CN104592440A - Preparation method for polymer nanoparticle with two-sided anisotropic structure - Google Patents
Preparation method for polymer nanoparticle with two-sided anisotropic structure Download PDFInfo
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- CN104592440A CN104592440A CN201510079386.4A CN201510079386A CN104592440A CN 104592440 A CN104592440 A CN 104592440A CN 201510079386 A CN201510079386 A CN 201510079386A CN 104592440 A CN104592440 A CN 104592440A
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Abstract
The invention discloses a preparation method for a polymer nanoparticle with a two-sided anisotropic structure, and relates to polymer nanoparticles. The preparation method comprises the following steps: (1) adding a hydrophilic monomer, a hydrophobic monomer and a cross-linking agent into a solvent, introducing nitrogen gas, heating, producing a polymerization reaction, adding a water-based initiator solution, and continuously introducing nitrogen gas for reaction to obtain mono-dispersed special-shaped polymer microspheres, namely 'seeds' for seed emulsion polymerization; (2) taking the special-shaped polymer microspheres obtained in the step 1) as the 'seeds' for seed emulsion polymerization, adding the hydrophobic monomer for swelling, heating, adding a surfactant and a polymerization inhibitor, adding an oily initiator, and introducing the nitrogen gas for reaction to obtain the polymer nanoparticle with the two-sided anisotropic structure. A product obtained by one-step seed emulsion polymerization has the advantages of simplicity and feasibility for operation and uniform and controllable grain size of the obtained special-shaped microspheres. The obtained polymer nanoparticle with the two-sided anisotropic structure is hydrophilic at one end and hydrophobic at the other end.
Description
Technical field
The present invention relates to polymer nano-particle, especially relate to the polymer particle preparation method being prepared structure and all asymmetric a kind of double-sided anisotropic structure of character by seeded emulsion polymerization.
Background technology
In recent years, double-sided anisotropic structured particles is favored widely because the asymmetry at its two ends receives.Report the method for multiple this structured particles of preparation at present, as: micro Process method, asymmetric modification, emulsion polymerization etc.But due to the existence of Pickeringemulsion interface effect, the transformation efficiency of asymmetric modification method is on the low side; Although micro Process method can overcome this shortcoming, the method is difficult to the particle diameter controlling particle.Comparatively speaking, emulsion polymerization prepares the polymer particle of double-sided anisotropic structure, and not only transformation efficiency is higher, and size is adjustable.At present, preparing double-sided anisotropic structure nano particle with letex polymerization has had certain development, if the people such as Ballauff are by dropwise adding the method for reaction monomers, has prepared the asymmetric double-sided anisotropic ball of PMMMA; Chen Tang by the method for monomer swell prepared PS the double-sided anisotropic polymer architecture nanoparticle of PAN hollow.
In document (Chem.Mater.2013,25,4348-4353), the people such as Bas G.P.van Ravensteijn by the method for seeded emulsion polymerization prepare vinylbenzene 1-chloro-4-methyl-benzene double-sided anisotropic structural polymer nanometer ball.The nanoparticle of this structure is only the two ends difference in performance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of double-sided anisotropic structural polymer nanoparticle.
Concrete steps of the present invention are as follows:
1) preparation of profiled polymer microballoon
Hydrophilic monomer, hydrophobic monomer, linking agent are added in solvent, carries out polyreaction after logical nitrogen heating, then add aqueous initiator solution, continue logical nitrogen reaction, obtain monodispersed profiled polymer microballoon, i.e. seeded emulsion polymerization " seed ";
2) preparation of the polymer nano-particle of double-sided anisotropic structure
Using step 1) the profiled polymer microballoon emulsion that obtains is as " seed " of seeded emulsion polymerization, and it is swelling to add hydrophobic monomer, heats up, add tensio-active agent and stopper again, then add oiliness initiator, logical nitrogen reaction, obtains the polymer nano-particle of double-sided anisotropic structure.
In step 1) in, described hydrophilic monomer, hydrophobic monomer, linking agent, solvent and initiator solution content is by mass percentage: hydrophilic monomer and hydrophobic monomer can be 1% ~ 20%, linking agent can be 2.5% ~ 25.4% of hydrophilic monomer and hydrophobic monomer total mass, initiator can be 0.1% ~ 5% of hydrophilic monomer and hydrophobic monomer total mass, and all the other are solvent; The volume ratio of described hydrophilic monomer and hydrophobic monomer can be 1: (3 ~ 20);
Described hydrophilic monomer can be selected from least one in glycidyl methacrylate, hydroxyethyl methylacrylate, NIPA, acrylamide, vinylformic acid etc.;
Described hydrophobic monomer can adopt vinylbenzene etc.;
Described linking agent can adopt the one in Vinylstyrene, N,N methylene bis acrylamide etc.;
Described solvent can adopt water;
Described aqueous initiator solution can adopt Potassium Persulphate, and the mass percentage concentration of aqueous initiator solution can be 0.2% ~ 2%;
The temperature of described heating can be 65 ~ 85 DEG C, and can stir during described polyreaction, stirring velocity can be 200 ~ 600rpm; The time that nitrogen reaction is led in described continuation can be 24h.
In step 2) in, the add-on of described hydrophobic monomer can be 40% ~ 70% of profiled polymer microballoon emulsion by mass percentage; The add-on of oiliness initiator can be 0.5% ~ 2.5% of profiled polymer microballoon emulsion by mass percentage; Described oiliness initiator can adopt Diisopropyl azodicarboxylate, and the mass percentage concentration of oiliness initiator is 0.5% ~ 2.5%; The temperature of described intensification can be 70 ~ 90 DEG C; The time of described logical nitrogen reaction can be 24h.
Double-sided anisotropic structural polymer nanoparticle of the present invention is the product that employing one step seeded emulsion polymerization obtains, and has that operation is simple, a homogeneous controlled advantage of products therefrom abnormity microspherulite diameter size.Owing to not adding any emulsifying agent and stablizer, products therefrom is pure, and the follow-up double-sided anisotropic structural polymer nanoparticle prepared does not need any process to use.By seeded emulsion polymerization, with the swelling asymmetric polymer nanocomposite ball seed of hydrophobic monomer.In swelling process, hydrophobic monomer is constantly swelling to be entered in seed polymer nanometer ball seed, finally reaches running balance with the hydrophobic monomer amount in solution.Subsequently under initiator effect, there is polymerization and finally form seed on asymmetric polymer nanocomposite ball surface in the monomer of Interior Seed.And its size can change the concentration of hydrophilic and oleophilic amount of monomer as required, change initiator amount degree and change polymeric reaction temperature and stirring velocity and control.
Double-sided anisotropic structural polymer nanoparticle that the present invention obtains breaks the performance of traditional double-sided anisotropic structure only symmetrical configuration, the polymorphic structure of water-wet side improves the specific surface area of particle, and particle diameter single stable is controlled, expand the application of double-sided anisotropic particle in tensio-active agent, selective catalysis.
The present invention, by a step seed emulsion polymerization, has prepared the polymer nano-particle being different from common double-sided anisotropic structure.With asymmetric polymer nanocomposite ball for seed, by with hydrophobic monomer this seed swelling, the effect that cooperative mechanical stirs, the double-sided anisotropic polymer nano-particle one end obtained is hydrophilic and the other end is hydrophobic, and this structure breaks the performance of traditional double-sided anisotropic structure only symmetrical configuration.Meanwhile, the polymorphic structure of water-wet side improves the specific surface area of particle, has expanded the application of double-sided anisotropic particle in tensio-active agent, selective catalysis.
Accompanying drawing explanation
The product double-sided anisotropic structural polymer nanoparticle SEM that Fig. 1 obtains for embodiment 1 schemes.
The product double-sided anisotropic structural polymer nanoparticle SEM that Fig. 2 obtains for embodiment 2 schemes.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1:
By hydrophilic monomer glycidyl methacrylate 0.2mL, hydrophobic monomer vinylbenzene 2mL and Vinylstyrene 0.05mL adds logical nitrogen gas stirring 30 ~ 60min logical nitrogen continuously in the three-necked bottle containing 30mL deionized water, be warming up to 75 DEG C, then add the aqueous solution being dissolved with 0.04g Potassium Persulphate initiator.Reaction 24h, obtains the special-shaped copolymer microsphere emulsion of monodispersed styrene-divinylbenzene-glycidyl methacrylate (PS-DVB-PGMA).After centrifuge washing, by solution dilution to 40ml.
Get 1/4 (i.e. 10ml) of above-mentioned profiled polymer microballoon emulsion, add 1ml vinylbenzene, the swelling 24h of normal temperature under the condition constantly stirred.Reaction is warming up to 80 DEG C, adds surfactant SDS and stopper Sodium Nitrite.After keeping temperature certain hour, add the styrene solution being dissolved with 0.005g AIBN, nitrogen protection reaction 24h.The SEM figure of the double-sided anisotropic structural polymer nanoparticle obtained as shown in Figure 1.
Embodiment 2 ~ 5: with the processing condition of embodiment 1, change the vinylbenzene add-on of swelling profiled polymer microballoon seed, the special-shaped copolymer microsphere emulsion of monodispersed styrene-divinylbenzene-glycidyl methacrylate (PS-DVB-PGMA) of synthesis different-grain diameter, the results are shown in Table 1.
Table 1
The product double-sided anisotropic structural polymer nanoparticle SEM figure that embodiment 2 obtains is see Fig. 2.
Embodiment 6 ~ 8: with the processing condition of embodiment 1, the add-on of water when changing swelling, the special-shaped copolymer microsphere emulsion of monodispersed styrene-divinylbenzene-glycidyl methacrylate (PS-DVB-PGMA) of synthesis different-shape, the results are shown in Table 2.
Table 2
The present invention, by seeded emulsion polymerization, is " seed " with asymmetric polymer nanocomposite ball, with hydrophobic monomer this seed swelling.In swelling process, hydrophobic monomer constantly enters in seed, finally reaches running balance with the hydrophobic monomer amount in solution.Add ionic stopper subsequently, and this stopper exists in solution and does not enter Interior Seed.Under initiator effect, there is polymerization and finally form projection on asymmetric polymer nanocomposite ball surface in the monomer of Interior Seed.Thus formed and all different double-sided anisotropic structural polymer nanoparticle of properity.And the monomer existed in solution due to the inhibition of ionic stopper cannot initiated polymerization, thus ensure the stable homogeneous of the product obtained.Double-sided anisotropic structural polymer nanoparticle one end that the method obtains is hydrophilic and the other end is hydrophobic, break the performance of traditional double-sided anisotropic structure only symmetrical configuration, the polymorphic structure of water-wet side improves the specific surface area of particle, and particle diameter single stable is controlled, expand the application of double-sided anisotropic particle in tensio-active agent, selective catalysis.
Claims (10)
1. a preparation method for double-sided anisotropic structural polymer nanoparticle, is characterized in that its concrete steps are as follows:
1) preparation of profiled polymer microballoon
Hydrophilic monomer, hydrophobic monomer, linking agent are added in solvent, carries out polyreaction after logical nitrogen heating, then add aqueous initiator solution, continue logical nitrogen reaction, obtain monodispersed profiled polymer microballoon, i.e. seeded emulsion polymerization " seed ";
2) preparation of the polymer nano-particle of double-sided anisotropic structure
Using step 1) the profiled polymer microballoon emulsion that obtains is as " seed " of seeded emulsion polymerization, and it is swelling to add hydrophobic monomer, heats up, add tensio-active agent and stopper again, then add oiliness initiator, logical nitrogen reaction, obtains the polymer nano-particle of double-sided anisotropic structure.
2. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, it is characterized in that in step 1) in, described hydrophilic monomer, hydrophobic monomer, linking agent, solvent and initiator solution content is by mass percentage: hydrophilic monomer and hydrophobic monomer are 1% ~ 20%, linking agent is 2.5% ~ 25.4% of hydrophilic monomer and hydrophobic monomer total mass, initiator is 0.1% ~ 5% of hydrophilic monomer and hydrophobic monomer total mass, and all the other are solvent; The volume ratio of described hydrophilic monomer and hydrophobic monomer is 1: (3 ~ 20).
3. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, it is characterized in that in step 1) in, described hydrophilic monomer is selected from least one in glycidyl methacrylate, hydroxyethyl methylacrylate, NIPA, acrylamide, vinylformic acid.
4. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, is characterized in that in step 1) in, described hydrophobic monomer adopts vinylbenzene.
5. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, is characterized in that in step 1) in, described linking agent adopts Vinylstyrene or N,N methylene bis acrylamide.
6. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, is characterized in that in step 1) in, described solvent adopts water.
7. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, is characterized in that in step 1) in, described aqueous initiator solution adopts Potassium Persulphate, and the mass percentage concentration of aqueous initiator solution is 0.2% ~ 2%.
8. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, is characterized in that in step 1) in, the temperature of described heating is 65 ~ 85 DEG C, stirs during described polyreaction, and stirring velocity is 200 ~ 600rpm; The time that nitrogen reaction is led in described continuation can be 24h.
9. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, is characterized in that in step 2) in, the add-on of described hydrophobic monomer is 40% ~ 70% of profiled polymer microballoon emulsion by mass percentage; The add-on of oiliness initiator is 0.5% ~ 2.5% of profiled polymer microballoon emulsion by mass percentage; The mass percentage concentration of oiliness initiator is 0.5% ~ 2.5%.
10. the preparation method of a kind of double-sided anisotropic structural polymer nanoparticle as claimed in claim 1, is characterized in that in step 2) in, described oiliness initiator is Diisopropyl azodicarboxylate; The temperature of described intensification can be 70 ~ 90 DEG C; The time of described logical nitrogen reaction can be 24h.
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Cited By (3)
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| CN105777967A (en) * | 2016-03-08 | 2016-07-20 | 西北师范大学 | Preparation method of two-sided polymer particulates with controllable shapes |
| CN107236070A (en) * | 2016-03-29 | 2017-10-10 | 积水化成品工业株式会社 | Polymer particle and its manufacture method and purposes |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
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| CN105777967B (en) * | 2016-03-08 | 2018-06-29 | 西北师范大学 | A kind of preparation method of morphology controllable double-sided polymerization object particle |
| CN107236070A (en) * | 2016-03-29 | 2017-10-10 | 积水化成品工业株式会社 | Polymer particle and its manufacture method and purposes |
| CN107236070B (en) * | 2016-03-29 | 2020-07-17 | 积水化成品工业株式会社 | Polymer particles, process for producing the same, and use thereof |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
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