CN102516463B - Method for preparing nano spherical polyelectrolyte brush - Google Patents
Method for preparing nano spherical polyelectrolyte brush Download PDFInfo
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- CN102516463B CN102516463B CN 201110377175 CN201110377175A CN102516463B CN 102516463 B CN102516463 B CN 102516463B CN 201110377175 CN201110377175 CN 201110377175 CN 201110377175 A CN201110377175 A CN 201110377175A CN 102516463 B CN102516463 B CN 102516463B
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- polybutadiene latex
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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 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 by surface and copolymerized modification and be applied to positively charged in concentrated and planar water metal ion or electronegative gegenion, react by in-situ reducing fields such as preparing nano metal particles, immobilized biological enzyme and isolated protein.
Background technology
Be fixed in certain interface when polymer chain with an end and while arranging densely, due to the volume excluding effect, their free end will outwards stretch and form a kind of structure as the brush, i.e. polymer brush.This brush structure of polymer can greatly change surface property, as cementability, oilness, wettability, frictional property, biocompatibility etc., has a wide range of applications in a lot of fields.If form charged polymer brush on the surface of nano level emulsion particle, just can obtain nanometer spherical polyelectrolyte brush.Polyelectrolyte brush can increase electrostatic repulsion on the basis that forms the polymer brush steric restriction, thereby can more effectively stop the mutually close of emulsion particle, not only can improve the emulsion particle surface property, can also greatly improve the stability of emulsion.And the microenvironment of polyelectrolyte brush inside (as gegenion concentration, pH value etc.) can keep relative stability and not change with the change of outside atmosphere, the extension degree of polymer chain can be by controls such as temperature, pH value, ionic concns.This just prepares nano metal particles for concentrated and adsorbing metal ions 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 core 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, as low as light-initiated efficiency, ultraviolet reactor is complicated and expensive, is unfavorable for realizing suitability for industrialized production.With traditional light-initiated emulsion polymerization, compare, have drawn from industrialization polybutadiene latex and only need simply to heat realization response of the present invention, raw materials cost is low, and the preparation method is simple, is the important channel that large-scale industrialization is produced nanometer spherical polyelectrolyte brush in the future.
Summary of the invention
The object of the invention is to overcome the light letex polymerization and prepare nanometer spherical polyelectrolyte brush and be difficult for industrialized technological deficiency, provide the industrial polybutadiene latex of a kind of direct utilization to there is the novel method of core-shell nanospheres shape polyelectrolyte brush by surface and copolymerized modification preparation.Concrete scheme is as follows:
A kind of preparation method of nanometer spherical polyelectrolyte brush, comprise the steps:
(1) by the deionized water purifying of dialysing for the technical grade polybutadiene latex, until outside electrical conductivity of water is substantially constant, the kind of dialysis membrane is selected according to the size of described polybutadiene latex particle;
(2) polybutadiene latex of dialysing in step (1) is added in reactor, add water-soluble thermal initiator, take out inflated with nitrogen 3～5 times, be warming up to 60～90 ℃ under nitrogen protection, then from constant pressure funnel, drip the water-soluble polyelectrolyte monomer, holding temperature is constant, and polyreaction 0.5～3 hour obtains having the nanometer spherical polyelectrolyte brush of nucleocapsid structure;
Wherein, described water-soluble thermal initiator is hydrogen peroxide or Potassium Persulphate, and its consumption is 1.5～3% of described polybutadiene latex solid content;
Described water-soluble polyelectrolyte monomer is vinylformic acid, methacrylic acid or sodium p styrene sulfonate, and its consumption is 20～120% of described polybutadiene latex solid content.
Above-mentionedly prepare metal ion or electronegative gegenion that nanometer spherical polyelectrolyte brush can be used for positively charged in concentrated and planar water, by in-situ reducing, react fields such as preparing nano metal particles, immobilized biological enzyme and isolated protein.
The accompanying drawing explanation
Fig. 1 is syntheti c route figure of the present invention.
Embodiment:
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to embodiment.Can make many other changes and modifications in the case of without departing from the spirit and scope of protection of the present invention to those skilled in the art, still be included in the scope of protecting in claims.
Syntheti c route of the present invention as shown in Figure 1.
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 (for the 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 after polymerase 10 .5 hour.After the dialysis tubing that is 14000 with molecular weight cut-off is dialysed in deionized water, the median size that records spherical polyelectrolyte brush is 612 nanometers (pH=5).
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 (for the 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 after polymerase 10 .5 hour.After the dialysis tubing that is 14000 with molecular weight cut-off is dialysed in deionized water, the median size that records spherical polyelectrolyte brush is 513 nanometers (pH=5).
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 (for the 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 after polymerase 10 .5 hour.After the dialysis tubing that is 14000 with molecular weight cut-off is dialysed in deionized water, the median size that records spherical polyelectrolyte brush is 477 nanometers (pH=5).
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 (for the polyhutadiene emulsion solid content 2%).Take out inflated with nitrogen 3～5 times, be warming up to 80 ℃, drip fast 5 gram Acrylic Acid Monomers (for the polyhutadiene emulsion solid content 100%) finish after polymerase 10 .5 hour.After the dialysis tubing that is 14000 with molecular weight cut-off is dialysed in deionized water, the median size that records spherical polyelectrolyte brush is 250.4 nanometers (pH=5).
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 (for the 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 after polymerase 10 .5 hour.After the dialysis tubing that is 14000 with molecular weight cut-off is dialysed in deionized water, the median size that records spherical polyelectrolyte brush is 180.9 nanometers (pH=5).
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 (for the 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 after polymerase 10 .5 hour.After the dialysis tubing that is 14000 with molecular weight cut-off is dialysed in deionized water, the median size that records spherical polyelectrolyte brush is 168 nanometers (pH=5).
Table 1 is particle diameter and the size distribution of the nanometer spherical polyelectrolyte brush that adopts the dynamic light scattering particle size instrument to record.
The particle diameter of table 1 spherical polyelectrolyte brush and size distribution
Claims (1)
1. the preparation method of a nanometer spherical polyelectrolyte brush, is characterized in that, comprises the steps:
(1) by the deionized water purifying of dialysing for the technical grade polybutadiene latex, until outside electrical conductivity of water is substantially constant, the kind of dialysis membrane is selected according to the size of described polybutadiene latex particle;
(2) polybutadiene latex of dialysing in step (1) is added in reactor, add water-soluble thermal initiator, take out inflated with nitrogen 3～5 times, be warming up to 60～90 ℃ under nitrogen protection, then from constant pressure funnel, drip the water-soluble polyelectrolyte monomer, holding temperature is constant, polyreaction 0.5～3 hour, after the dialysis tubing that is 14000 with molecular weight cut-off is dialysed in deionized water, obtain having the nanometer spherical polyelectrolyte brush of nucleocapsid structure;
Wherein, described water-soluble thermal initiator is hydrogen peroxide or Potassium Persulphate, and its consumption is 1.5～3% of described polybutadiene latex solid content;
Described water-soluble polyelectrolyte monomer is vinylformic acid, methacrylic acid or sodium p styrene sulfonate, and its consumption is 20～120% of described 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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| CN102516463B true CN102516463B (en) | 2013-12-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN112679665B (en) * | 2020-12-24 | 2022-07-15 | 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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| 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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