to the photo-electro-magnetic field after being dispersed with conductive micropartical in this dispersion liquid, as be used for battery, can also be applied to aspects such as polymer catalyst, pharmaceutical carrier as electrode materials.
Description of drawings
The stereoscan photograph of the resin microparticle of the multilayered structure that Fig. 1 obtains for the embodiment of the invention 2.
The transmission electron microscope photo of the resin microparticle of the multilayered structure that Fig. 2 obtains for the embodiment of the invention 2.
The atomic size distribution of thermosetting resin that Fig. 3 obtains for the embodiment of the invention 2 processes (1).Testing tool be Microtrac S3500 Particle Size Analyzer (NIKKISO Company, Japan).
The thermoset micropartical thermogravimetric analysis curve (TGA) that Fig. 4 obtains for the embodiment of the invention 2.
The thermoset micropartical differential scanning calorimeter curve (DSC) that Fig. 5 obtains for the embodiment of the invention 2.
Fig. 6 is a thermoset micropartical infrared spectrum in the embodiment of the invention 2 processes (1) reaction process.
The stereoscan photograph of the resin microparticle of the multilayered structure that Fig. 7 obtains for the embodiment of the invention 4.
The transmission electron microscope photo of the resin microparticle of the multilayered structure that Fig. 8 obtains for the embodiment of the invention 4.
The optical microscope photograph of the resin microparticle of the multilayered structure that Fig. 9 obtains for the embodiment of the invention 7.
The optical microscope photograph of the resin microparticle of the multilayered structure that Figure 10 obtains for Comparative Examples of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed introduction, but embodiment of the present invention is not limited thereto.
Embodiment 1:
Emulsion preparation process (1):
(to call in the following text: emulsifying agent) join in the reaction vessel, 60 ℃ of stirrings, stirring velocity is 320rpm with 100 weight part bisphenol A type epoxy resins (EP828) and 16 weight part polyoxyethylene nonylphenol emulsifying agents.React after 20 minutes, the adjustment stirring velocity adds 20 parts by weight of deionized water to 450rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 10 weight part piperazines and 111.6 parts by weight of deionized water.Under 25 ℃, 320rpm stirs to solidify and promptly obtained epoxy micropartical emulsion in 24 hours.
Surface-treated process (2):
Get the 100 weight part epoxy micropartical emulsions that obtain in (1); 100 parts by weight of deionized water; 1 weight part NSC 20956 and 0.03 weight part BPO (BPO) join in the 250ml there-necked flask; Under room temperature and nitrogen protection, it was mixed in 30 minutes with the 300rpm stirring.Elevated temperature to 80 ℃ makes polymerization reaction take place, stopped reaction after 5 hours.Filter, vacuum-drying obtains the resin microparticle of multilayered structure.Its particle directly is distributed as: 0.05～0.35 μ m, the mass ratio of thermoplastic resin and thermosetting resin is: 3/97.
Dispersion process (3):
The resin microparticle of the multilayered structure that obtains in (2) is dry, take by weighing 1 weight part, join in the toluene that fills 100 weight parts, ultrasonic frequency 55Hz shakes 5min, mixed solution homogeneous transparent.Not having deposition after 12 hours produces.
Embodiment 2:
Emulsion preparation process (1):
100 weight part bisphenol A type epoxy resins (EP828) and 16 weight part emulsifying agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, the adjustment stirring velocity adds 20 parts by weight of deionized water to 500rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 25 ℃, 320rpm stirs to solidify and promptly obtained epoxy micropartical emulsion in 24 hours.
Surface-treated process (2):
Get the 100 weight part epoxy micropartical emulsions that obtain in (1); 100 parts by weight of deionized water; 1 parts by weight of acrylic acid butyl ester and 0.03 weight part BPO join in the 250ml there-necked flask, under nitrogen protection and room temperature, it are mixed in 30 minutes with the 300rpm stirring.Elevated temperature to 80 a ℃ generation polymerization is sent out and is answered stopped reaction after 5 hours.Filter, vacuum-drying obtains the resin microparticle of multilayered structure.Its particle directly is distributed as: 0.05～0.2 μ m, the mass ratio of thermoplastic resin and thermosetting resin is: 2.5/97.5.
Dispersion process (3):
The resin microparticle of the multilayered structure that obtains in (2) is dry, take by weighing 1 weight part, join in the SL 1332 that fills 100 weight parts, ultrasonic frequency 55Hz shakes 5min, mixed solution homogeneous transparent.Not having deposition after 12 hours produces.
Embodiment 3:
Emulsion preparation process (1):
100 weight part bisphenol f type epoxy resins and 16 weight part emulsifying agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 300rpm.React after 20 minutes, the adjustment stirring velocity adds 20 parts by weight of deionized water to 600rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 20 ℃, 320rpm stirs to solidify and promptly obtained epoxy micropartical emulsion in 24 hours.
Surface-treated process (2):
Get the 100 weight part epoxy micropartical emulsions that obtain in (1); 100 parts by weight of deionized water; 1 parts by weight of styrene and 0.04 weight part Diisopropyl azodicarboxylate (AIBN) join in the 250ml there-necked flask, under nitrogen protection and room temperature, it are mixed in 30 minutes with the 300rpm stirring.Elevated temperature to 60 a ℃ generation polymerization is sent out and is answered stopped reaction after 5 hours.Filter, vacuum-drying obtains the resin microparticle of multilayered structure.Its particle directly is distributed as: 0.01～0.2 μ m, the mass ratio of thermoplastic resin and thermosetting resin is: 2.5/97.5
Dispersion process (3):
The resin microparticle of the multilayered structure that obtains in (2) is dry, take by weighing 1 weight part, join in the hexanaphthene that fills 100 weight parts, ultrasonic frequency 55Hz shakes 5min, mixed solution homogeneous transparent.Not having deposition after 12 hours produces.
Embodiment 4:
Emulsion preparation process (1):
100 weight part bisphenol A type epoxy resins (EP828) and 1.1 weight part emulsifying agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, the adjustment stirring velocity adds 20 parts by weight of deionized water to 500rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 20 ℃, 320rpm stirs to solidify and promptly obtained epoxy micropartical emulsion in 24 hours.
Surface-treated process (2):
Get the 100 weight part epoxy micropartical emulsions that obtain in (1); 100 parts by weight of deionized water; 1 parts by weight of acrylic acid butyl ester and 0.03 weight part BPO join in the 250ml there-necked flask, under nitrogen protection and room temperature, it are mixed in 30 minutes with the 300rpm stirring.Elevated temperature to 80 a ℃ generation polymerization is sent out and is answered stopped reaction after 5 hours.Filter, vacuum-drying obtains the resin microparticle of multilayered structure.Its particle directly is distributed as: 5～10 μ m, the mass ratio of thermoplastic resin and thermosetting resin is: 2.5/97.5.
Dispersion process (3):
The resin microparticle of the multilayered structure that obtains in (2) is dry, take by weighing 1 weight part, join in the toluene that fills 100 weight parts ultrasonic frequency 55Hz concussion.Get this mixing solutions with dropper behind the 5min and observe down in opticmicroscope, particle is uniformly dispersed in toluene.
Embodiment 5:
Emulsion preparation process (1):
100 weight part bisphenol-A epoxy resins and 16 weight part emulsifying agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, the adjustment stirring velocity adds 20 parts by weight of deionized water to 500rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 7 weight part piperazines and 111.6 parts by weight of deionized water.Under 20 ℃, 320rpm stirs to solidify and promptly obtained epoxy micropartical emulsion in 24 hours.
Surface-treated process (2):
Get the 100 weight part epoxy micropartical emulsions that obtain in (1); 100 parts by weight of deionized water; 1 weight part methacrylic acid ester and 0.03 weight part BPO join in the 250ml there-necked flask, under nitrogen protection and room temperature, it are mixed in 30 minutes with the 300rpm stirring.Elevated temperature to 80 a ℃ generation polymerization is sent out and is answered stopped reaction after 5 hours.Filter, vacuum-drying obtains the resin microparticle of multilayered structure.Its particle directly is distributed as: 0.05～0.2 μ m, the mass ratio of thermoplastic resin and thermosetting resin is: 2.5/97.5.
Dispersion process (3):
The resin microparticle of the multilayered structure that obtains in (2) is dry, take by weighing 1 weight part, join in the trichloromethane that fills 100 weight parts, ultrasonic frequency 55Hz shakes 5min, mixed solution homogeneous transparent.Not having deposition after 24 hours produces.
Embodiment 6:
Emulsion preparation process (1):
100 weight part bisphenol A type epoxy resins and 16 weight part emulsifying agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, the adjustment stirring velocity adds 20 parts by weight of deionized water to 500rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 20 ℃, 320rpm stirs to solidify and promptly obtained epoxy micropartical emulsion in 24 hours.
Surface-treated process (2):
Get the 100 weight part epoxy micropartical emulsions that obtain in (1); 100 parts by weight of deionized water; 2 parts by weight of acrylic acid butyl esters and 0.04 weight part Diisopropyl azodicarboxylate (AIBN) join in the 250ml there-necked flask, under nitrogen protection and room temperature, it are mixed in 30 minutes with the 300rpm stirring.Elevated temperature to 60 a ℃ generation polymerization is sent out and is answered stopped reaction after 5 hours.Filter, vacuum-drying obtains the resin microparticle of multilayered structure.Its particle directly is distributed as: 0.05～0.2 μ m, the mass ratio of thermoplastic resin and thermosetting resin is: 5/95.
Dispersion process (3):
The resin microparticle of the multilayered structure that obtains in (2) is dry, take by weighing 1 weight part, join in the octane that fills 100 weight parts, ultrasonic frequency 55Hz shakes 5min, mixed solution homogeneous transparent.Not having deposition after 12 hours produces.
Embodiment 7:
Emulsion preparation process (1):
100 weight part bisphenol A type epoxy resins (EP828) and 1.1 weight part emulsifying agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, the adjustment stirring velocity adds 20 parts by weight of deionized water to 500rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 20 ℃, 320rpm stirs to solidify and promptly obtained epoxy micropartical emulsion in 24 hours.
Surface-treated process (2):
Get the 100 weight part epoxy micropartical emulsions that obtain in (1), 100 parts by weight of deionized water, 1 parts by weight of acrylic acid butyl ester and 0.03 weight part BPO join in the 250ml there-necked flask, under room temperature and nitrogen protection, stir and it are mixed in 30 minutes.Elevated temperature to 80 a ℃ generation polymerization is sent out and is answered stopped reaction after 5 hours.Filter, vacuum-drying obtains the resin microparticle of multilayered structure.Its particle directly is distributed as: 5～10 μ m, the mass ratio of thermoplastic resin and thermosetting resin is: 2.5/97.5.Dispersion process (3):
The resin microparticle of the multilayered structure that obtains in (2) is dry, take by weighing 1 weight part, join in the toluene that fills 100 weight parts ultrasonic frequency 55Hz concussion.Get this mixing solutions with dropper behind the 5min and observe down in opticmicroscope, particle is uniformly dispersed in toluene, like Fig. 9.
Comparative Examples:
Emulsion preparation process (1):
100 weight part bisphenol A type epoxy resins (EP828) and 1.1 weight part emulsifying agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, the adjustment stirring velocity adds 20 parts by weight of deionized water to 500rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 20 ℃, 320rpm stirs to solidify and promptly obtained epoxy micropartical emulsion in 24 hours.
Surface-treated process (2):
Get the 100 weight part epoxy micropartical emulsions that obtain in (1), 100 parts by weight of deionized water, 1 parts by weight of acrylic acid butyl ester and 0.03 weight part BPO join in the 250ml there-necked flask, under room temperature and nitrogen protection, stir and it are mixed in 30 minutes.Elevated temperature to 80 a ℃ generation polymerization is sent out and is answered stopped reaction after 5 hours.Filter, vacuum-drying obtains the resin microparticle of multilayered structure.Its particle directly is distributed as: 5～10 μ m, the mass ratio of thermoplastic resin and thermosetting resin is: 2.5/97.5.Dispersion process (3):
The resin microparticle of the multilayered structure that obtains in (2) is dry, take by weighing 1 weight part, join in the deionized water that fills 100 weight parts ultrasonic frequency 55Hz concussion.Get this mixing solutions with dropper behind the 5min and observe down in opticmicroscope, reuniting appears in deionized water in particle, like Figure 10.
Claims (6)
1. the resin microparticle of a multilayered structure, it is characterized in that: the outermost layer of this resin microparticle is a thermoplastic resin, and innermost layer is a thermosetting resin, and the mass ratio of wherein said thermoplastic resin and thermosetting resin is 0.1/99.9～50/50; Also contain solidifying agent in this resin microparticle;
Wherein, described thermosetting resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin or brominated epoxy resin;
Described thermoplastic resin is that acrylic ester resin, acrylic resin, methacrylic acid ester are that resin, methylacrylic acid are resin or phenylethylene resin series.
2. the resin microparticle of multilayered structure according to claim 1, it is characterized in that: the mass ratio of described thermoplastic resin and thermosetting resin is 0.1/99.9～20/80.
3. the resin microparticle of multilayered structure according to claim 1 and 2, it is characterized in that: the median size of this resin microparticle is 0.01～50 μ m.
4. the dispersion liquid of the resin microparticle of a multilayered structure, the solvent that it is characterized in that this micro-dispersed liquid is one or more in aromatic hydrocarbon solvent, fat hydrocarbon solvent, halogenated hydrocarbon solvent, alcoholic solvent, ether solvent, crassitude ketones solvent or the aqueous solution that contains tensio-active agent; The outermost layer of this resin microparticle is a thermoplastic resin, and innermost layer is a thermosetting resin, and the mass ratio of wherein said thermoplastic resin and thermosetting resin is 0.1/99.9～50/50; Also contain solidifying agent in this resin microparticle; Wherein, described thermosetting resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin or brominated epoxy resin; Described thermoplastic resin is that acrylic ester resin, acrylic resin, methacrylic acid ester are that resin, methylacrylic acid are resin or phenylethylene resin series.
5. the preparation method of the resin microparticle of a multilayered structure is characterized in that thermoset micropartical emulsion is added in the deionized water, then adds olefin(e) acid class ester and initiator; Under nitrogen protection, mix; Elevated temperature to 40～100 ℃ take place down polymerization send out should, after reaction stops, filtering; Drying obtains the resin microparticle of multilayered structure; Described thermoset micropartical emulsion is with after epoxy resin and the emulsifier mix, divides 3 times and adds deionized water, behind the emulsion reaction, adds the aqueous solution of curing agent reaction again and makes; Described epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin or brominated epoxy resin.
6. the preparation method of the resin microparticle of multilayered structure according to claim 5; It is characterized in that: described olefin(e) acid class ester is propenoate or methacrylic acid ester; Described initiator is azo class or peroxo-two acyl class initiators, and described emulsifying agent is a non-ionics.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100249926A CN101585898B (en) | 2008-05-23 | 2008-05-23 | Resin microparticle in multilayered structure, dispersion liquid and preparation method thereof |
| JP2008305531A JP2009280791A (en) | 2008-05-23 | 2008-11-28 | Resin fine particle having multilayered structure, dispersion liquid thereof and manufacturing method thereof |
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| CN2008100249926A CN101585898B (en) | 2008-05-23 | 2008-05-23 | Resin microparticle in multilayered structure, dispersion liquid and preparation method thereof |
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| CN101585898A CN101585898A (en) | 2009-11-25 |
| CN101585898B true CN101585898B (en) | 2012-05-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973614A (en) * | 1987-03-13 | 1990-11-27 | Dainippon Ink And Chemicals, Inc. | Process for producing emulsion polymer composition |
| CN1800225A (en) * | 2005-12-28 | 2006-07-12 | 中国化工建设总公司常州涂料化工研究院 | Latex type hydroxy acryl acid resin possessing core-shell configuration |
-
2008
- 2008-05-23 CN CN2008100249926A patent/CN101585898B/en not_active Expired - Fee Related
- 2008-11-28 JP JP2008305531A patent/JP2009280791A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973614A (en) * | 1987-03-13 | 1990-11-27 | Dainippon Ink And Chemicals, Inc. | Process for producing emulsion polymer composition |
| CN1800225A (en) * | 2005-12-28 | 2006-07-12 | 中国化工建设总公司常州涂料化工研究院 | Latex type hydroxy acryl acid resin possessing core-shell configuration |
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| JP2009280791A (en) | 2009-12-03 |
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