CN102617757B - Method for preparing polymer nanometer particles - Google Patents
Method for preparing polymer nanometer particles Download PDFInfo
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- CN102617757B CN102617757B CN 201210072217 CN201210072217A CN102617757B CN 102617757 B CN102617757 B CN 102617757B CN 201210072217 CN201210072217 CN 201210072217 CN 201210072217 A CN201210072217 A CN 201210072217A CN 102617757 B CN102617757 B CN 102617757B
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Abstract
The invention discloses a method for preparing polymer nanometer particles, belonging to the technical field of chemistry and chemical industry. The method comprises the steps of: starting with polymer monomer containing an initiating agent and a cross-linking agent and a water solution containing a surfactant, taking a microporous film as a dispersion medium, firstly preparing oil-in-water initial emulsion by utilizing a cross flow shearing method, repeatedly pressing the initial emulsion to permeate the film so as to prepare miniemulsion, heating the miniemulsion to complete a thermal initiation polymerization reaction, and finally demulsifying and washing to obtain the polymer nanometer particles. The method has the advantages that the involved system is easy to construct; the application range is wide; the preparation time is short; the average particle size of the obtained product is adjustable between 30-300nm; the particle size distribution is narrow; and the scale preparation and application of the polymer nanometer particles are benefited.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, particularly a kind of method for preparing polymer nano granules.
Background technology
Polymer nano granules shows wide application prospect because of its superior physics and chemical property in fields such as photoelectric material, conducting polymer, sensor, environmental improvement, biological medicines.At present, the preparation method of polymer nano granules can be divided into two big classes: polymer dispersed method and monomer polymerization method.The polymer dispersed method refers to the polymkeric substance to be thereby that raw material makes it finish the method that the pattern change prepares polymer nano granules by physical methods such as solvent evaporates, solute crystallization, nanometer precipitation, electrolysis or supercritical fluid technologys; Process for polymerizing monomers refers to that polymer monomer directly generates the nano shape polymkeric substance after polyreaction.Comprise conventional emulsion polymerization, thin newborn polymerization, micro emulsion polymerization, interfacial polymerization etc. in this method.Advantages such as wherein, thin newborn polymerization has that rate of polymerization is fast, dosage of surfactant is few, composition and pattern regulation and control are convenient.
The prerequisite of thin newborn polymerization is that the preparation drop size is received emulsion (also claiming miniemulsion) at 20-500nm.Conventional preparation is received the method for emulsion and is mainly contained high-speed mixing method, high pressure homogenization method and ultrasonic method.These methods all exist energy consumption height, droplets size distribution wide, be difficult for defectives such as serialization production and engineering amplification.In recent years, the film emulsifying technology has obtained to study widely and use because it has advantages such as the narrow and easy-regulating of low, the prepared droplets size distribution of energy consumption.Yet, utilize film emulsification to prepare miniemulsion and but rarely have report.If film emulsification and thin newborn polymerization can be combined, be expected to develop a kind of efficient, simple to operate, easily realize the controllable method for preparing of the polymer nano granules that engineering is amplified, to the large-scale production that promotes polymer nano granules with use significant.
Summary of the invention
The present invention is intended to propose a kind of method for preparing polymer nano granules, its principle is: (1) is from the polymer monomer that contains initiator and linking agent and the aqueous solution that contains tensio-active agent, be dispersion medium with the microporous membrane, at first utilize the cross-flow cutting method to prepare oil-in-water colostric fluid, again colostric fluid was pressed repeatedly membrane prepare emulsion droplet size control tens of between hundreds of nanometers, surpass the miniemulsion of 4h steady time; (2) make the miniemulsion system fast, controllably finish polymerization by the thermal initiation method, each drop is equivalent to a nano level microreactor, the forming process of polymer nano granules is all finished in drop, can realize drop accurately copying to the solid nano particle.
A kind of method for preparing polymer nano granules that the present invention proposes, can realize as follows:
(1) with the polymer monomer that is dissolved with initiator, linking agent as raw material A.
(2) with the aqueous solution that is dissolved with tensio-active agent as raw material B.
(3) raw material A is entered at the microporous membrane opposite side under differential pressure action by a side of microporous membrane with linear velocity 0.1-1.5m/s by fenestra and be parallel to linear velocity 0.5-5m/s among the raw material B that face flows, form colostric fluid.
(4) make colostric fluid speed with 0.2-3m/s under differential pressure action pass through microporous membrane, obtain the secondary emulsion.
(5) with the secondary emulsion as colostric fluid, repeating step (4) 0-4 time obtains miniemulsion C.
(6) heating miniemulsion C carries out polyreaction, obtains containing the emulsion D of polymer nano granules.
(7) add emulsion splitter emulsion D is carried out breakdown of emulsion, throw out obtains polymer nano granules through washing.
Described polymer monomer is vinylbenzene, styrene derivatives or their mixture.
Described initiator is Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO); Described linking agent is Vinylstyrene (DVB).
The massfraction of initiator is 0.2-5% in the described raw material A, and the massfraction of linking agent is 0-20%.
Tensio-active agent is sodium lauryl sulphate (SDS), polyvinyl alcohol (PVA) or their mixture among the described raw material B.
The massfraction of tensio-active agent is 0.2-10% among the described raw material B.
The volume flow ratio of described raw material B and raw material A is (1-20): 1.
The time of described polyreaction is 0.5-5 hour; Polymeric reaction temperature is 60-100 ℃.
Described emulsion splitter is the Fatty Alcohol(C12-C14 and C12-C18) of C1-C4, and is preferred: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol.
The aperture of described microporous membrane is 0.2-5 μ m.
Beneficial effect of the present invention is: (1) by make up multiple film system breast process prepare fast drop size at tens nanometer to the miniemulsion between hundreds of nanometers, have characteristics such as energy consumption is low, turndown ratio is big, droplets size distribution is narrow; (2) by regulating phase content, surfactant concentration, cross the film number of times, cross operational conditions such as film flow velocity, membrane pore size, the drop size of adjustable miniemulsion, thereby the size of regulation and control polymer nano granules; Be applicable to and the immiscible various monomers of water that (3) designability of polymkeric substance composition and function is strong.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
Preparation contains that Diisopropyl azodicarboxylate (AIBN) massfraction is 0.2%, Vinylstyrene (DVB) massfraction is that 20% styrene monomer solution obtains raw material A.Preparation sodium lauryl sulphate (SDS) massfraction is that 0.2% the aqueous solution obtains raw material B.Use the microfiltration membrane of aperture 0.2 μ m as dispersion medium.Raw material A is entered at the microporous membrane opposite side by fenestra by a side of microporous membrane under differential pressure action to be parallel among the raw material B that face flows, the preparation colostric fluid, raw material A is 0.1m/s by the linear velocity of fenestra during the preparation colostric fluid, it is 0.5m/s that raw material B is parallel to the mobile linear velocity of face, and the volume flow ratio of raw material A and raw material B is 1: 20.Colostric fluid is crossed film repeatedly and is obtained miniemulsion C 2 times, and each linear velocity of crossing film is 0.2m/s.Under 60 ℃ of conditions, make miniemulsion C polyase 13 hour, obtain containing the emulsion D of polymer nano granules.Utilize methyl alcohol that emulsion D is implemented breakdown of emulsion, obtain polystyrene nanoparticles by the pure water washing, median size is at 30nm, and the variation coefficient of grain size (CV) is less than 15%.
Embodiment 2:
It is that 5% vinylbenzene, p-methylstyrene monomer mixture solution (wherein, the volume ratio of vinylbenzene and p-methylstyrene is 1: 1) obtain raw material A that preparation contains Diisopropyl azodicarboxylate (AIBN) massfraction.Preparation polyvinyl alcohol (PVA) mass percent is that 10% the aqueous solution obtains raw material B.Use the microfiltration membrane of aperture 1.0 μ m as dispersion medium.Raw material A is entered at the microporous membrane opposite side by fenestra by a side of microporous membrane under differential pressure action to be parallel among the raw material B that face flows, the preparation colostric fluid, raw material A is 0.5m/s by the linear velocity of fenestra during the preparation colostric fluid, it is 2.0m/s that raw material B is parallel to the mobile linear velocity of face, and the volume flow ratio of raw material A and raw material B is 1: 5.Colostric fluid is crossed film and is obtained miniemulsion C 1 time, and the linear velocity of crossing film is 1.0m/s.Under 90 ℃ of conditions, make miniemulsion C polymerization 2.5 hours, obtain containing the emulsion D of polymer nano granules.Utilize ethanol that emulsion D is implemented breakdown of emulsion, gathered (vinylbenzene/p-methylstyrene) nano particle by the pure water washing, median size is at 300nm, and the variation coefficient of grain size (CV) is less than 15%.
Embodiment 3:
Preparation contains that dibenzoyl peroxide (BPO) massfraction is 0.2%, Vinylstyrene (DVB) massfraction is that 5% p-methylstyrene monomer solution obtains raw material A.Preparation sodium lauryl sulphate (SDS) massfraction is 5%, polyvinyl alcohol (PVA) mass percent is that 5% the aqueous solution obtains raw material B.Use the microfiltration membrane of aperture 2.0 μ m as dispersion medium.Raw material A is entered at the microporous membrane opposite side by fenestra by a side of microporous membrane under differential pressure action to be parallel among the raw material B that face flows, the preparation colostric fluid, raw material A is 1.0m/s by the linear velocity of fenestra during the preparation colostric fluid, it is 3.0m/s that raw material B is parallel to the mobile linear velocity of face, and the volume flow ratio of raw material A and raw material B is 1: 2.Colostric fluid is crossed film repeatedly and is obtained miniemulsion C 3 times, and each linear velocity of crossing film is 1.5m/s.Under 80 ℃ of conditions, make miniemulsion C polymerization 4 hours, obtain containing the emulsion D of polymer nano granules.Utilize n-propyl alcohol that emulsion D is implemented breakdown of emulsion, obtain poly-p-methylstyrene nano particle by the pure water washing, median size is at 50nm, and the variation coefficient of grain size (CV) is less than 15%.
Embodiment 4:
Preparation contains that dibenzoyl peroxide (BPO) massfraction is 5%, Vinylstyrene (DVB) massfraction is that 5% vinyl toluene monomer solution obtains raw material A.Preparation sodium lauryl sulphate (SDS) massfraction is that 5% the aqueous solution obtains raw material B.Use the microfiltration membrane of aperture 5.0 μ m as dispersion medium.Raw material A is entered at the microporous membrane opposite side by fenestra by a side of microporous membrane under differential pressure action to be parallel among the raw material B that face flows, the preparation colostric fluid, raw material A is 1.5m/s by the linear velocity of fenestra during the preparation colostric fluid, it is 5m/s that raw material B is parallel to the mobile linear velocity of face, and the volume flow ratio of raw material A and raw material B is 1: 1.Colostric fluid is crossed film repeatedly and is obtained miniemulsion C 3 times, and each linear velocity of crossing film is 3.0m/s.Under 60 ℃ of conditions, make miniemulsion C polymerization 5 hours, obtain containing the emulsion D of polymer nano granules.Utilize propyl carbinol that emulsion D is implemented breakdown of emulsion, obtain the polyvinyltoluene nano particle by the pure water washing, median size is at 120nm, and the variation coefficient of grain size (CV) is less than 15%.
Embodiment 5:
Preparation contains that Diisopropyl azodicarboxylate (AIBN) massfraction is 0.2%, dibenzoyl peroxide (BPO) massfraction is that 0.2% vinylbenzene, vinyl toluene monomer mixture solution (wherein, the volume ratio of vinylbenzene and vinyl toluene is 3: 1) obtain raw material A.Preparation sodium lauryl sulphate (SDS) massfraction is 0.2%, polyvinyl alcohol (PVA) mass percent is that 10% the aqueous solution obtains raw material B.Use the microfiltration membrane of aperture 2 μ m as dispersion medium.Raw material A is entered at the microporous membrane opposite side by fenestra by a side of microporous membrane under differential pressure action to be parallel among the raw material B that face flows, the preparation colostric fluid, raw material A is 0.5m/s by the linear velocity of fenestra during the preparation colostric fluid, it is 2.0m/s that raw material B is parallel to the mobile linear velocity of face, and the volume flow ratio of raw material A and raw material B is 1: 4.Colostric fluid is crossed film repeatedly and is obtained miniemulsion C 2 times, and each linear velocity of crossing film is 1.0m/s.Under 85 ℃ of conditions, make miniemulsion C polymerization 2 hours, obtain containing the emulsion D of polymer nano granules.Utilize ethanol that emulsion D is implemented breakdown of emulsion, gathered (vinylbenzene/vinyl toluene) nano particle by the pure water washing, median size is at 150nm, and the variation coefficient of grain size (CV) is less than 15%.
Embodiment 6:
Preparation contains that Diisopropyl azodicarboxylate (AIBN) massfraction is 2.5%, dibenzoyl peroxide (BPO) massfraction is 2.5%, Vinylstyrene (DVB) massfraction is that 5% p-methylstyrene, vinyl toluene monomer mixture solution (volume ratio of p-methylstyrene and vinyl toluene is 1: 1) obtain raw material A.Preparation polyvinyl alcohol (PVA) mass percent is that 5% the aqueous solution obtains raw material B.Use the microfiltration membrane of aperture 1 μ m as dispersion medium.Raw material A is entered at the microporous membrane opposite side by fenestra by a side of microporous membrane under differential pressure action to be parallel among the raw material B that face flows, the preparation colostric fluid, raw material A is 0.5m/s by the linear velocity of fenestra during the preparation colostric fluid, it is 2.0m/s that raw material B is parallel to the mobile linear velocity of face, and the volume flow ratio of raw material A and raw material B is 1: 8.Colostric fluid is crossed film repeatedly and is obtained miniemulsion C 4 times, and each linear velocity of crossing film is 1.0m/s.Under 100 ℃ of conditions, make miniemulsion C polymerase 10 .5 hour, obtain containing the emulsion D of polymer nano granules.Utilize ethanol that emulsion D is implemented breakdown of emulsion, gathered (p-methylstyrene/vinyl toluene) nano particle by the pure water washing, median size is at 60nm, and the variation coefficient of grain size (CV) is less than 15%.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, the ordinary person in affiliated field can make some modifications or improvements it, and this it will be apparent to those skilled in the art that.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (2)
1. method for preparing polymer nano granules, it is characterized in that: this method realizes as follows:
(1) with the polymer monomer that is dissolved with initiator, linking agent as raw material A;
(2) with the aqueous solution that is dissolved with tensio-active agent as raw material B;
(3) raw material A is entered at the microporous membrane opposite side under differential pressure action by a side of microporous membrane with linear velocity 0.1-1.5m/s by fenestra and be parallel to linear velocity 0.5-5m/s among the raw material B that face flows, form colostric fluid;
(4) make colostric fluid linear velocity with 0.2-3m/s under differential pressure action pass through microporous membrane, obtain the secondary emulsion;
(5) with the secondary emulsion as colostric fluid, repeating step (4) 0-4 time obtains miniemulsion C;
(6) heating miniemulsion C carries out polyreaction, obtains containing the emulsion D of polymer nano granules;
(7) add emulsion splitter emulsion D is carried out breakdown of emulsion, throw out obtains polymer nano granules through washing;
Described polymer monomer is vinylbenzene, styrene derivatives or their mixture;
Described initiator is Diisopropyl azodicarboxylate, dibenzoyl peroxide; Described linking agent is Vinylstyrene;
The massfraction of initiator is 0.2-5% in the described raw material A, and the massfraction of linking agent is 0-20%;
Tensio-active agent is sodium lauryl sulphate, polyvinyl alcohol or their mixture among the described raw material B;
The massfraction of tensio-active agent is 0.2-10% among the described raw material B;
The volume flow ratio of described raw material B and raw material A is (1-20): 1;
The time of described polyreaction is 0.5-5 hour; Polymeric reaction temperature is 60-100
oC;
The aperture of described microporous membrane is 0.2-5 μ m.
2. method according to claim 1, it is characterized in that: described emulsion splitter is the Fatty Alcohol(C12-C14 and C12-C18) of C1-C4.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613883A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
| CN101899126A (en) * | 2010-07-21 | 2010-12-01 | 常州大学 | Miniemulsion with fluorinated block copolymers as co-stabilizers and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613883A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
| CN101899126A (en) * | 2010-07-21 | 2010-12-01 | 常州大学 | Miniemulsion with fluorinated block copolymers as co-stabilizers and preparation method thereof |
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