CN100567345C - A kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification - Google Patents
A kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification Download PDFInfo
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- CN100567345C CN100567345C CNB2008100194783A CN200810019478A CN100567345C CN 100567345 C CN100567345 C CN 100567345C CN B2008100194783 A CNB2008100194783 A CN B2008100194783A CN 200810019478 A CN200810019478 A CN 200810019478A CN 100567345 C CN100567345 C CN 100567345C
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Abstract
A kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification belongs to technical field of macromolecule polymerization.The present invention utilizes the monomeric strong alternating polymerization tendency of phenylethylene/maleic anhydride, and/or at (methyl) Hydroxyethyl acrylate and/or other (methyl) alkyl acrylate, and/or under the participation to the Vinylstyrene difunctional monomer, do not add any emulsifying agent and inorganic salt and organic solvent, be initiator with the Potassium Persulphate, in the aqueous solution by radical polymerization, directly preparation adjustable grain control and the cross-linking type that is evenly distributed or non-crosslinked type " green, cleaning " polymer nano micelle can be used for aspects such as drug loading release, catalysis load.The present invention has saved the purification of polymkeric substance and the step of micellization, does not introduce organic solvent, can not bring pollution, easy and simple to handle, cost is low, by regulating monomeric kind of hydrophilic and ratio, initiator amount, to obtain the nano micellar solution of polymer of various size, structure and performance.
Description
Technical field
A kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification belongs to technical field of macromolecule polymerization.The present invention relates to a kind of " green, cleaning " polymer nano micelle, preparation process is simply pollution-free, and its application comprises the existing application and the potential application of nano-micelles such as drug loading release, polymer modification and chemical reaction load.
Background technology
Polymer nano micelle is a kind of novel multifunctional nano material, has nanometer or submicron-scale, is by parents' polymkeric substance microphase-separated to take place in selective solvent, a kind of self-assembled structures with thin solvent borne nuclear and solvation shell of formation.The impellent that causes dredging the formation of solvent microcell has hydrophobic interaction, electrostatic interaction, hydrogen bond action or metal complexation etc.Compare with small molecules micella such as surfactant micelle, polymer micelle also is made up of hydrophilic hydrophobic two portions, but its micelle-forming concentration is lower, and because its segment movement is little, it is littler that it separates association rate, it can be divided into sphere, bar-shaped, vesica shape, tubulose, two-dimentional micella and compound big micella etc. by form.The amphiphilic polymer micella has extremely tempting application prospect, in fields such as biomedicine, chemical reaction, environment protection many application is arranged, as the protection carriers of biomacromolecules such as restricted reaction vessel, load release vehicle, catalyzer and enzyme etc.Aspect biological and medical, the load that the carrier made from polymer micelle can be used for various medicines discharges, and, can make this polymer nanocomposite carrier under effect, carry out controlled delivery of pharmaceutical agents and discharge such as external stimuluss such as temperature, pH, ionic strength (ionogen), electric field, light when in polymkeric substance, introducing various environmental sensitivity primitives.Because generally there is nucleocapsid structure in polymer micelle, both make can be by design polymer micelle nuclear structure and composition to adapt to aspect requirements such as load, release, can design micellar shell structure and composition again to satisfy the requirement of life entity intermiscibility.Its performance is much better than load and the slow-releasing system by the polymer overmold preparation.At chemical field, polymer micelle can be used for the particle diameter of nano material and the control of form as template; As microreactor can be used for that the control of polymkeric substance is synthetic, the preparation of catalyzed reaction and high-performance catalyst system; And, can be used for load of photoelectric functional species or the like in the special material field.Therefore, for the preparation and the correlative study of polymer nano micelle, people have given the attention of height.
Although people have great amount of manpower and material resources input to the research of polymer micelle, and the trend that continues increase is arranged, up to the present, the polymer micelle or the related products of real invested in plantization do not appear in the newspapers so far.Following two reasons are arranged.One, complex steps and organic solvent problem.The preparation method of polymer micelle has a variety of, and wherein most important method is to prepare by the deliquescent difference of close and distant water section in parents' multipolymer in selective solvent.Generally be that parents' polymkeric substance is dissolved in certain organic solvent earlier, in system, drip water again, also need at last to remove organic solvent by means such as dialysis to form polymer micelle.And the existence of organic solvent may bring injury to medicine or human body.Problem two is that concentration is too low.The existence of parents' polymer micelle is that strictness is limited in the certain solvent composition and temperature range, can not adapt to the requirement of application usually.The polymer concentration that existing method obtains is generally in 0.01%～0.1% scope or lower.In order to address the above problem, people have paid a lot of effort.Representative work is the K.L.Wooley by the U.S., Canadian G.J.Liu, and the K.Kataoka of Japan etc. makes.Method is to prepare earlier to form micella in selective solvent, and cross-linked polymer micellar shell or nuclear fix micella then.But, the concentration of the polymer micelle of acquisition still lower (being lower than 0.1%).Armes etc. are by the segmented copolymer of preparation three blocks, and the method for crosslinked mid-block is brought up to 0.1g/mL with cross-linked polymer micellar concentration then.In addition, the preparation of the polymer micelle of this Stability Analysis of Structuresization still is through first micellization and then such two steps of cross-linked polymer micella.Chen Daoyong, Jiang Ming etc. are dissolved in crosslinkable amphiphilic block copolymer in one solvent, and it is crosslinked to add linking agent then, form polymer micelle by crosslinked action, thereby have simplified the micella step.But the above various methodologies has all been used organic solvent, and residual organic solvent is brought injury to medicine or people's cognition.Therefore it is the task of top priority that the polymerization process of developing a kind of organic solvent-free, the particularly aqueous solution prepares polymer nano micelle.
Emulsifier-free emulsion polymerization is meant the emulsion polymerization process that does not add emulsifying agent fully or only add micro-emulsifying agent (concentration is less than micelle-forming concentration CMC) in reaction process.Claim emulsifier-free emulsion polymerization again.People such as nineteen sixty-five Matsumoto are not adding under the situation of emulsifying agent first fully, have synthesized serial latex particle size narrowly distributing, emulsion that system is stable.No free emulsifying agent in this polymerization system, the stable trigger monomer that depends on of micelle gathers hydrophilic persulfuric acid salt initiator the fragment (～OSO that merge key is connected in polymer ends
3 -) or the reactive ionic of tool, non-ionic type comonomer in hydrophilic radical.Because this polymerization process can obtain the latex of " cleaning ", and give the micelle surface different functional groups.Therefore, emulsifier-free emulsion polymerization is subjected to paying close attention to widely as function latex microsphere or polymkeric substance synthetic means.In recent years, to the attention of environmental issue, effectively promoted the flow of research of emulsifier-free emulsion polymerization, solvent type coating and tackiness agent are substituted by water-latex type gradually, to the also increase day by day of demand of soap-free emulsion.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing polymer nano micelle by water solution polymerization self-emulsification with easy method, has regular " green, cleaning " the polymer nano micelle particle of particle diameter with lower cost single stage method preparation.
Technical scheme of the present invention: the monomer among the present invention is based on transfer transport complexing series monomers such as phenylethylene/maleic anhydrides, hydrophilic or lipophilicity monomer (need add the 4th kind in case of necessity) telomerized polymer nano-micelle particle is water-soluble with the third, carries out crosslinked to Vinylstyrene to the polymer nano micelle particle with what can carry out cross-linking polymerization.Reaction scheme is:
Reaction formula 1.
In the formula, a, b, c, d and e represent the molar feed ratio of various reaction monomers, and wherein a/b is 1.5-1: 1, and the amount of c, d, e accounts for the 1%-30% or zero of total moles monomer, and the content of e will be less than 2%.The consumption of initiator potassium persulfate is the 0.2%-2% of total moles monomer.Reaction solvent is a deionized water, and temperature of reaction is 60～70 ℃, and polymerization reaction time is 6-24 hour.
A kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification, utilize the strong alternating polymerization tendency of styrene monomer and maleic anhydride, under the situation of not adding any emulsifying agent and inorganic salt and organic solvent, with the Potassium Persulphate, be initiator, in the aqueous solution by radical polymerization, make the phenylethylene-maleic anhydride polymer nano micelle; The mol ratio of styrene monomer and maleic anhydride is 1.5-1: 1, the weight percentage of total monomer is 0.1%-30% in the aqueous solution, the Potassium Persulphate mole dosage is the 0.2%-2% of total moles monomer, under 60～70 ℃ of conditions, react 6-24h, the polymer nano micelle that directly prepares the adjustable grain control and be evenly distributed.
Described method, utilize the strong alternating polymerization tendency of styrene monomer and maleic anhydride, add (methyl) alkyl acrylate of (methyl) Hydroxyethyl acrylate and/or other type, under the situation of not adding any emulsifying agent and inorganic salt and organic solvent, with the Potassium Persulphate, be initiator, in the aqueous solution by radical polymerization, (methyl) alkyl acrylate mole dosage of (methyl) Hydroxyethyl acrylate and/or other type is the 1%-30% of total moles monomer, the polymer nano micelle that directly prepares the adjustable grain control and be evenly distributed.
Described method, utilize the strong alternating polymerization tendency of styrene monomer and maleic anhydride, add Vinylstyrene, under the situation of not adding any emulsifying agent and inorganic salt and organic solvent, with the Potassium Persulphate, be initiator, in the aqueous solution by radical polymerization, the Vinylstyrene mole dosage is the 0.1%-2% of total moles monomer, the polymer nano micelle that directly prepares the adjustable grain control and be evenly distributed.
Described method, utilize the strong alternating polymerization tendency of styrene monomer and maleic anhydride, add (methyl) alkyl acrylate of (methyl) Hydroxyethyl acrylate and/or other type, and Vinylstyrene, under the situation of not adding any emulsifying agent and inorganic salt and organic solvent, with the Potassium Persulphate is initiator, in the aqueous solution by radical polymerization, (methyl) alkyl acrylate of (methyl) Hydroxyethyl acrylate and/or other type, and Vinylstyrene, their mole dosage is the 1%-30% of total moles monomer, and the Vinylstyrene mole dosage is the 0.1%-2% of total moles monomer, directly prepares the adjustable grain control, and the polymer nano micelle that is evenly distributed.
The method of described preparing polymer nano micelle by water solution polymerization self-emulsification, this polymkeric substance are random parents polymkeric substance and contain the alternating polymerization segment.
The method of described preparing polymer nano micelle by water solution polymerization self-emulsification, the adjustable grain control and the size distribution of this polymer nano micelle are even, and its adjustable grain control is by the monomeric ratio of the hydrophilic of whole aqueous solution polymerization system, and the consumption of initiator potassium persulfate decision.
The application of the polymer nano micelle of described method preparation, this polymer nano micelle are used for drug loading release, polymer modification and chemical reaction loaded with nano micellar to be had to use and potential application the sixth of the twelve Earthly Branches.
The present invention is based on the understanding of the strong alternating polymerization tendency that transfer transport complexing series monomers such as phenylethylene/maleic anhydride are had, work out and in the aqueous solution, utilize the direct single stage method of radical polymerization to prepare regular " green, cleaning " the polymer nano micelle particle of particle diameter.
Above-mentioned preparation condition all can be realized for this area scientific and technical personnel.
Beneficial effect of the present invention: existing polymer nano micelle technology needs first synthesis of amphoteric polymkeric substance, and then through the micellization process (above process generally all can be introduced organic solvent, bring problems such as pollution), have that preparation method's complexity is loaded down with trivial details, the high deficiency of cost.The present invention has made a kind of " green, cleaning " polymer nano micelle with one step of simple and direct method.Because the present invention is the polymer nano micelle (crosslinked or non-crosslinked type) that directly prepares high density from monomer, the purification of polymkeric substance and the step of micellization have been saved, owing to adopted the pure water solution polymerization, do not introduce organic solvent, can not bring pollution, easy and simple to handle, cost is low, by regulating monomeric kind of hydrophilic and ratio, initiator amount, to obtain the nano micellar solution of polymer of various size, structure and performance.The present invention comes from a kind of brand-new thinking, and method is easy, and is respond well, has immeasurable application prospect.
Description of drawings
Fig. 1. various monomer ratio condition polymerization resulting polymers nano-micelle stable liquids.
Specific embodiments
Basic polymerization process is: (methyl) alkyl acrylate of phenylethylene/maleic anhydride/(methyl) Hydroxyethyl acrylate/other type/Vinylstyrene/Potassium Persulphate (KPS) is placed a single port reactor under certain proportion adds an amount of water as reaction solvent.Add one or two logical valve on the single port reactor, decompression after removing oxygen in the system is sealed system.Then system 60～70 ℃ and at the uniform velocity stir under reaction 6-24 hour or the longer time, guarantee that all monomers all participate in polymerization.Stopped reaction, the gained system is polymer micelle solution.Gained micellar solution is oyster white stable homogeneous liquid, and placing did not have any sedimentation, demixing phenomenon in one month.
Embodiment 1. phenylethylene/maleic anhydride mol ratios are 1.5: 1, and to add butyl acrylate (account for all monomer molar consumptions 5%) be the 3rd monomer, with the Potassium Persulphate initiator (consumption be total moles monomer 2%), with the deionized water is reaction solvent, and monomeric weight percentage is 15% in the aqueous solution, reacts 20 hours down to guarantee all monomer complete reactions at 60 ℃.Its polymer micelle solution is seen accompanying drawing 1-A.
Embodiment 2. phenylethylene/maleic anhydride mol ratios are 1.5: 1, and add Hydroxyethyl acrylate (account for all monomer molar consumptions 10%), butyl acrylate (account for all monomer molar consumptions 10%), be initiator (consumption be total moles monomer 1.5%) for linking agent, with the Potassium Persulphate to Vinylstyrene (account for all monomer molar consumptions 1.5%), with the deionized water is reaction solvent, and monomeric weight percentage is 30% in the aqueous solution, reacts 20 hours down to guarantee all monomer complete reactions at 60 ℃.Its polymer micelle solution is seen accompanying drawing 1-B.
Embodiment 3. phenylethylene/maleic anhydride mol ratios are 1.5: 1, and to add Hydroxyethyl acrylate (account for all monomer molar consumptions 10%) be the 3rd monomer, with the Potassium Persulphate initiator (consumption be total moles monomer 1%), with the deionized water is reaction solvent, and monomeric weight percentage is 25% in the aqueous solution, reacts 20 hours down to guarantee all monomer complete reactions at 60 ℃.Its polymer micelle solution is seen accompanying drawing 1-C.
Embodiment 4. phenylethylene/maleic anhydride mol ratios are 1.5: 1, and add Vinylstyrene (account for all monomer molar consumptions 1%) is linking agent, with the Potassium Persulphate initiator (consumption be total moles monomer 2%), with the deionized water is reaction solvent, and monomeric weight percentage is 15% in the aqueous solution, reacts 20 hours down to guarantee all monomer complete reactions at 60 ℃.Its polymer micelle solution is seen accompanying drawing 1-D.
Embodiment 5. phenylethylene/maleic anhydride mol ratios are 1.5: 1, and add Hydroxyethyl acrylate (account for all monomer molar consumptions 10%), butyl acrylate (account for all monomer molar consumptions 10%), be initiator (consumption be total moles monomer 1.5%) for linking agent, with the Potassium Persulphate to Vinylstyrene (account for all monomer molar consumptions 1.5%), with the deionized water is reaction solvent, and monomeric weight percentage is 5% in the aqueous solution, reacts 20 hours down to guarantee all monomer complete reactions at 60 ℃.Its polymer micelle solution is seen accompanying drawing 1-E.
Embodiment 6. phenylethylene/maleic anhydride mol ratios are 1: 1, with the Potassium Persulphate initiator (consumption be total moles monomer 1.5%), with the deionized water is reaction solvent, and monomeric weight percentage is 5% in the aqueous solution, reacts 10 hours down to guarantee all monomer complete reactions at 70 ℃.Its polymer micelle solution is seen accompanying drawing 1-F.
Claims (7)
1, a kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification, it is characterized in that utilizing the strong alternating polymerization tendency of styrene monomer and maleic anhydride, under the situation of not adding any emulsifying agent and inorganic salt and organic solvent, with the Potassium Persulphate, be initiator, in the aqueous solution by radical polymerization, make the phenylethylene-maleic anhydride polymer nano micelle; The mol ratio of styrene monomer and maleic anhydride is 1.5-1: 1, the weight percentage of total monomer is 0.1%-30% in the aqueous solution, the Potassium Persulphate mole dosage is the 0.2%-2% of total moles monomer, under 60～70 ℃ of conditions, react 6-24h, the polymer nano micelle that directly prepares the adjustable grain control and be evenly distributed.
2, a kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification, it is characterized in that utilizing the strong alternating polymerization tendency of styrene monomer and maleic anhydride, add (methyl) alkyl acrylate of (methyl) Hydroxyethyl acrylate and/or other type, under the situation of not adding any emulsifying agent and inorganic salt and organic solvent, with the Potassium Persulphate is initiator, in the aqueous solution by radical polymerization, the mol ratio of styrene monomer and maleic anhydride is 1.5-1: 1, the weight percentage of total monomer is 0.1%-30% in the aqueous solution, (methyl) alkyl acrylate mole dosage of (methyl) Hydroxyethyl acrylate and/or other type is the 1%-30% of total moles monomer, the Potassium Persulphate mole dosage is the 0.2%-2% of total moles monomer, under 60～70 ℃ of conditions, react 6-24h, directly prepare the adjustable grain control, and the polymer nano micelle that is evenly distributed.
3, a kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification, it is characterized in that utilizing the strong alternating polymerization tendency of styrene monomer and maleic anhydride, add Vinylstyrene, under the situation of not adding any emulsifying agent and inorganic salt and organic solvent, with the Potassium Persulphate is initiator, in the aqueous solution by radical polymerization, the mol ratio of styrene monomer and maleic anhydride is 1.5-1: 1, the weight percentage of total monomer is 0.1%-30% in the aqueous solution, the Vinylstyrene mole dosage is the 0.1%-2% of total moles monomer, the Potassium Persulphate mole dosage is the 0.2%-2% of total moles monomer, under 60～70 ℃ of conditions, react 6-24h, directly prepare the adjustable grain control, and the polymer nano micelle that is evenly distributed.
4, a kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification, it is characterized in that utilizing the strong alternating polymerization tendency of styrene monomer and maleic anhydride, add (methyl) alkyl acrylate of (methyl) Hydroxyethyl acrylate and/or other type, and Vinylstyrene, under the situation of not adding any emulsifying agent and inorganic salt and organic solvent, with the Potassium Persulphate is initiator, in the aqueous solution by radical polymerization, the mol ratio of styrene monomer and maleic anhydride is 1.5-1: 1, the weight percentage of total monomer is 0.1%-30% in the aqueous solution, (methyl) alkyl acrylate of (methyl) Hydroxyethyl acrylate and/or other type, and Vinylstyrene, their mole dosage is the 1%-30% of total moles monomer, and the Vinylstyrene mole dosage is the 0.1%-2% of total moles monomer, the Potassium Persulphate mole dosage is the 0.2%-2% of total moles monomer, under 60～70 ℃ of conditions, react 6-24h, directly prepare the adjustable grain control, and the polymer nano micelle that is evenly distributed.
5,, it is characterized in that this polymkeric substance is random parents polymkeric substance and contains the alternating polymerization segment according to the method for the described preparing polymer nano micelle by water solution polymerization self-emulsification of arbitrary claim among the claim 1-4.
6, according to the method for the described preparing polymer nano micelle by water solution polymerization self-emulsification of arbitrary claim among the claim 1-4, the adjustable grain control and the size distribution that it is characterized in that this polymer nano micelle are even, and its adjustable grain control is by the monomeric ratio of the hydrophilic of whole aqueous solution polymerization system, and the consumption of initiator potassium persulfate decision.
7, the application of the polymer nano micelle of the described method preparation of arbitrary claim among the claim 1-4 is characterized in that this polymer nano micelle is used for drug loading release, polymer modification and chemical reaction loaded with nano micella.
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| CN102718976B (en) * | 2012-06-29 | 2017-04-26 | 江南大学 | Preparation method of in-situ induced hyaluronic acid micelle |
| CN102807643B (en) * | 2012-08-27 | 2014-01-29 | 中国海洋石油总公司 | Emulsifying agent for emulsion polymerization and preparation method thereof |
| CN103846064A (en) * | 2012-11-29 | 2014-06-11 | 江南大学 | Method for preparing solid particle emulsifying agent by using micro-channel mixer |
| CN106075460B (en) * | 2016-07-01 | 2021-03-23 | 安徽大学 | Novel ortho-ester cross-linking agent monomer and method for preparing acid-sensitive nano-drug carrier by using same |
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