CN107417833B - Amino modified nano polystyrene and preparation method thereof - Google Patents
Amino modified nano polystyrene and preparation method thereof Download PDFInfo
- Publication number
- CN107417833B CN107417833B CN201710609812.XA CN201710609812A CN107417833B CN 107417833 B CN107417833 B CN 107417833B CN 201710609812 A CN201710609812 A CN 201710609812A CN 107417833 B CN107417833 B CN 107417833B
- Authority
- CN
- China
- Prior art keywords
- polystyrene
- modified nano
- amino
- hydrochloride
- water
- 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.)
- Active
Links
Images
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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses amino-modified nano-polystyrene and a preparation method thereof, belonging to the field of nano-material preparation, wherein the amino-modified nano-polystyrene comprises the following components in percentage by weight: 2-8% of monomer styrene, 0.5-1.5% of dodecylamine hydrochloride, 0.3-0.5% of azo diisobutyl amidine hydrochloride and the balance of water. The method has the characteristics of simple and convenient process, mild reaction conditions, simple reaction equipment, controllable particle size and environmental protection.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to amino modified nano polystyrene and a preparation method thereof.
Background
Surface functionalized polymer microspheres have received increasing attention, and such microspheres can be widely used in many fields, such as biochemistry and biomedicine, pharmacology, chromatography column packing, clinical examination, and the like. To date, researchers have prepared polymeric microspheres with a variety of different functional groups including carboxyl, hydroxyl, amino, vinyl, azo, and the like. These surface functionalized polymer microspheres can be used for immobilizing and detecting biological macromolecules, such as proteins like antibodies and enzymes.
Introduction of amino groups on the surfaces of metal or semiconductor nanoparticles is relatively easy, so that most of the current researches are limited to amination of metal or semiconductor nanoparticles, and the researches on amination of the surfaces of polymer nanoparticles are relatively few. At present, microemulsion polymerization is the most common method for preparing polymer nanoparticles with the particle size of below 60nm, and the particle size of the polymer nanoparticles is influenced by the concentration of an initiator, the amount of a monomer and the amount of an emulsifier, so that the particle size of the polymer is uncontrollable.
Musyanovich adopts terpolymer HAS as an initiating emulsifier, and prepares stable monodisperse polystyrene nanoparticles with the particle size of 90nm to 150nm through emulsion polymerization. Then, monomers with amino groups are added into the system for copolymerization to prepare aminated polystyrene particles with the particle size of 100 nm. Although the method is simple and easy, the particle size of the obtained product is still larger, and the application of the aminated polystyrene nano particles is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing the amino-modified nano-polystyrene with simple and convenient process, controllable particle size and environmental protection and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
on the one hand, the amino modified nano-polystyrene is provided, which comprises the following components in percentage by weight: 2-8% of monomer styrene, 0.5-1.5% of dodecylamine hydrochloride, 0.3-0.5% of azo diisobutyl amidine hydrochloride and the balance of water.
Further, the amino modified nano-polystyrene comprises the following components in percentage by weight: 5-6% of monomer styrene, 0.5-1.0% of dodecylamine hydrochloride, 0.3-0.36% of azo-diisobutyl amidine hydrochloride and the balance of water.
On the other hand, the preparation method of the amino modified nano-polystyrene is also provided, namely, under the action of dodecylamine hydrochloride, styrene monomers are dispersed in water to form an emulsion state, and then the free radical addition polymerization is initiated by azodiisobutyl amidine hydrochloride to generate the polystyrene microspheres, and the method comprises the following steps:
step 1: mixing monomer styrene, surfactant and water, stirring and emulsifying; adding an initiator, wherein the mass percent of monomer styrene, surfactant and initiator in the reaction system is 5-6%: 0.5-1.5%: 0.3-0.36%;
step 2: and (3) placing the reaction system in the step 1 at 75 ℃, and stirring for polymerization reaction for 5 hours. Cooling to room temperature under natural conditions to prepare amino modified nano-polystyrene;
wherein the surfactant is dodecylamine hydrochloride.
Further, the initiator is azodiisobutyl amidine hydrochloride.
Further, the initiator is added for three times when the reaction is carried out for 30min, 60min and 120 min.
Further, the water is distilled water or deionized water, and the mass ratio of the water to the surfactant is 70-90: 1.
Further, the stirring speed is 300 revolutions per minute.
Further, the initiator is added dropwise at the dropping speed of 20-30 d/min.
The invention has the following beneficial effects:
1) the scheme provided by the invention realizes the controllable preparation of the polystyrene, the particle size of the polystyrene is controlled at a nanometer level, and the particle size distribution basically conforms to normal distribution;
2) the scheme provided by the invention has the advantages of small using amount of the initiator and the surfactant, low cost and easy acquisition of medicines;
3) the scheme provided by the invention does not need high-temperature violent reaction conditions and has low requirements on reaction devices and equipment.
Drawings
FIG. 1 is a schematic structural diagram of a reaction apparatus for preparing amino-modified nano-polystyrene according to the present invention;
FIG. 2 is a transmission electron microscope image of amino-modified nano-polystyrene of the present invention;
FIG. 3 is a graph of the effect of dodecylamine hydrochloride usage on the particle size distribution of the product;
FIG. 4 Effect of the amount of dodecylamine hydrochloride used on the average particle size of the product.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides amino-modified nano-polystyrene and a preparation method thereof, aiming at the problems of uncontrollable particle size and large particle size of aminated polystyrene nanoparticles in the prior art.
The structure schematic diagram of the preparation reaction device of amino modified nano-polystyrene is shown in figure 1, wherein 1 is a water bath device, 2 is a condensing device, 3 is a stirring motor, 4 is a three-neck flask, and 5 is a stirring paddle.
Example 1
The amino modified nano-polystyrene comprises the following components in percentage by mass: 8 percent of monomer styrene, 1.5 percent of dodecylamine hydrochloride, 0.45 percent of azo-diisobutyl amidine hydrochloride and the balance of water.
The preparation method of the amino-modified nano-polystyrene comprises the following steps:
1) weighing 1.5g of dodecylamine hydrochloride and 85g of deionized water, adding into a reaction bottle, mixing, wherein the reaction temperature is 75 ℃, and the stirring speed is 300 revolutions per minute;
2) weighing 8g of styrene, adding into a reactor and sealing;
3) a mixture of 0.15g of azobisisobutylamidine hydrochloride and 1.68g of deionized water was added dropwise while the reaction was carried out for 30min, 60min and 120min, respectively;
4) and stopping stirring after the reaction is carried out for 5 hours, and cooling to room temperature to obtain the amino modified nano-polystyrene.
As shown in FIG. 2, the amino-modified nano-polystyrene prepared in this example has an average particle size of 40 nm.
Example 2
The amino modified nano-polystyrene comprises the following components in percentage by mass: monomer styrene 2%, dodecylamine hydrochloride 1%, azobisisobutylamidine hydrochloride 0.3%, and the balance of water.
The preparation method of the amino-modified nano-polystyrene comprises the following steps:
1) weighing 1g of dodecylamine hydrochloride and 85g of deionized water, adding into a reaction bottle, mixing, wherein the reaction temperature is 75 ℃, and the stirring speed is 300 revolutions per minute;
2) weighing 2g of styrene, adding the styrene into a reactor and sealing the reactor;
3) a mixture of 0.1g of azobisisobutylamidine hydrochloride and 3.9g of deionized water was added dropwise while the reaction was carried out for 30min, 60min and 120min, respectively;
4) and stopping stirring after the reaction is carried out for 5 hours, and cooling to room temperature to obtain the amino modified nano-polystyrene.
The amino-modified nano-polystyrene prepared in this example had an average particle size of 20 nm.
Example 3
The amino modified nano-polystyrene comprises the following components in percentage by mass: 5.6 percent of monomer styrene, 0.5 percent of dodecylamine hydrochloride, 0.36 percent of azo-diisobutyl amidine hydrochloride and the balance of water.
The preparation method of the amino-modified nano-polystyrene comprises the following steps:
1) weighing 0.5g of dodecylamine hydrochloride and 85g of deionized water, adding into a reaction bottle, mixing, wherein the reaction temperature is 75 ℃, and the stirring speed is 300 r/min;
2) weighing 6.3g of styrene, adding the styrene into a reactor and sealing the reactor;
3) a mixture of 0.12g of azobisisobutylamidine hydrochloride and 2.61g of deionized water was added dropwise while the reaction was carried out for 30min, 60min and 120min, respectively;
4) and stopping stirring after the reaction is carried out for 5 hours, and cooling to room temperature to obtain the amino modified nano-polystyrene.
The amino-modified nano-polystyrene prepared in this example had an average particle size of 35 nm.
Example 4
In order to study the influence of different masses of dodecylamine hydrochloride on the particle size of the amino-modified nano-polystyrene, the amino-modified nano-polystyrene was prepared according to the following method and dosage:
1) weighing 0.1g, 0.2 g, 0.3g, 0.4 g, 0.5g, 0.7 g and 1.0g of dodecylamine hydrochloride and 80g of deionized water respectively, adding the weighed materials into different reaction bottles, mixing, wherein the reaction temperature is 75 ℃, and the stirring speed is 300 revolutions per minute;
2) weighing 5g of styrene, adding the styrene into a reactor and sealing the reactor;
3) a mixture of 0.3g of azobisisobutylamidine hydrochloride and 3g of deionized water was added dropwise at 30min, 60min and 120min of reaction, respectively;
4) and stopping stirring after the reaction is carried out for 5 hours, and cooling to room temperature to obtain the amino modified nano-polystyrene.
5) After the reaction is finished, amino group modified nano-polystyrene under dodecylamine hydrochloride with different masses is measured.
The particle size of the prepared nano-polystyrene is measured, and as can be seen from figure 3, the product is nano-scale and has good uniformity. As can be seen from FIG. 4, the amount of the dodecylamine hydrochloride is increased within a certain range, the surface tension of the system is obviously reduced, so that the average particle size of the product is reduced, the average particle size of the prepared product is 0.5-1.5%, the uniformity of the prepared product is good, the average particle size is 20-45nm, and when the concentration of the dodecylamine hydrochloride exceeds the range, the prepared product is poor in uniformity, and some products even cannot be formed.
To further illustrate the beneficial effects of the present invention, a corresponding comparative example was constructed by taking example 3 as an example only.
Comparative example 1
The amino modified nano-polystyrene comprises the following components in percentage by mass: 5.6 percent of monomer styrene, 0.5 percent of hexadecyl trimethyl ammonium bromide, 0.36 percent of azo-diisobutyl amidine hydrochloride and the balance of water.
The preparation method is the same as in example 3.
The particle size of the amino-modified nano-polystyrene measured was 121 nm.
Comparative example 2
The amino modified nano-polystyrene comprises the following components in percentage by mass: 5.6 percent of styrene monomer, 1 percent of hexadecyl trimethyl ammonium bromide, 0.36 percent of azo-diisobutyl amidine hydrochloride and the balance of water.
The preparation method is the same as in example 3.
The particle size of the amino-modified nano-polystyrene measured was 118 nm.
The scheme provided by the invention realizes the controllable preparation of the polystyrene, the particle size of the polystyrene is controlled at a nanometer level, and the particle size distribution basically conforms to normal distribution; the initiator and the surfactant are less in dosage, the cost is low, and the medicine is easy to obtain; does not need high-temperature violent reaction conditions and has low requirements on reaction devices and equipment.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. The amino-modified nano polystyrene is characterized by being prepared from the following components in percentage by weight: 2-8% of monomer styrene, 0.5-1.5% of dodecylamine hydrochloride, 0.3-0.5% of azo diisobutyl amidine hydrochloride and the balance of water;
the preparation method of the amino-modified nano-polystyrene comprises the following steps:
step 1: mixing monomer styrene, surfactant dodecylamine hydrochloride and water, stirring and emulsifying; adding initiator azobisisobutylamidine hydrochloride, wherein the mass ratio of monomer styrene, surfactant dodecylamine hydrochloride and initiator azobisisobutylamidine hydrochloride in the reaction system is 2-8: 0.5-1.5: 0.3-0.5;
step 2: placing the reaction system in the step 1 at 65-80 ℃, stirring for polymerization reaction for 4-6 hours, and cooling to room temperature under natural conditions to prepare the amino-modified nano-polystyrene;
wherein the initiator is added for three times when the reaction is carried out for 30min, 60min and 120 min.
2. The amino-modified nano-polystyrene according to claim 1, which is prepared from the following components in percentage by weight: 5-6% of monomer styrene, 0.5-1% of dodecylamine hydrochloride, 0.3-0.36% of azo-diisobutyl amidine hydrochloride and the balance of water.
3. The method for preparing amino-modified nano-polystyrene as claimed in claim 1 or 2, which comprises:
step 1: mixing monomer styrene, surfactant and water, stirring and emulsifying; adding an initiator, wherein the mass ratio of monomer styrene, surfactant and initiator in the reaction system is 2-8: 0.5-1.5: 0.3-0.5;
step 2: placing the reaction system in the step 1 at 65-80 ℃, stirring for polymerization reaction for 4-6 hours, and cooling to room temperature under natural conditions to prepare amino-modified nano-polystyrene;
wherein the surfactant is dodecylamine hydrochloride; .
The initiator is azodiisobutyl amidine hydrochloride;
the initiator is added for three times when the reaction is carried out for 30min, 60min and 120 min.
4. The method for preparing amino-modified nano-polystyrene as claimed in claim 3, wherein the water is distilled water or deionized water, and the mass ratio of the water to the surfactant is 70-90: 1.
5. The method for preparing amino-modified nano-polystyrene as claimed in claim 3, wherein the stirring speed is 300 rpm.
6. The method for preparing amino-modified nano-polystyrene as claimed in any one of claims 3 to 5, wherein said initiator is added dropwise at a rate of 20 to 30 d/min.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017101290927 | 2017-03-06 | ||
| CN201710129092 | 2017-03-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107417833A CN107417833A (en) | 2017-12-01 |
| CN107417833B true CN107417833B (en) | 2020-04-17 |
Family
ID=60430532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710609812.XA Active CN107417833B (en) | 2017-03-06 | 2017-07-25 | Amino modified nano polystyrene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107417833B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56109208A (en) * | 1980-02-01 | 1981-08-29 | Sekisui Chem Co Ltd | Preparation of latex for serological diagnosis reagent |
| JPH01210406A (en) * | 1988-02-18 | 1989-08-24 | Idemitsu Petrochem Co Ltd | Suspension polymerization of styrene resin |
| CN101591407A (en) * | 2008-05-30 | 2009-12-02 | 北京化工大学 | A kind of preparation method of polystyrene nanoparticle |
| CN101880343A (en) * | 2010-06-30 | 2010-11-10 | 广州市香港科大霍英东研究院 | Fluorescent polymer environment-friendly material with Beta-dione aggregative luminous structure |
| CN105061649A (en) * | 2015-08-07 | 2015-11-18 | 武汉理工大学 | Synthetic method of polystyrene emulsion with extra-high solid content |
| US9512248B1 (en) * | 2015-12-28 | 2016-12-06 | Chevron Phillips Chemical Company Lp | Mixed decyl mercaptans compositions and use thereof as chain transfer agents |
-
2017
- 2017-07-25 CN CN201710609812.XA patent/CN107417833B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56109208A (en) * | 1980-02-01 | 1981-08-29 | Sekisui Chem Co Ltd | Preparation of latex for serological diagnosis reagent |
| JPH01210406A (en) * | 1988-02-18 | 1989-08-24 | Idemitsu Petrochem Co Ltd | Suspension polymerization of styrene resin |
| CN101591407A (en) * | 2008-05-30 | 2009-12-02 | 北京化工大学 | A kind of preparation method of polystyrene nanoparticle |
| CN101880343A (en) * | 2010-06-30 | 2010-11-10 | 广州市香港科大霍英东研究院 | Fluorescent polymer environment-friendly material with Beta-dione aggregative luminous structure |
| CN105061649A (en) * | 2015-08-07 | 2015-11-18 | 武汉理工大学 | Synthetic method of polystyrene emulsion with extra-high solid content |
| US9512248B1 (en) * | 2015-12-28 | 2016-12-06 | Chevron Phillips Chemical Company Lp | Mixed decyl mercaptans compositions and use thereof as chain transfer agents |
Non-Patent Citations (1)
| Title |
|---|
| 乳液聚合法制备聚苯乙烯微球;于晓辉等;《长春理工大学学报》;20061231;第29卷(第4期);94-96 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107417833A (en) | 2017-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105131309B (en) | Nano combined latex particle dispersion liquid of lithium metasilicate magnesium of polymer/artificial synthesized and preparation method thereof | |
| CN102649826A (en) | Preparation method of particle diameter controllable monodisperse polystyrene microspheres | |
| Rymaruk et al. | Raft dispersion polymerization of benzyl methacrylate in silicone oil using a silicone-based methacrylic stabilizer provides convenient access to spheres, worms, and vesicles | |
| CN105418835A (en) | Preparing method for core-shell structure functionality acrylate polymer particles for toughening polycarbonate | |
| CN106589464A (en) | Preparation method for vinyl polymer coated nano-silica microsphere and modified epoxy resin | |
| CN106832097B (en) | One kind being based on SiO2PH responsiveness composite microgel and preparation method thereof | |
| Zhang et al. | Acrylic emulsifier-free emulsion polymerization containing hydrophilic hydroxyl monomer in the presence or absence of nano-SiO2 | |
| Gao et al. | Preparation of thermoresponsive poly (N‐vinylcaprolactam‐co‐2‐methoxyethyl acrylate) nanogels via inverse miniemulsion polymerization | |
| CN105778383A (en) | Preparation method of core-shell particle reinforced hydrophobically associating hydrogel | |
| Takafuji et al. | Microspherical hydrogel particles based on silica nanoparticle-webbed polymer networks | |
| CN103275268A (en) | Preparation method of pH responsive cation nanogel | |
| CN103772598B (en) | A kind of regulate and control method of single dispersing functional polymer microsphere surfaceness | |
| CN107417833B (en) | Amino modified nano polystyrene and preparation method thereof | |
| CN102453260A (en) | Preparation method of alpha-olefin anti-drag polymer solid-phase storage-stable particle | |
| Trzebicka et al. | Mesoglobules of random copolyethers as templates for nanoparticles | |
| CN103396505A (en) | Preparation method of pure cationic nanosphere | |
| Zhu et al. | Preparation of monodisperse polystyrene nanoparticles with tunable sizes based on soap-free emulsion polymerization technology | |
| CN1300190C (en) | Method for preparing mono dispersed functionalized polymer microsphere | |
| Zou et al. | Synthesis and characterization of amphoteric polyacrylamide by dispersion polymerization in aqueous salts solution | |
| CN102174145B (en) | Temperature-sensitive core-shell acrylate functional microspheres and preparation method thereof | |
| CN107236078A (en) | A kind of preparation method of flexible soft monomer colloidal photon crystal emulsion | |
| CN104031210A (en) | Method for preparing quaternary ammonium salt surface-modified monodisperse polystyrene microsphere emulsion | |
| CN109180844B (en) | Polystyrene microsphere with rough surface as well as preparation method and application thereof | |
| CN107955092A (en) | A kind of gas hydrate nanometer accelerating agent of size tunable and preparation method thereof | |
| Imaz et al. | Synthesis and characterization of saccharide‐based latex particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |