CN102977266A - Preparation method of temperature and pH value dual responsive microgel - Google Patents
Preparation method of temperature and pH value dual responsive microgel Download PDFInfo
- Publication number
- CN102977266A CN102977266A CN2012105069201A CN201210506920A CN102977266A CN 102977266 A CN102977266 A CN 102977266A CN 2012105069201 A CN2012105069201 A CN 2012105069201A CN 201210506920 A CN201210506920 A CN 201210506920A CN 102977266 A CN102977266 A CN 102977266A
- Authority
- CN
- China
- Prior art keywords
- temperature
- preparation
- microgel
- value dual
- dual responsiveness
- 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.)
- Pending
Links
Images
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a preparation method of temperature and pH value dual responsive microgel. The preparation method comprises the steps of: (1) mixing N-isopropyl acrylamide, 4-vinylpyridine, a cross-linking agent and an emulsifier, completely dissolving the mixture into water; and (2) stably heating the solution, simultaneously leading in nitrogen to deoxidize, and adding an initiator to react and dialyze under the protection of the nitrogen, so as to obtain the temperature and pH value dual responsive microgel with even grain diameter. The preparation method is concise in synthetic route, short in technological process, mild in reaction condition, low in toxicity, and easy to industrialize; the cost is also reduced; the used polymerizing monomer is abundant in source, low in price and low in cost; a series of high polymer materials with different phase transition temperatures are obtained by controlling the feed ratio of two comonomers; the obtained temperature and pH value dual responsive microgel is even in grain diameter, bright and clean in surface, rapid in temperature and pH response and obvious in effect.
Description
Technical field
The invention belongs to the preparation field of microgel, particularly the preparation method of a kind of temperature and pH value dual responsiveness microgel.
Background technology
Novel material is basic substance and the gordian technique of many new and high technologies, and novel material itself is again new high-tech product, so research and development and the application of novel material are all very paid attention in countries in the world.Intelligent material refers to make the variation of surrounding environment the novel material of respective response, all has great application prospect in the every field of modern society.The sorting technique of intelligent material has a variety of, and according to the source of material, intelligent material comprises that metal is that intelligent material, inorganic non-metallic are intelligent material and macromolecular intelligent material.Intelligent macromolecule material is a class wherein, so-called intelligent macromolecule is exactly when the physics that is subject to external environment, chemistry and even bio signal change stimulation, the polymkeric substance of respective change can occur in some physics of self or chemical property, also often is called as " stimulating responsive polymer " or " environmental sensitivity polymkeric substance " etc.In the stimuli responsive type polymkeric substance, temperature and pH response type polymer are owing to its realization condition simply gains great popularity.
NIPA, its about 32 ° of C in the aqueous solution have a reversible phase transition temperature, are referred to as lower critical solution temperature (LCST).When outside temperature was lower than its LCST, NIPA was water miscible, showed as the chain conformation of stretching, extension; And be elevated to its LCST when above when outside temperature, the chain of NIPA shrinks, experience is transformed into insoluble, hydrophobic aggregate mutually, and this special heat sensitivity of NIPA has been applied to the many-sides such as control release, immobilized enzyme and immunoassay of medicine.P4VP is a kind of polycation, can well be dissolved in the sour environment, but surpassing at pH is water-fast more than 5, thereby be a kind of pH sensitive polymer, can predict the multipolymer that has simultaneously NIPA and P4VP and in the aqueous solution, can have simultaneously temperature and pH value response, therefore can be used as the environment sensitive type intelligent material and used.
Letex polymerization refers to the each other isolated latex particle that exists that generates according to colloid mechanism or oligopolymer mechanism in as the emulsion of medium at water or other liquid, then carry out therein radical addition polymerization or ion addition polymerization and produce a kind of method of polymkeric substance, the characteristics of letex polymerization take water as medium have represented current developing direction by solvent-borne type product hydrotropisms production interchange, thereby have given emulsion polymerization technology and used powerful vitality.
In view of above reason, research by letex polymerization preparation temperature and pH value dual responsiveness microgel seems significant, present Research Literature and patent, and stimulating responsive polymer exists preparation process complicated, the shortcomings such as experiment condition is too high, and industrialization difficulty etc. are not enough.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of temperature and pH value dual responsiveness microgel, the method synthetic route is succinct, technical process is short, reaction conditions is gentle, toxicity is low, is easy to industrialization, has further reduced the used polymerization single polymerization monomer of cost source and has enriched, cheap, cost is lower; Obtain the macromolecular material of a series of different phase transition temperatures by the feed ratio of controlling two comonomers; Gained temperature and pH value dual responsiveness microgel particle diameter are even, any surface finish, and temperature and pH response are quick, successful.
The preparation method of a kind of temperature of the present invention and pH value dual responsiveness microgel comprises:
(1) with NIPA and N, the removal of impurities that refluxes in N '-methylene-bisacrylamide organic solvent, stopper is removed in the 4-vinylpridine underpressure distillation, and Potassium Persulphate is recrystallization in deionized water;
(2) NIPA, 4-vinylpridine, linking agent, emulsifying agent are mixed, and fully soluble in water; Wherein the ratio of the amount of substance of NIPA, 4-vinylpridine is 1:1～1:100; It is 1%～10% that linking agent and emulsifying agent charging capacity account for polymerization single polymerization monomer amount of substance per-cent;
(3) mentioned solution is heated to 30 ~ 130 ℃ and stablizes 10 ~ 60min; logical nitrogen deoxygenation; add initiator; under the nitrogen protection; under 30 ~ 130 ℃ of conditions, reaction 0.5 ~ 10h, dialysis; namely get temperature and pH value dual responsiveness microgel, wherein to account for polymerization single polymerization monomer amount of substance per-cent be 0.5%～5% to initiator.
Organic solvent described in the described step (1) is a kind of in toluene, dimethylbenzene, normal hexane, pyridine, DMF, methyl-sulphoxide, acetone, the N,N-dimethylacetamide.
Linking agent in the described step (2) is N, N '-methylene-bisacrylamide, N, a kind of in N '-two (methylol) urea, quadrol, polyoxyethylene glycol, ethylene glycol, diglycidyl ether, the glycerine.
Emulsifying agent in the described step (2) is a kind of in cetyl alcohol, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyoxyethylene alkyl aryl ether, sorbester p17, sorbester p18, the sodium stearate.
Initiator is N in the described step (3), a kind of in N '-xylidine, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, benzoyl peroxide, the titanium tetrachloride.
The dialysis tubing molecular weight cut-off is 3000～14000 in the described step (3), and dialysis time is 2 ~ 7 days.
The temperature of gained and the phase transition temperature of pH value dual responsiveness microgel are 32～50 ℃ in the described step (3).
The lyophilize of gained microgel gets the microgel powder in the described step (3).
The preparation method of a kind of temperature of the present invention and pH value dual responsiveness microgel; with NIPA; 4-vinylpridine; linking agent; emulsifying agent mixes with certain proportion; and be dissolved in the deionized water fully; the reacting by heating monomer solution is to certain temperature; and maintenance certain hour; pass into the nitrogen deoxygenation; add initiator; under nitrogen protection, obtained polymer emulsion in some hours in 30～130 ℃ of lower reactions, at last above-mentioned polymer emulsion is placed in the impouring dialysis tubing; deionized water dialysis 2～7 days can obtain the uniform temperature of particle diameter and pH value dual responsiveness microgel.
Beneficial effect
(1) preparation method of the present invention is simple, and reaction conditions is gentle, and equipment is simple and easy to control, and is easy to operation, and gained nano microgel size is controlled, even, and good stability is easy to industrialization;
(2) the used polymerization single polymerization monomer of the present invention source is abundant, and cheap, cost is lower;
(3) gained temperature of the present invention and pH value dual responsiveness microgel particle diameter are even, any surface finish, and temperature and pH response are quick, successful;
(4) the present invention obtains the macromolecular material of a series of different phase transition temperatures by the feed ratio of controlling two comonomers;
(5) the dual responsiveness microgel of the present invention's preparation can be applicable to the fields such as decorative paint, targeted drug delivery, emulsion binding agent, bioseparation and fabric treating.
Description of drawings
Fig. 1 is temperature and the pH value dual responsiveness microgel scanning electron microscope (SEM) photograph that the present invention prepares;
Fig. 2 is that microgel hydromeehanics diameter varies with temperature trend map (pH=7) among the embodiment 2;
Fig. 3 be among the embodiment 2 microgel hydromeehanics diameter with pH value changing trend diagram (25 ℃ of temperature).
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
NIPA 11.3g, 4-vinylpridine 10.5g, N, N '-two (methylol) urea 1g, Sodium dodecylbenzene sulfonate 1.2g mixes, and is dissolved in the deionized water fully; Above-mentioned reaction monomers solution is heated to 60 ℃, and kept 30 minutes, pass into simultaneously the nitrogen deoxygenation, add Potassium Persulfate 0.8g, under the nitrogen atmosphere protection, obtained polymer emulsion in 6 hours in 60 ℃ of lower reactions; It is in 8000 the dialysis tubing that above-mentioned polymer emulsion is placed the impouring molecular weight cut-off, and deionized water dialysis 4 days can obtain the uniform temperature of particle diameter and pH value dual responsiveness microgel.
NIPA 11.3g, 4-vinylpridine 5.3g, N, N '-two (methylol) urea 0.7g, Sodium dodecylbenzene sulfonate 1.0g mixes, and is dissolved in the deionized water fully; Above-mentioned reaction monomers solution is heated to 50 ℃, and kept 30 minutes, pass into simultaneously the nitrogen deoxygenation, add Potassium Persulfate 0.6g, under the nitrogen atmosphere protection, magnetic agitation obtained polymer emulsion in 6 hours in 50 ℃ of lower reactions; It is in 8000 the dialysis tubing that above-mentioned polymer emulsion is placed the impouring molecular weight cut-off, and deionized water dialysis 6 days can obtain the uniform temperature of particle diameter and pH value dual responsiveness microgel.
NIPA 11.3g, 4-vinylpridine 2.4g, N, N '-two (methylol) urea 0.4g, Sodium dodecylbenzene sulfonate 0.7g mixes, and is dissolved in the deionized water fully; Above-mentioned reaction monomers solution is heated to 80 ℃, and kept 40 minutes, pass into simultaneously the nitrogen deoxygenation, add Potassium Persulfate 0.5g, under the nitrogen atmosphere protection, magnetic agitation obtained polymer emulsion in 4 hours in 80 ℃ of lower reactions; It is in 8000 the dialysis tubing that above-mentioned polymer emulsion is placed the impouring molecular weight cut-off, and deionized water dialysis 4 days can obtain the uniform temperature of particle diameter and pH value dual responsiveness microgel.
NIPA 11.3g, 4-vinylpridine 1.2g, N, N '-methylene-bisacrylamide 0.8g, Sodium dodecylbenzene sulfonate 0.6g mixes, and is dissolved in the deionized water fully; Above-mentioned reaction monomers solution is heated to 130 ℃, and kept 10 minutes, pass into simultaneously the nitrogen deoxygenation, add Potassium Persulfate 0.4g, under the nitrogen atmosphere protection, magnetic agitation obtained polymer emulsion in 0.5 hour in 130 ℃ of lower reactions; It is in 8000 the dialysis tubing that above-mentioned polymer emulsion is placed the impouring molecular weight cut-off, and deionized water dialysis 7 days can obtain the uniform temperature of particle diameter and pH value dual responsiveness microgel.
Claims (7)
1. the preparation method of a temperature and pH value dual responsiveness microgel comprises:
(1) NIPA, 4-vinylpridine, linking agent, emulsifying agent are mixed, and fully soluble in water; Wherein the ratio of the amount of substance of NIPA, 4-vinylpridine is 1:1～1:100; It is 1%～10% that linking agent and emulsifying agent charging capacity account for polymerization single polymerization monomer amount of substance per-cent;
(2) mentioned solution is heated to 30 ~ 130 ℃ and stablizes 10 ~ 60min; logical nitrogen deoxygenation; add initiator; under the nitrogen protection; under 30 ~ 130 ℃ of conditions, reaction 0.5 ~ 10h, dialysis; namely get temperature and pH value dual responsiveness microgel, wherein to account for polymerization single polymerization monomer amount of substance per-cent be 0.5%～5% to initiator.
2. the preparation method of a kind of temperature according to claim 1 and pH value dual responsiveness microgel, it is characterized in that: the linking agent in the described step (1) is N, N '-methylene-bisacrylamide, N, a kind of in N '-two (methylol) urea, quadrol, polyoxyethylene glycol, ethylene glycol, diglycidyl ether, the glycerine.
3. the preparation method of a kind of temperature according to claim 1 and pH value dual responsiveness microgel is characterized in that: the emulsifying agent in the described step (1) is a kind of in cetyl alcohol, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyoxyethylene alkyl aryl ether, sorbester p17, sorbester p18, the sodium stearate.
4. the preparation method of a kind of temperature according to claim 1 and pH value dual responsiveness microgel, it is characterized in that: initiator is N in the described step (2), a kind of in N '-xylidine, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, benzoyl peroxide, the titanium tetrachloride.
5. the preparation method of a kind of temperature according to claim 1 and pH value dual responsiveness microgel is characterized in that: the dialysis tubing molecular weight cut-off is 3000～14000 in the described step (2), and dialysis time is 2 ~ 7 days.
6. the preparation method of a kind of temperature according to claim 1 and pH value dual responsiveness microgel is characterized in that: the temperature of gained and the phase transition temperature of pH value dual responsiveness microgel are 32～50 ℃ in the described step (2).
7. the preparation method of a kind of temperature according to claim 1 and pH value dual responsiveness microgel is characterized in that: the lyophilize of gained microgel gets the microgel powder in the described step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105069201A CN102977266A (en) | 2012-11-30 | 2012-11-30 | Preparation method of temperature and pH value dual responsive microgel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105069201A CN102977266A (en) | 2012-11-30 | 2012-11-30 | Preparation method of temperature and pH value dual responsive microgel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102977266A true CN102977266A (en) | 2013-03-20 |
Family
ID=47851639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105069201A Pending CN102977266A (en) | 2012-11-30 | 2012-11-30 | Preparation method of temperature and pH value dual responsive microgel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102977266A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191680A (en) * | 2013-03-26 | 2013-07-10 | 厦门大学 | PH-sensitive composite hollow microsphere and preparation method thereof |
| CN106397654A (en) * | 2015-07-27 | 2017-02-15 | 北京服装学院 | Asymmetric responsive polymer particle and preparation method thereof |
| CN107151319A (en) * | 2017-04-26 | 2017-09-12 | 哈尔滨工业大学无锡新材料研究院 | A kind of multiple stimulation response crosslinking polymer nano-hydrogel, its preparation method and application |
| CN108341910A (en) * | 2017-01-23 | 2018-07-31 | 中国科学院化学研究所 | Nucleocapsid microgel and its improve colloidal materials aspect of performance application |
| CN108653196A (en) * | 2018-04-11 | 2018-10-16 | 燕山大学 | A kind of liposome Composite Double response carries the preparation method of liquid medicine gel |
| CN109385137A (en) * | 2018-11-27 | 2019-02-26 | 常州大学 | A kind of water-borne UV-curing ink and preparation method thereof that reactive and Temperature-Sensitive Microgel is modified |
| CN109554019A (en) * | 2018-09-21 | 2019-04-02 | 南京格沃新材料科技有限公司 | A kind of water-borne UV-curing ink of temperature response type polymer modification and its preparation method and application |
| CN110982623A (en) * | 2019-12-10 | 2020-04-10 | 中国科学院过程工程研究所 | Temperature and pH dual-response slow-release aromatic nanogel, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633712A (en) * | 2009-04-10 | 2010-01-27 | 孟智平 | Point-and-click temperature/pH-sensibility microgel |
-
2012
- 2012-11-30 CN CN2012105069201A patent/CN102977266A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633712A (en) * | 2009-04-10 | 2010-01-27 | 孟智平 | Point-and-click temperature/pH-sensibility microgel |
Non-Patent Citations (2)
| Title |
|---|
| KIM K S,VINCENT B: "pH and temperature-sensitive behaviors of poly (4-vinyl pyridine-co-N-isopropyl acrylamide) microgels", 《POLYMER JOURNAL》 * |
| PINKRAH V T, SNOWDEN M J, MITCHELL J C，等: "Physicochemical properties of poly (N-isopropylacrylamide-co-4-vinylpyridine) cationic polyelectrolyte colloidal microgels", 《LANGMUIR》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191680A (en) * | 2013-03-26 | 2013-07-10 | 厦门大学 | PH-sensitive composite hollow microsphere and preparation method thereof |
| CN103191680B (en) * | 2013-03-26 | 2016-02-24 | 厦门大学 | Composite hollow microballoon of a kind of pH sensitivity and preparation method thereof |
| CN106397654A (en) * | 2015-07-27 | 2017-02-15 | 北京服装学院 | Asymmetric responsive polymer particle and preparation method thereof |
| CN106397654B (en) * | 2015-07-27 | 2018-08-07 | 北京服装学院 | A kind of asymmetrical response polymer beads and preparation method thereof |
| CN108341910A (en) * | 2017-01-23 | 2018-07-31 | 中国科学院化学研究所 | Nucleocapsid microgel and its improve colloidal materials aspect of performance application |
| CN107151319A (en) * | 2017-04-26 | 2017-09-12 | 哈尔滨工业大学无锡新材料研究院 | A kind of multiple stimulation response crosslinking polymer nano-hydrogel, its preparation method and application |
| CN108653196A (en) * | 2018-04-11 | 2018-10-16 | 燕山大学 | A kind of liposome Composite Double response carries the preparation method of liquid medicine gel |
| CN109554019A (en) * | 2018-09-21 | 2019-04-02 | 南京格沃新材料科技有限公司 | A kind of water-borne UV-curing ink of temperature response type polymer modification and its preparation method and application |
| CN109385137A (en) * | 2018-11-27 | 2019-02-26 | 常州大学 | A kind of water-borne UV-curing ink and preparation method thereof that reactive and Temperature-Sensitive Microgel is modified |
| CN109385137B (en) * | 2018-11-27 | 2022-01-25 | 常州大学 | Reactive and temperature-sensitive microgel modified aqueous UV curing ink and preparation method thereof |
| CN110982623A (en) * | 2019-12-10 | 2020-04-10 | 中国科学院过程工程研究所 | Temperature and pH dual-response slow-release aromatic nanogel, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102977266A (en) | Preparation method of temperature and pH value dual responsive microgel | |
| Shibuya et al. | Advanced soap-free emulsion polymerization for highly pure, micron-sized, monodisperse polymer particles | |
| CN103554376B (en) | The preparation method of monodisperse cross-linked poly (methyl methacrylate) micro-sphere | |
| CN104558321A (en) | Preparation method for POSS/PDMAEMA organic/inorganic hybrid material according to thiol-ene click chemistry method | |
| CN101289522B (en) | Method for preparing hollow ball with temperature response or temperature and pH responses | |
| CN102649826A (en) | Preparation method of particle diameter controllable monodisperse polystyrene microspheres | |
| CN103613706B (en) | Monodisperse ternary copolymer microspheres and preparation method thereof | |
| CN105646789A (en) | Method for preparing fluorescent polymer rare earth complex nano-microsphere | |
| CN111992151B (en) | preparation method of pH stimulation responsive slow-release hybrid microspheres | |
| CN106478904A (en) | A kind of preparation method of the segmented copolymer material with temperature and pH-sensitivity | |
| CN104787994B (en) | Modified Nano chlorapatite is utilized to stablize the method for heavy metal lead in bed mud | |
| CN102718894A (en) | Low temperature synthesis method for monodisperse polymer microsphere | |
| CN103694379B (en) | A kind of have di-block copolymer of light and pH response characteristic and preparation method thereof | |
| CN104558383B (en) | Fluorescent complex containing carboxylic acid type high polymer and rare earth, preparation method of fluorescent complex, fluorescent chemical carbon powder and preparation method of fluorescent chemical carbon powder | |
| Wang et al. | Preparation of a novel light-sensitive copolymer and its application in recycling aqueous two-phase systems | |
| CN103254373A (en) | Preparation method of stable segmented copolymer PAPMA (Polymethyl Acrylate P-acetamide Phenyl Ester)-b-PNIPAM (Polyisopropyl Acrylamide) based Au nanometer particle | |
| CN108034073B (en) | Intelligently-changed particles and preparation method thereof | |
| CN103396505A (en) | Preparation method of pure cationic nanosphere | |
| CN107082844B (en) | For ore dressing and the amphoteric polyacrylamide flocculating agent and preparation method of tailings glass | |
| CN106749805B (en) | A kind of atom transfer radical polymerization method acted on using low temperature eutectic | |
| CN108070060A (en) | A kind of microballoon powder of the high cross-linked polymer of micron order and its preparation method and application | |
| CN104774287A (en) | Polyacrylate emulsion microgel and preparation method thereof | |
| CN102086266B (en) | Polypeptide-containing asymmetric hyperbranched amphoteric polyelectrolyte and preparation method thereof | |
| CN103483477B (en) | The preparation method of single dispersing surface chain transfer activity functionalized polymer microsphere | |
| CN103613697A (en) | Preparation method of pH-sensitive polymer nano-latex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130320 |