CN102516463A - Method for preparing nano spherical polyelectrolyte brush - Google Patents
Method for preparing nano spherical polyelectrolyte brush Download PDFInfo
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- CN102516463A CN102516463A CN2011103771750A CN201110377175A CN102516463A CN 102516463 A CN102516463 A CN 102516463A CN 2011103771750 A CN2011103771750 A CN 2011103771750A CN 201110377175 A CN201110377175 A CN 201110377175A CN 102516463 A CN102516463 A CN 102516463A
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Abstract
The invention relates to a novel method for preparing a nano spherical polyelectrolyte brush. The method can be used for preparing the spherical polyelectrolyte brush with the particle size of 200 to 600 nanometers by using polybutadiene emulsion particles with the particle sizes of 110 to 320 nanometers as cores and utilizing rich double bonds on the surfaces of the polybutadiene emulsion particles through carrying out copolymerization on the polybutadiene emulsion particles and added electrolyte monomers such as acrylic acid, sodium styrene sulfonate and the like under the initiation of an initiator. The polyelectrolyte brush can be applied to the fields of concentration and adsorption of metal ions with positive electricity and counter ions with negative electricity in water, preparation of nano metal particles by the in-situ reduction reaction, immobilization of a biological enzyme, separation of proteins and the like.
Description
Technical field
The present invention relates to the preparation method and the application thereof of polymkeric substance, specifically utilize a kind of industrial copolymer latex to prepare the novel method of nanometer spherical polyelectrolyte brush through surface and copolymerized modification and be applied to concentrate with planar water in positively charged metals ion or electronegative gegenion, through fields such as in-situ reducing prepared in reaction nano metal particles, immobilized enzyme and separating proteins.
Background technology
When polymer chain was fixed in certain interface with an end and arranges densely, because the volume excluding effect, their free end will outwards stretch and form a kind of structure as brush, i.e. polymer brush.This brush structure of polymer can greatly change surface property, like cementability, oilness, wettability, frictional property, biocompatibility etc., has a wide range of applications in a lot of fields.If form charged polymer brush, just can obtain nanometer spherical polyelectrolyte brush on the surface of nano level emulsion particle.Polyelectrolyte brush can increase the Coulomb repulsion effect on the basis that forms the polymer brush steric restriction, thus can stop more effectively emulsion particle each other near, not only can improve the emulsion particle surface property, can also improve the stability of emulsion greatly.And the inner microenvironment (like gegenion concentration, pH value etc.) of polyelectrolyte brush can keep relative stability and not change with the change of outside atmosphere, and the extension degree of polymer chain can be by controls such as temperature, pH value, ionic concns.This just prepares nano metal particles for concentrating with adsorbing metal ions and in-situ reducing, for preparing controlled nano-device, for protein, enzyme, medicine and diagnosis group etc. immobilized opened up a new way.
At present, the preparation method of nanometer spherical polyelectrolyte brush comparative maturity is the light letex polymerization, and soon light trigger is connected on the nuclear surface and trigger monomer in-situ polymerization formation spherical polyelectrolyte brush under UV-irradiation.But also there are some problems that are difficult to overcome in the light emulsion polymerisation process, and is low like light-initiated efficient, and ultraviolet reactor is complicated and expensive, is unfavorable for realizing suitability for industrialized production.Compare with traditional light-initiated emulsion polymerization; Have drawn from industriallization polybutadiene latex and only need the simple heating realization response of the present invention; Raw materials cost is low, and the preparation method is simple, is the important channel of the nanometer spherical polyelectrolyte brush of large-scale industrialization production in the future.
Summary of the invention
The objective of the invention is to overcome light emulsion polymerization prepared nanometer spherical polyelectrolyte brush and be difficult for industrialized technological deficiency, provide the industrial polybutadiene latex of a kind of direct utilization to have the novel method of core-shell nanospheres shape polyelectrolyte brush through surface and copolymerized modification preparation.Concrete scheme is following:
A kind of preparation method of nanometer spherical polyelectrolyte brush comprises the steps:
(1) with the technical grade polybutadiene latex with the deionized water purifying of dialysing, constant basically up to outside electrical conductivity of water, the kind of dialysis membrane is selected according to the size of said polybutadiene latex particle;
(2) polybutadiene latex of dialysing in the step (1) is added in the reactor drum; Add water-soluble thermal initiator, take out inflated with nitrogen 3～5 times, under nitrogen protection, be warming up to 60～90 ℃; Then drip the water-soluble polyelectrolyte monomer from constant pressure funnel; Holding temperature is constant, and polyreaction 0.5～3 hour promptly obtains having the nanometer spherical polyelectrolyte brush of nucleocapsid structure;
Wherein, said water-soluble thermal initiator is hydrogen peroxide or Potassium Persulphate, and its consumption is 1.5～3% of a said polybutadiene latex solid content;
Said water-soluble polyelectrolyte monomer is vinylformic acid, methylacrylic acid or sodium p styrene sulfonate, and its consumption is 20～120% of a said polybutadiene latex solid content.
Above-mentioned prepare nanometer spherical polyelectrolyte brush can be used for concentrating with planar water in positively charged metals ion or electronegative gegenion, through fields such as in-situ reducing prepared in reaction nano metal particles, immobilized enzyme and separating proteins.
Description of drawings
Fig. 1 is a preparation route map of the present invention.
Embodiment:
The present invention further specifies the present invention with the following example, but protection scope of the present invention is not limited to embodiment.Under the situation that does not deviate from spirit of the present invention and protection domain, can make many other variation and modifications to those skilled in the art, still be included in the scope of protecting in claims.
At first, explain that the preparation route is following:
Embodiment 1
Get 300 gram polyhutadiene emulsions (recording its solid content is 2%, and particle diameter is 312 nanometers), add 0.12 gram Potassium Persulphate (be polyhutadiene emulsion solid content 2%).Take out inflated with nitrogen 3～5 times, be warming up to 80 ℃, drip fast 6 gram Acrylic Acid Monomers (for the polyhutadiene emulsion solid content 100%) finish behind the polymerase 10 .5 hour.Using molecular weight cut-off is that the median size that records spherical polyelectrolyte brush was 612 nanometers (pH=5) after 14000 dialysis tubing was dialysed in deionized water.
Embodiment 2
Get 300 gram polyhutadiene emulsions (recording its solid content is 2%, and particle diameter is 312 nanometers), add 0.12 gram Potassium Persulphate (be polyhutadiene emulsion solid content 2%).Take out inflated with nitrogen 3～5 times, be warming up to 80 ℃, drip fast 4.5 gram Acrylic Acid Monomers (for the polyhutadiene emulsion solid content 75%) finish behind the polymerase 10 .5 hour.Using molecular weight cut-off is that the median size that records spherical polyelectrolyte brush was 513 nanometers (pH=5) after 14000 dialysis tubing was dialysed in deionized water.
Embodiment 3
Get 300 gram polyhutadiene emulsions (recording its solid content is 2%, and particle diameter is 312 nanometers), add 0.12 gram Potassium Persulphate (be polyhutadiene emulsion solid content 2%).Take out inflated with nitrogen 3～5 times, be warming up to 80 ℃, drip fast 3 gram Acrylic Acid Monomers (for the polyhutadiene emulsion solid content 50%) finish behind the polymerase 10 .5 hour.Using molecular weight cut-off is that the median size that records spherical polyelectrolyte brush was 477 nanometers (pH=5) after 14000 dialysis tubing was dialysed in deionized water.
Embodiment 4
Get 250 gram polyhutadiene emulsions (recording its solid content is 2%, and particle diameter is 112 nanometers), add 0.1 gram Potassium Persulphate (be polyhutadiene emulsion solid content 2%).Take out inflated with nitrogen 3～5 times, be warming up to 80 ℃, fast Dropwise 5 gram Acrylic Acid Monomer (be polyhutadiene emulsion solid content 100%) end after polymerase 10 .5 hour.Using molecular weight cut-off is that the median size that records spherical polyelectrolyte brush was 250.4 nanometers (pH=5) after 14000 dialysis tubing was dialysed in deionized water.
Embodiment 5
Get 250 gram polyhutadiene emulsions (recording its solid content is 2%, and particle diameter is 112 nanometers), add 0.1 gram Potassium Persulphate (be polyhutadiene emulsion solid content 2%).Take out inflated with nitrogen 3～5 times, be warming up to 80 ℃, drip fast 3.75 gram Acrylic Acid Monomers (for the polyhutadiene emulsion solid content 75%) finish behind the polymerase 10 .5 hour.Using molecular weight cut-off is that the median size that records spherical polyelectrolyte brush was 180.9 nanometers (pH=5) after 14000 dialysis tubing was dialysed in deionized water.
Embodiment 6
Get 250 gram polyhutadiene emulsions (recording its solid content is 2%, and particle diameter is 112 nanometers), add 0.1 gram Potassium Persulphate (be polyhutadiene emulsion solid content 2%).Take out inflated with nitrogen 3～5 times, be warming up to 80 ℃, drip fast 2.5 gram Acrylic Acid Monomers (for the polyhutadiene emulsion solid content 50%) finish behind the polymerase 10 .5 hour.Using molecular weight cut-off is that the median size that records spherical polyelectrolyte brush was 168 nanometers (pH=5) after 14000 dialysis tubing was dialysed in deionized water.
Table 1 is particle diameter and the size distribution that adopts the nanometer spherical polyelectrolyte brush that the dynamic light scattering particle size appearance records.
Claims (1)
1. the preparation method of a nanometer spherical polyelectrolyte brush is characterized in that, comprises the steps:
(1) with the technical grade polybutadiene latex with the deionized water purifying of dialysing, constant basically up to outside electrical conductivity of water, the kind of dialysis membrane is selected according to the size of said polybutadiene latex particle;
(2) polybutadiene latex of dialysing in the step (1) is added in the reactor drum; Add water-soluble thermal initiator, take out inflated with nitrogen 3～5 times, under nitrogen protection, be warming up to 60～90 ℃; Then drip the water-soluble polyelectrolyte monomer from constant pressure funnel; Holding temperature is constant, and polyreaction 0.5～3 hour promptly obtains having the nanometer spherical polyelectrolyte brush of nucleocapsid structure;
Wherein, said water-soluble thermal initiator is hydrogen peroxide or Potassium Persulphate, and its consumption is 1.5～3% of a said polybutadiene latex solid content;
Said water-soluble polyelectrolyte monomer is vinylformic acid, methylacrylic acid or sodium p styrene sulfonate, and its consumption is 20～120% of a said polybutadiene latex solid content.
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| CN 201110377175 CN102516463B (en) | 2011-11-24 | 2011-11-24 | Method for preparing nano spherical polyelectrolyte brush |
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| CN 201110377175 CN102516463B (en) | 2011-11-24 | 2011-11-24 | Method for preparing nano spherical polyelectrolyte brush |
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| CN102516463A true CN102516463A (en) | 2012-06-27 |
| CN102516463B CN102516463B (en) | 2013-12-18 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827330A (en) * | 2012-09-11 | 2012-12-19 | 华东理工大学 | Preparation method of gel nano particles in thermosensitivie nuclear shell structure and application of product thereof |
| CN102976391A (en) * | 2012-12-07 | 2013-03-20 | 华东理工大学 | Method for preparing nano zinc oxide by taking nano spherical polyelectrolyte brush as microreactor and application of nano zinc oxide |
| CN112679665A (en) * | 2020-12-24 | 2021-04-20 | 华东理工大学 | Preparation method of nano spherical polyelectrolyte brush |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768111A (en) * | 2003-05-02 | 2006-05-03 | Lg化学株式会社 | Thermoplastic resin composition |
| CN101381435A (en) * | 2008-10-22 | 2009-03-11 | 华东理工大学 | Preparation method of spherical polyelectrolyte brush and use thereof |
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2011
- 2011-11-24 CN CN 201110377175 patent/CN102516463B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768111A (en) * | 2003-05-02 | 2006-05-03 | Lg化学株式会社 | Thermoplastic resin composition |
| CN101381435A (en) * | 2008-10-22 | 2009-03-11 | 华东理工大学 | Preparation method of spherical polyelectrolyte brush and use thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827330A (en) * | 2012-09-11 | 2012-12-19 | 华东理工大学 | Preparation method of gel nano particles in thermosensitivie nuclear shell structure and application of product thereof |
| CN102976391A (en) * | 2012-12-07 | 2013-03-20 | 华东理工大学 | Method for preparing nano zinc oxide by taking nano spherical polyelectrolyte brush as microreactor and application of nano zinc oxide |
| CN112679665A (en) * | 2020-12-24 | 2021-04-20 | 华东理工大学 | Preparation method of nano spherical polyelectrolyte brush |
| CN112679665B (en) * | 2020-12-24 | 2022-07-15 | 华东理工大学 | Preparation method of nano spherical polyelectrolyte brush |
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| CN102516463B (en) | 2013-12-18 |
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