CN105949368A - Multi-responsiveness amphiphilic polymer microparticle and preparation method thereof - Google Patents
Multi-responsiveness amphiphilic polymer microparticle and preparation method thereof Download PDFInfo
- Publication number
- CN105949368A CN105949368A CN201610379309.5A CN201610379309A CN105949368A CN 105949368 A CN105949368 A CN 105949368A CN 201610379309 A CN201610379309 A CN 201610379309A CN 105949368 A CN105949368 A CN 105949368A
- Authority
- CN
- China
- Prior art keywords
- amphipathic polymer
- preparation
- multiple response
- microgranule
- polymer microgranule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention provides a preparation method of an amphiphilic polymer microparticle with multi-responsiveness, and belongs to the field of novel high polymer materials. The method comprises the steps that acrylic acid, acrylic ester and substituted acrylamide are adopted as comonomers, water is adopted as a reaction medium, and under the effect of an initiator, the amphiphilic polymer microparticle with the temperature, pH and salt responsiveness is obtained through an environment-friendly one-step soap-free emulsion polymerization method. The amphiphilic polymer microparticle is uniform in particle size, the emulsion can form a stable organic solvent in water (O/W) or water in organic solvent (W/O) emulsion through an organic solvent (O) and water (W), and the amphiphilic polymer microparticle has the multi-responsiveness of temperature sensibility, pH responsiveness, salt sensibility and the like, and the wide application prospect is achieved in the fields such as solid surface active agents, biomedicine, intelligent coatings and environmental response materials.
Description
Technical field
The invention belongs to polymeric material field, relate to the preparation of a kind of amphipathic polymer microgranule；Particularly relate to a kind of preparation with multiple response amphipathic polymer microgranules such as pH, temperature, ionic strengths, be mainly used in the fields such as solid surfactant, biomedicine, intelligent coatings, environment-responsive material.
Background technology
Amphipathic microgranule is that a kind of Surface Physical Chemistry character has anisotropy or the asymmetric microgranule of structure.Excellent physical and chemical performance has shown huge application prospect in the field such as chemistry, biomedicine, sensor, solid surfactant, intelligent coatings.The character of amphipathic polymer microgranule and function depend on its pattern and chemical characteristic, and as at fluid boundary, pattern anisotropy is to determine its configuration, and the key factor of emulsion particle interphase interaction.Some amphipathic polymer microgranules are as solid surfactant, by changing its pattern and amphipathic, outside stimulus is responded, such as the stimulation of temperature, light, pH, ionic strength etc., and then its characteristic and function also change, it is the amphipathic polymer microgranule with multiple response.The amphipathic polymer microgranule of the multiple response that surface is rolled into a ball with carboxylate radical or amine foundation or the good chemical material of a class; it is combined with other nanoparticle by surface functional group; can be used to synthesize and there is the advanced polymer composites of excellent properties, composite organic-inorganic material, can be applicable to the fields such as solid surfactant, medicine delivery, Display Technique, environment-responsive material.
There is the amphipathic polymer microgranule of multiple response because of its special appearance and the anisotropy of chemical property, cause the stimulating responsive of its uniqueness, and these performances do not observe in isotropic homogenizing microgranule.Up to the present, the amphipathic polymer particle research of multiple response is achieved with remarkable progress, and existing different synthetic method, such as selectivity modification, emulsion polymerization, wet chemistry synthesis, self assembly etc..Such as a kind of nanoparticle (patent of invention CN102294212A) with pH sensitivity；A kind of temperature response type polymer particles (patent of invention CN104629059A) for medicine controlled releasing and genophore.Some have in the amphipathic polymer microgranule building-up process of stimuli responsive needs to add cross-linking agent, and needs swelling, sometimes also needs to organic solvent induction and is separated.But, during synthesis has the amphipathic polymer microparticle technologies of stimuli responsive at present, partial reaction needs organic solvent, and environment can be worked the mischief by this.There is the shortcomings such as building-up process is complicated, productivity is low in part preparation method.
Summary of the invention
The present invention seeks to the weak point existed for prior art, it is provided that a kind of simple, efficiently, environmental protection prepare the method with multiple response amphipathic polymer microgranule.
One, there is the preparation of multiple response amphipathic polymer microgranule
The present invention is with acrylic acid and derivant acrylate thereof and substituted acrylamide as comonomer, with water as solvent, under initiator effect, a simple and eco-friendly step surfactant-free emulsion polymerization is used to prepare the amphipathic polymer microgranule with responses such as pH, temperature, ionic strengths.Its synthetic method is as follows:
In reaction medium, first add part initiator solution, be warming up to 55 ~ 95 DEG C, stir 5 ~ 30 min；The most under agitation add mixture and the residue initiator solution of comonomer, continuing stirring at 55 ~ 95 DEG C makes it react complete, obtain the emulsion with the amphipathic polymer microgranule of multiple response, centrifugation, obtain the amphipathic polymer microgranule with multiple response.
In the mixture of described comonomer, the mass ratio of three class monomeric acrylic, acrylate and substituted acrylamide is 1: 0.5: 0.1 ~ 1:8:0.6；Wherein, acrylic acid is acrylic or methacrylic acid；Acrylate is at least two in acrylic acid methyl ester., methyl methacrylate, butyl acrylate, butyl methacrylate；Substituted acrylamide is at least one in N, N-acrylamide, NIPA.
The rate of addition of the mixture of described comonomer is 10 ~ 50 d/min, and time for adding is 0.5 ~ 2 h.
Described initiator ammonium persulfate or potassium peroxydisulfate, its total consumption is the 0.15% ~ 3% of comonomer gross mass.Wherein add amount is initiator total amount the 1/6 ~ 1/3 of initiator for the first time.
Two, the microscopic appearance of multiple response amphipathic polymer microgranule and structural characterization
1, macroscopic view and microscopic appearance
Fig. 1 is scanning electron microscope (SEM) figure (a) and transmission electron microscope (TEM) figure (b) of the multiple response amphipathic polymer microgranule of preparation.From SEM figure it can be seen that the ball-type pattern that polymer particles is uniform particle sizes, mean diameter is between 350 ~ 400 nm.From TEM it can be seen that the ball-type pattern that polymer particles is uniform particle sizes, mean diameter is about 350 nm, basically identical with the data of SEM.Can be additionally seen polymer particles from TEM is bilateral structure, and the similar hemisphere face of character is close to each other, and the different hemisphere face of character is mutually become estranged, and this two-sided microsphere is one of its amphipathic form of expression.
2, infrared spectrum analysis
Fig. 2 is the infrared absorption spectroscopy of the amphipathic polymer microgranule of preparation.It can be seen that 2959 cm-1With 2875 cm-1It is the stretching vibration absworption peak of saturated C-H, 1383 cm-1It it is the bending vibration absworption peak of saturated C-H；1733 cm-1Place is the stretching vibration absworption peak of ester C=O, 1265 cm-1With 1167 cm-1It is antisymmetry and the symmetrical stretching vibration characteristic peak of C-O-C in ester group.Owing to there is stronger hydrogen bond action in polymer, the C=O in amido link moves to low frequency, 1636 cm-1Place is its stretching vibration absworption peak.1453 cm-1Place is carboxylate radical (-COO-) symmetrical stretching vibration peak in conjugated system.Infrared spectrogram illustrates, monomeric acrylic, acrylate and substituted acrylamide have both participated in polyreaction.
Three, the amphipathic and emulsifiability test of amphipathic polymer microgranule
In order to evaluate the amphipathic of polymer particles, test polymer particles dispersity in water.Fig. 3 is the emulsifiability of multiple response amphipathic polymer corpuscle emulsion.Use water as solvent, polymer particles can be made white emulsion (figure a1), thus there is good dispersibility and emulsifiability；It is heated to 70 DEG C of (figure a2), emulsion, without significant change, has good emulsibility (figure a at oil-water interfaces simultaneously3), illustrate that double-sided polymerization thing microgranule is a kind of stable solid surfactant, existing water-wet side, there is again hydrophobic end.Therefore, this amphipathic polymer microgranule can make organic solvent (O) and water (W) form stable oil-in-water (O/W) or Water-In-Oil (W/O) emulsion.
Four, the multiple response test of amphipathic polymer microgranule
1, pH response
In order to evaluate the relation of amphipathic polymer microgranule and pH, test the emulsibility of polymer particles in different pH environment.Fig. 4 is containing multiple response amphipathic polymer corpuscle emulsion emulsifiability under different pH, wherein b1、b2、b3It is respectively the emulsifiability figure of the amphipathic polymer microgranule of pH 6.7, pH 11.4, pH 2.3.Result shows, changes the pH value of solution, it is also possible to change the emulsibility of microgranule.Illustrate that it has good emulsibility (b neutral in alkaline environment2, b3)；Emulsibility (figure b is not had in sour environment1).Therefore this amphipathic polymer microgranule has certain pH response.
2, salt response
In order to evaluate the relation of amphipathic polymer microgranule and salinity, test the emulsibility of polymer particles in different salinity environment.Fig. 5 is containing multiple response amphipathic polymer corpuscle emulsion emulsifiability in different salinity, wherein c1、c2、c3Be respectively concentration be 0.03 mol/L(M), 0.10 M, the amphipathic polymer microgranule emulsifiability figure of 0.30 M.Result shows, the concentration of saline solution has considerable influence to the emulsibility of amphipathic polymer microgranule.When the concentration of saline solution is relatively low, the stable emulsion of polymer particles is O/W(c1)；Increase the concentration of saline solution, the emulsion generation phase in version that polymer particles is stable, form W/O emulsion (c2)；Continue to increase the concentration of saline solution, the emulsifying capacity variation (c of polymer particles3).Therefore this amphipathic polymer microgranule has certain salinity response.Fig. 5 also illustrates, in the saline solution of variable concentrations, polymer particles shows different emulsifiabilities at oil-water interfaces.Therefore, polymer particles is two-sided and has amphipathic.
3, diameter of particle and the relation of temperature
In order to evaluate the relation of amphipathic polymer microgranule and temperature, test emulsion particle diameter and the relation (Fig. 6) of temperature under different temperatures.Can be seen that, under room temperature (20 DEG C ~ 25 DEG C), this polymer particles is in aqueous, mean diameter is surveyed numerical value by 460 these particle diameters of nm ~ 470 nm(higher than SEM, the TEM recorded under drying regime, has been because portion swells or adhesion), after emulsion temperature is increased to 35 DEG C, mean diameter is suddenlyd change to 800 nm, when temperature further rises to 50 DEG C, mean diameter change is less, still between 800 ~ 830 nm.Illustrate that during more than 35 DEG C, polymer particle diameter significantly increases along with temperature raises.After temperature reduces, mean diameter is reduced to original numerical value.Therefore, this amphipathic polymer microgranule has temperature-responsive.
In sum, the present invention, with acrylic acid, acrylate and substituted acrylamide etc. as monomer, is prepared for a class by a step surfactant-free emulsion polymerization and has the amphipathic nature polyalcohol microgranule of multiple response.This based fine particles has pH response, Thermo-sensitive and the ionic strength response of excellence, and emulsifying capacity is controlled.It is with a wide range of applications in fields such as solid surfactant, biomedicine, electronics, environment-responsive materials.Additionally, present invention distillation water as solvent, it is not added with emulsifying agent and cross-linking agent, Environmental Safety；Using a step surfactant-free emulsion polymerization synthetic technology, technique is simple, efficient, clean, beneficially industrialization.
Accompanying drawing explanation
Fig. 1 is SEM and the TEM figure of multiple response amphipathic polymer microgranule.
Fig. 2 is the infrared absorpting light spectra of multiple response amphipathic polymer microgranule.
Fig. 3 is the emulsifiability figure of multiple response amphipathic polymer corpuscle emulsion.
Fig. 4 is multiple response amphipathic polymer corpuscle emulsion emulsifiability figure under different pH, wherein b1、b2、b3It is respectively pH 6.7, pH 11.4, the amphipathic polymer microgranule emulsifiability figure of pH 2.3.
Fig. 5 is multiple response amphipathic polymer corpuscle emulsion emulsifiability figure in different salinity, wherein c1、c2、c3Be respectively concentration be 0.03 M, the amphipathic polymer microgranule emulsifiability figure of 0.10 M, 0.30 M.
Fig. 6 is the temperature graph of a relation with particle diameter of multiple response amphipathic polymer microgranule.
Detailed description of the invention
Below by specific embodiment, the preparation of amphipathic polymer microgranule of the present invention is described further.
Embodiment 1
In the reactor equipped with agitator, condensing tube and Dropping funnel, add 30 mL water, under stirring, be warming up to 90 DEG C.Acrylic acid, acrylate and the mixture (mass ratio of three is 1:0.5:0.1) of substituted acrylamide is laid in Dropping funnel.It is initially charged 4 mL 1 mg/mL ammonium persulfate aqueous solutions in the reactor, at 90 DEG C, stirs 25 min.Then, under agitation it is simultaneously added dropwise mixture and the 16 mL 1 mg/mL ammonium persulfate aqueous solutions of 10 g comonomers, controls rate of addition, time for adding 1.0 h.After dropping, continue stirring 3 h at maintaining 90 DEG C and make reaction complete, obtain the emulsion of amphipathic polymer microgranule, centrifugation, obtain the amphipathic polymer microgranule with multiple response.
Temperature-responsive: this polymer particles is the ball-type pattern of uniform particle sizes, this polymer particles is when 25 DEG C, and mean diameter is 460 nm；Increasing the temperature to when 35 DEG C, mean diameter increases to 800 nm；When increasing the temperature to 50 DEG C further, mean diameter the most slightly change, about 830 nm.After temperature reduces, particle diameter is decreased to original numerical value therewith.
PH response: in the weakly acidic pH environment of pH=6.7, can make water and toluene form stable O/W emulsion；In the sour environment of pH=2.3, polymer particles loses emulsifying capacity, water and toluene layering；In the alkaline environment of pH=11.4, the emulsibility of polymer particles strengthens.Therefore, illustrate that amphipathic polymer microgranule has certain pH response.
Salt response: when NaCl concentration is 0.03 M in aqueous solution, the stable emulsion of polymer particles is O/W；When the concentration of NaCl increases to 0.1 M, the emulsion generation phase in version that polymer particles is stable, form W/O emulsion, when the concentration of NaCl increases to 0.3 M, the emulsifying capacity of microgranule is deteriorated.
Embodiment 2
In the reactor equipped with agitator, condensing tube and Dropping funnel, add 60 mL water, under stirring, be warming up to 85 DEG C.Acrylic acid, acrylate and the mixture (mass ratio of three is 1:2:0.2) of substituted acrylamide comonomer is laid in Dropping funnel.It is initially charged 6 mL 1 mg/mL ammonium persulfate aqueous solutions, at 85 DEG C, stirs 15 min.The most under agitation being simultaneously added dropwise mixture and the 17 mL 1 mg/mL ammonium persulfate aqueous solutions of 15 g comonomers, control rate of addition, time for adding is 1.5 h.After dropping, continue stirring 2 h at maintaining 85 DEG C and make reaction complete, obtain the emulsion of amphipathic polymer microgranule, centrifugation, obtain the amphipathic polymer microgranule with multiple response.The pattern of this polymer particles, pH response, salt response etc. are similar to Example 1.
Embodiment 3
In the reactor equipped with agitator, condensing tube and Dropping funnel, add 80 mL water, under stirring, be warming up to 75 DEG C.Acrylic acid, acrylate and the mixture (mass ratio of three is 1:5:0.3) of substituted acrylamide comonomer is laid in Dropping funnel.It is initially charged 7 mL 1 mg/mL persulfate aqueous solutions in the reactor, at 75 DEG C, stirs 25 min.Then, under agitation it is simultaneously added dropwise mixture and the 25 mL 1 mg/mL ammonium persulfate aqueous solutions of 25 g comonomers, controls rate of addition, time for adding 2 h.After dropping, continue stirring 2 h at maintaining 75 DEG C and make reaction complete, obtain the emulsion with the amphipathic polymer microgranule of multiple response, further centrifugation, obtain the amphipathic polymer microgranule with multiple response.The pattern of this polymer particles, pH response, salt response etc. are similar to Example 1.
Embodiment 4
In the reactor equipped with agitator, condensing tube and Dropping funnel, add 45 mL water, under stirring, be warming up to 92 DEG C.Acrylic acid, acrylate and the mixture (mass ratio of three is 1: 8: 0.6) of substituted acrylamide comonomer is laid in Dropping funnel.It is initially charged 4 mL 1mg/mL ammonium persulfate aqueous solutions in the reactor, at 92 DEG C, stirs 15 min.Then, under agitation it is simultaneously added dropwise mixture and the 14 mL 1 mg/mL ammonium persulfate aqueous solutions of 8 g comonomers, controls rate of addition, time for adding 50 min.After dropping, continue stirring 1.5 h at maintaining 92 DEG C and make reaction complete, obtain the emulsion with the amphipathic polymer microgranule of multiple response, further centrifugation, obtain the amphipathic polymer microgranule with multiple response.The pattern of this polymer particles, pH response, salt response etc. are similar to Example 1.
Claims (9)
1. a preparation method with multiple response amphipathic polymer microgranule, it is with acrylic acid, acrylate, substituted acrylamide as comonomer, water is reaction medium, under initiator effect, prepared the amphipathic polymer microgranule with pH, temperature, salt response by a step surfactant-free emulsion polymerization.
A kind of preparation method with multiple response amphipathic polymer microgranule, it is characterised in that: in reaction medium, first add part initiator solution, be warming up to 55 ~ 95 DEG C, stir 5 ~ 30 min；The most under agitation add mixture and the residue initiator solution of comonomer, continuing stirring at 55 ~ 95 DEG C makes it react complete, obtain the emulsion with the amphipathic polymer microgranule of multiple response, centrifugation, obtain the amphipathic polymer microgranule with multiple response.
There is the preparation method of multiple response amphipathic polymer microgranule the most as claimed in claim 1 or 2, it is characterized in that: in the mixture of described comonomer, the mass ratio of three class monomeric acrylic, acrylate and substituted acrylamide is 1:0.5:0.1 ~ 1:8:0.6.
There is the preparation method of multiple response amphipathic polymer microgranule the most as claimed in claim 1 or 2, it is characterised in that: in described comonomer, acrylic acid is acrylic or methacrylic acid.
There is the preparation method of multiple response amphipathic polymer microgranule the most as claimed in claim 1 or 2, it is characterized in that: in described comonomer, acrylate is at least two in acrylic acid methyl ester., methyl methacrylate, butyl acrylate, butyl methacrylate.
There is the preparation method of multiple response amphipathic polymer microgranule the most as claimed in claim 1 or 2, it is characterised in that: in described comonomer, substituted acrylamide is at least one in N, N-acrylamide, NIPA.
There is the preparation method of multiple response amphipathic polymer microgranule the most as claimed in claim 1 or 2, it is characterised in that: initiator is Ammonium persulfate. or potassium peroxydisulfate, and its total consumption is the 0.15% ~ 3% of comonomer gross mass.
There is the preparation method of multiple response amphipathic polymer microgranule the most as claimed in claim 2, it is characterised in that: add amount is initiator total amount the 1/3 ~ 1/6 of initiator for the first time.
There is the preparation method of multiple response amphipathic polymer microgranule the most as claimed in claim 2, it is characterised in that: the rate of addition of the mixture of comonomer is 10 ~ 50 d/min, and time for adding is 0.5 ~ 2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610379309.5A CN105949368B (en) | 2016-05-31 | 2016-05-31 | A kind of multiple response amphipathic polymer particle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610379309.5A CN105949368B (en) | 2016-05-31 | 2016-05-31 | A kind of multiple response amphipathic polymer particle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105949368A true CN105949368A (en) | 2016-09-21 |
| CN105949368B CN105949368B (en) | 2018-05-25 |
Family
ID=56907418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610379309.5A Active CN105949368B (en) | 2016-05-31 | 2016-05-31 | A kind of multiple response amphipathic polymer particle and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105949368B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034073A (en) * | 2017-12-06 | 2018-05-15 | 北京服装学院 | A kind of particle intelligently changed and preparation method thereof |
| CN110183686A (en) * | 2019-05-21 | 2019-08-30 | 华南理工大学 | Controllable lotion of one seed type and preparation method thereof |
| CN110669164A (en) * | 2019-08-14 | 2020-01-10 | 中国船舶重工集团公司第七二五研究所 | Coated antifouling agent nanocapsule with DCOIT release rate controlled by temperature and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037494A (en) * | 2007-04-02 | 2007-09-19 | 东华大学 | Microgel with nanometer grade sensitivity of temperature and PH value and preparation method thereof |
| CN101838375A (en) * | 2010-04-23 | 2010-09-22 | 东华大学 | Temperature and pH stimuli-responsive intelligent polymer microcapsule and preparation thereof |
| CN104645357A (en) * | 2015-01-31 | 2015-05-27 | 湖北大学 | MRI (magnetic resonance imaging) contrast agent as well as preparation method and application thereof |
| CN104693345A (en) * | 2015-03-30 | 2015-06-10 | 河北工业大学 | Polymer dispersion and preparation method thereof |
-
2016
- 2016-05-31 CN CN201610379309.5A patent/CN105949368B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037494A (en) * | 2007-04-02 | 2007-09-19 | 东华大学 | Microgel with nanometer grade sensitivity of temperature and PH value and preparation method thereof |
| CN101838375A (en) * | 2010-04-23 | 2010-09-22 | 东华大学 | Temperature and pH stimuli-responsive intelligent polymer microcapsule and preparation thereof |
| CN104645357A (en) * | 2015-01-31 | 2015-05-27 | 湖北大学 | MRI (magnetic resonance imaging) contrast agent as well as preparation method and application thereof |
| CN104693345A (en) * | 2015-03-30 | 2015-06-10 | 河北工业大学 | Polymer dispersion and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈瑜 等: "N- 异丙基丙烯酰胺共聚物的温度敏感性研究", 《胶体与聚合物》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034073A (en) * | 2017-12-06 | 2018-05-15 | 北京服装学院 | A kind of particle intelligently changed and preparation method thereof |
| CN108034073B (en) * | 2017-12-06 | 2021-04-06 | 北京服装学院 | Intelligently-changed particles and preparation method thereof |
| CN110183686A (en) * | 2019-05-21 | 2019-08-30 | 华南理工大学 | Controllable lotion of one seed type and preparation method thereof |
| CN110183686B (en) * | 2019-05-21 | 2021-12-17 | 华南理工大学 | Type-adjustable emulsion and preparation method thereof |
| CN110669164A (en) * | 2019-08-14 | 2020-01-10 | 中国船舶重工集团公司第七二五研究所 | Coated antifouling agent nanocapsule with DCOIT release rate controlled by temperature and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105949368B (en) | 2018-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Musyanovych et al. | Effect of hydrophilic comonomer and surfactant type on the colloidal stability and size distribution of carboxyl-and amino-functionalized polystyrene particles prepared by miniemulsion polymerization | |
| CN107652441B (en) | A kind of SiO2Enhanced polymer method for preparing microsphere | |
| CN102861541B (en) | Preparation method of surface-modified fluorescent magnetic polymer composite microspheres | |
| CN103980506B (en) | A kind of preparation method of the magnetic microsphere based on PLEG | |
| CN105949368A (en) | Multi-responsiveness amphiphilic polymer microparticle and preparation method thereof | |
| CN108395504B (en) | Method for preparing double-response polymer Janus microspheres by soap-free emulsion polymerization | |
| CN106749990B (en) | A kind of magnetic coupling gel micro-ball and preparation method thereof | |
| CN103509161A (en) | Preparation method of hydrophilic magnetic halloysite surface molecularly-imprinted nano composite material | |
| Watanabe et al. | Impact of spatial distribution of charged groups in core poly (N-isopropylacrylamide)-based microgels on the resultant composite structures prepared by seeded emulsion polymerization of styrene | |
| CN104072656B (en) | A kind of method preparing ferroso-ferric oxide-composite magnetic microsp Heres | |
| CN103819608A (en) | Preparation method for cyhalothrin fluorescent surface molecular imprinting nanomaterial | |
| Asadi et al. | Synthesis, recognition and evaluation of molecularly imprinted polymer nanoparticle using miniemulsion polymerization for controlled release and analysis of risperidone in human plasma samples | |
| CN109154609A (en) | Compound particle, coated particle, the manufacturing method of compound particle, the solid phase carrier containing ligand and the target substance in sample is detected or isolated method | |
| CN105777967B (en) | A kind of preparation method of morphology controllable double-sided polymerization object particle | |
| CN107522798A (en) | A kind of method that emulsion polymerization is carried out using carbonitride as solid emulsifier | |
| Lin et al. | Synthesis and mass cytometric analysis of lanthanide-encoded polyelectrolyte microgels | |
| Zhang et al. | Preparation, application and development of poly (ionic liquid) microspheres | |
| CN104151492A (en) | Preparation method for cyhalothrin fluorescent surface molecular imprinting sub-micron material | |
| CN103755968B (en) | A kind of pH and the ternary molecular brush polymer of temperature dual response and the Nano capsule of preparation thereof | |
| CN106633057B (en) | The preparation of core-shell structure particle with cavity | |
| CN108659161A (en) | A kind of CO2Responsive polymer tiny balloon and preparation method thereof | |
| CN103354144A (en) | Magnetic composite microsphere as well as preparation method and application thereof | |
| CN103007844A (en) | Preparation method of magnetic sepharose gel microspheres | |
| CN102897826B (en) | Method for preparing nanometer zinc oxide composite material from super concentrated emulsion | |
| CN106084110A (en) | There is fluorescent nanometer microsphere and the application thereof of pH response and aggregation inducing Fluorescence Increasing character |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190628 Address after: 528000 Room 330, 3 Chuangyue Times Cultural Creative Park, 61 Xia Nan Road, Guicheng Street, Nanhai District, Foshan City, Guangdong Province (Residence Declaration) Patentee after: Foshan Nanhai Dual-Dimensional Water-based Materials Co., Ltd. Address before: 730070 No. 967 Ning Ning Road, Anning District, Lanzhou, Gansu Patentee before: Northwest Normal University |