CN102604310B - Water-phase preparing method of silica-coating polymer nano particles - Google Patents
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Abstract
The invention belongs to the technical field of organic/inorganic hybrid nano materials, and particularly relates to a water-phase preparing method of silica-coating polymer nano particles. The silica-coating polymer nano particles have nanoscale structures and good heat stability, have the advantages of both organic polymer and inorganic material, and have special optical, magnetic, electrical and mechanical performances. According to the preparing method provided by the invention, the production cost of the silica-coating polymer nano particles is reduced, the method has the advantages of simple process, high input-output ratio and the like, the product has high quality and wide application prospects, and products prepared by the invention accord with the requirements of contemporary society on environment-friendly high-performance chemical products and can be used in fields such as nano drug carriers.
Description
Technical field
The invention belongs to organic-inorganic hybrid nanometer material technology field, be specifically related to a kind of aqueous phase preparation method of silicon coated polymer nanoparticle.
Background technology
RAFT polymerization, because it is to freely the selecting and structure that can good control polymkeric substance of functional monomer, is widely used in the preparation of block polymer.Yet, due to the required chain-transfer agent very easily hydrolysis in aqueous environment of RAFT polymerization, greatly reduce the transformation efficiency of monomer.Investigators' major part is that RAFT polymerization is prepared segmented copolymer under oil phase environment at present, and in this process organic reagent add the theme of having run counter to undoubtedly current environmental protection, even if there is small part investigator to attempt RAFT polymerization under aqueous conditions, prepare amphiphilic block polymer, after reaction 48h, the transformation efficiency of monomer is very low [Chen Weixing still, Fan Xiaodong, Liu Yuyang. the synthetic and sign of responsive to temperature type amphipathic nature block polymer. polymer material science and engineering, 2006,22:44-47; Pan Jingyun, He Junpo, Yang Yuliang etc. synthesizing of the MMA controllable free-radical polymerisation based on RAFT process and segmented copolymer. SCI, 2004,9:1759-1764].
In addition, in micella self assembling process, when polymer concentration is during lower than micelle-forming concentration, the dilution effect of micella has a strong impact on the controllable release efficiency of medicine.And in order to improve the stability of polymer micelle and the integrity of supermolecule nano structure, so that their better application in coenocorrelation, in recent years, people are devoted to the research of shell-crosslinked polymeric micelles by using always.Liu seminar is after making amphiphilic block polymer micelle, add a certain amount of 1, two (the 2-iodo oxyethyl group) ethane of 2-, this linking agent has well been controlled the form of polymer micelle, but the bad control of the consumption of linking agent, all products need to be by being used for next step experiment [Luo S Z after micro-filtrate membrane filtration, Liu S Y, Wu C, et al. Double Hydrophilic Block Copolymer Monolayer Protected Hybrid Gold Nanoparticles and Their Shell Cross-Linking. J. Phys. Chem. B, 2005, 109:22159-22166].Armes seminar utilizes the complexing action between polyelectrolyte, by regulating pH to obtain after block polymer micelle, add divinylsulfone, make the hydroxyl generation crosslinking reaction on itself and polymer chain, successfully made the crosslinked micella of shell, the method has been avoided the generation of by product, preparation process nontoxicity, and can realize the reversing process that polymer micelle is crosslinked and solution is crosslinked by adding salt, yet the intermicellar gathering of simultaneously following makes unsatisfactory [the Liu S Y of the method, Save M, Armes S P, et al. Synthesis of pH-Responsive Shell Cross-Linked Micelles and Their Use as Nanoreactors for the Preparation of Gold Nanoparticles. Langmuir, 2002, 18:8350-8357], this has caused scholars' extensive concern.Up to the present; preparing the method that the crosslinked micella of shell mainly adopts is the coupling of uv induction cinnyl, carbodiimide coupled method, 1; two (the 2-iodo oxyethyl group) ethane of 2-makes that amine is quaternized, hydroxyl is cross-linked with divinylsulfone; [the Li Y T such as click chemistry and the reaction of multivalence gold ion in-situ reducing; Armes S P; McCormick C L; et al. Synthesis of Reversible Shell Cross-Linked Micelles for Controlled Release of Bioactive Agents. Macromolecules; 2006,39:2726-2728; Hernandez J R; Babin J, Lecommandoux S, et al.Preparation of Shell Cross-Linked Nano-Objects from Hybrid-Peptide Block Copolymers. Biomacromolecules; 2005,6:2213 – 2220; Joralemon M J; Hawker C J; Wooley K L; et al. Shell Click-Crosslinked (SCC) Nanoparticles:A New Methodology for Synthesis and Orthogonal Functionalization. J. Am. Chem. Soc.; 2005,127:16892 – 16899; Liu S Y, Weaver J V M, Armes S P, et al. Synthesis of Shell Cross-Linked Micelles with pH-Responsive Cores Using ABC Triblock Copolymers. Macromolecules, 2002,35:6121 – 6131] yet. because reagent material is expensive, require to be further purified to remove small molecule by-product simultaneously, limited their extensive use.Utilizing under aqueous conditions organic inorganic hybridization to prepare that silicon clad nano polymer micelle carrying out simplifying production technique, environment protection health and reducing costs is the research of target, and the polymer micelle that the fast development of organic-inorganic hybrid material also makes research and development have premium properties becomes one of the study hotspot in this field.
In order to prepare constitutionally stable shell-crosslinked polymeric micelles by using, people are doing unremitting effort always.2005, McCormick seminar has synthesized triblock copolymer polyethylene oxide-b-(N,N-DMAA-s-sodium aluminium silicate)-b-NIPA (PEO-b-(DMA-s-NAS)-b-NIPAM) by RAFT polymerization.When temperature is during higher than the lower critical solution temperature of Thermo-sensitive block NIPAM, polymkeric substance is self-assembled into take the micella that NIPAM is shell as core and wetting ability PEO, add diethylamine, it is reacted with remaining NAS, can make crosslinked micella [the Li Y T of shell, Lokitz B Z, McCormick C L. RAFT Synthesis of a Thermally Responsive ABC Triblock Copolymer Incorporating N-Acryloxysuccinimide for Facile in Situ Formation of Shell Cross-Linked Micelles in Aqueous Media. Macromolecules, 2006, 39:81-89].2007, Wang has been synthesized and has been had temperature sensitivity block NIPAM-co-NAS(N-N-isopropylacrylamide-co-sodium aluminium silicate by RAFT polymerization) polymkeric substance, when temperature is during higher than the lower critical solution temperature of Thermo-sensitive block, it is the micella that core and wetting ability PEO are shell that polymkeric substance is self-assembled into NIPAM-co-NAS, add cystamine, it is reacted with remaining NAS, also can make crosslinked micella [the Wang R of shell, Lowe A B. RAFT polymerization of styrenic-based phosphonium monomers and a new family of well-defined statistical and block polyampholytes. J Polym Sci Polym Chem, 2007, 45:2468 – 2483].
Organic/inorganic hybridization material especially silicon-containing nano material because nano level optics, magnetics and the electric property of its very attractive causes people's extensive concern.In recent years, in succession there is report to set forth the preparation method of the crosslinked micella of silicon encasement.First the Zhang Xianzheng of Wuhan University in 2008 and the auspiciousness teach problem group of Zhuo Ren select the functional monomer that contains silica (Si-O) key in polymerization process, then by acid catalysis collosol and gel in polymkeric substance self assembling process, form Si-O-Si reticulated structure, take the lead in having prepared crosslinked thermo-responsive hybridized polymer micella [the Wei H of shell, Chang C, Zhuo R X, et al. Synthesis and Applications of Shell Cross-Linked Thermoresponsive Hybrid Micelles Based on Poly (
n-isopropylacrylamide-
co-3-(trimethoxysilyl) propyl methacrylate)-
b-poly (methyl methacrylate). Langmuir, 2008,24:4564-4570], within 2009, Li will gather ((2-(dimethyl amine) ethyl-methyl vinylformic acid)-b-(2-(diisopropylamine) ethyl-methyl vinylformic acid)) (PDMA-b-PDPA) polymer micelle and silane coupling agent reaction, the reticulated structure coated polymer micella that utilizes silane coupling agent hydrolytic condensation to form, controlled well morphological structure [the Li Y T of polymer micelle, Du J Z, Armes S P. Shell Cross-Linked Micelles as Cationic Templates for the Preparation of Silica-Coated Nanoparticles:Strategies for Controlling the Mean Particle Diameter. Macromol. Rapid. Commun., 2009, 30:464 – 468].The crosslinked micella of shell of selecting silicon cross-linking system to prepare has the structure of organic polymer and the feature of inorganic materials concurrently, has the following advantages: the first, inorganic silicon reticulated structure is introduced to organic polymer chain, and can improve the rigidity of the crosslinked micella of shell, make it more stable; The second, than other organic " small molecules " linking agents, silane coupling agent cost is lower, and toxicity is less, and the commercial applications that makes the crosslinked micella of shell is property more likely, and this is also consistent with the theory of Green Chemistry; The 3rd, do not need to add organic molecule reagent, purification process is simple and convenient.Therefore the crosslinked micella of silicon encasement had both had optics, magnetics, electricity and the mechanical property of inorganics, had again workability, compatibility and the stimuli responsive performance of polymkeric substance, had wide development space.These new thinkings have been broken the inertia of traditional design, and larger facility is provided for material is synthetic.But environment is as more single in the responsiveness of temperature, pH etc. to external world for the crosslinked block polymer micelle of the shell that these methods obtain, and there is no both at home and abroad at present about prepare document and the patent of the coated shell-crosslinked polymeric micelles by using of silicon under aqueous environments.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, a kind of aqueous phase preparation method of silicon coated polymer nanoparticle is provided.
The aqueous phase preparation method of a kind of silicon coated polymer nanoparticle that the present invention proposes, adopt RAFT polymerization, take water as medium, dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA) and NIPA (NIPAM) are as functional monomer, synthesize PDMAEMA-b-NIPAM block polymer, by regulating the molar ratio of two kinds of monomers to control micella or capsule form that block polymer forms in self assembling process when temperature or the pH environmental change; Then using this block polymer micelle as template, react with silane coupling agent, the Si-O-Si reticulated structure that silane coupling agent hydrolytic condensation forms is well coated on the surface of polymer micelle, this process is both without the introducing of organic reagent, again complete nano level precision architecture of having preserved block polymer micelle; Concrete steps are as follows:
(1) 1-2 g pH sensitive monomer is added in 25 mL reaction flasks, concentrated hydrochloric acid regulates pH to 5-6,0 ℃ of preservation; In another sample bottle, add 19-20 mg chain-transfer agent and 4-5 mg water soluble starter, slowly add 0.5-1 mL solvent that chain-transfer agent is dissolved, then add 4-5 mL ice deionized water; After all substances in sample bottle are all dissolved; this mixing solutions is poured in reaction flask; 0 ℃ of logical nitrogen 30 min, in 75-80 ℃ of reaction 3-6 h, is cooled to room temperature by reaction flask while finishing reaction under magnetic agitation nitrogen protection; logical atmosphere; in the deionized water that is 6-7 at pH by product, dialyse 3 days, revolve steaming, 25 ℃ of vacuum-drying 12-48 h; obtain a kind of macromolecular chain transfer agent, productive rate is 75%-95%.Wherein: chain-transfer agent is four cyano valeric acid dithiobenzoic acid, and water soluble starter is 4,4
,-azo-4-cyanopentanoic acid.
(2) by the prepared macromolecular chain transfer agent of 1-1.5g step (1), 0.5-2 g temperature sensitivity monomer; 5-15 mg water-soluble azo class initiator and 2-8 mL deionized water add in reaction flask; logical nitrogen 30 min; under the nitrogen protection of normal temperature magnetic agitation, react 6-8 h, while finishing reaction, make reaction flask lead to atmosphere, product is dialysed in deionized water 3 days; revolve steaming; 25 ℃ of vacuum-drying 12-48 h, obtain block polymer, and productive rate is 80%-96%.Wherein: water-soluble azo class initiator is azo two isobutyl imidazoline salt hydrochlorates.
(3) by the prepared block polymer of 0.1-0.2 g step (2), 20-30 mg linking agent and 2-3 mL deionized water normal temperature lower magnetic force stirring reaction 3 days, product is dialysed in deionized water 3 days, revolve steaming, 25 ℃ of vacuum-drying 12-48 h, obtain the crosslinked block polymer of shell.Wherein: described linking agent is two (the 2-iodo oxyethyl group) ethane of 1,2-.
(4) the crosslinked block polymer of the prepared shell of 0.1-0.2g step (3) is dissolved in 2 mL deionized waters and 0.2-0.4 g silane coupling agent normal temperature lower magnetic force stirring reaction 20 min, product is dialysed in deionized water 3 days, obtain silicon coated polymer nanoparticle.
In the present invention, pH sensitive monomer described in step (1) can be to contain a large amount of ionogen (COO
-,-NR
3 +,-NR
2h
+,-NRH
2 +deng), as vinylformic acid, dimethylaminoethyl acrylate methyl ammonia ethyl ester or dimethylaminoethyl acrylate methyl ammonia methyl esters etc.
In the present invention, temperature sensitivity monomer described in step (2) can be acrylamide or its similar monomer being replaced by N, such as NIPA, N-n-propyl acrylamide or N,N-DMAA etc.
In the present invention, described in step (1), solvent can be the mixing solutions of dioxane, water and dioxane, the mixing solutions of the mixing solutions of the mixing solutions of water and tetrahydrofuran (THF), water and methyl alcohol or water and dimethyl formamide.
In the present invention, silane coupling agent described in step (4) can be in aminopropyl triethoxysilane, 3-glycidyl ether oxygen base propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane or tetraethoxy etc. any.
In the present invention, the described reaction of step (4) can be that steaming is revolved in dialysis while finishing after-treatment products, can be also dialysis postlyophilization, or dry after precipitation agent precipitation.
Advantage of the present invention is: 1. the present invention is a kind of aqueous phase preparation method of silicon coated polymer nanoparticle, under aqueous environments, prepare this segmented copolymer, both adding without a large amount of organic solvents, reaction conditions is environment protection health more, monomer conversion is high again, can conveniently obtain the desirable block polymer of narrow distribution and is the silicon clad nano particle product (PDI coefficient is 1.07) of template; 2. utilize silicon coated polymer nanoparticle product prepared by the present invention to have nano level precision architecture, performance is more stable, and with organic polymer and special optics, magnetics, electricity and the mechanical property of inorganic materials; 3. preparation method of the present invention has reduced the production cost of producing the crosslinked micella of shell, there is the advantages such as technique is simple, input-output ratio is high, quality product is high, application prospect is extensive, the product that utilizes the present invention to prepare, meet the demand of society to environmental protection high performance chemical product, can be used for the fields such as nano biomedical material.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic spectrogram of block polymer polymethyl acrylic acid diformazan ammonia ethyl ester-b-N-N-isopropylacrylamide.
Block polymer PDMAEMA when Fig. 2 is 25 ℃
50-b-PNIPAM
170the dynamic light scattering collection of illustrative plates that the particle diameter of aggregate changes with pH.
Block polymer PDMAEMA when Fig. 3 is pH=7
50-b-PNIPAM
170the temperature variant dynamic light scattering collection of illustrative plates of particle diameter of aggregate.
Fig. 4 is 25 ℃, the TEM spectrogram of silicon clad nano particle during pH=9: (a) with block polymer PDMAEMA
50-b-PNIPAM
170silicon coated polymer nanoparticle for template; (b) with block polymer PDMAEMA
50-b-PNIPAM
80silicon coated polymer nanoparticle for template.
Embodiment
Embodiment 1
2 g dimethylaminoethyl acrylate methyl ammonia ethyl ester monomers are added in 25 mL reaction flasks, and concentrated hydrochloric acid regulates pH to 5,0 ℃ of preservation; In another sample bottle, add 19 mg chain-transfer agent four cyano valeric acid dithiobenzoic acids, 5 mg water soluble starter azo dicyano valeric acids, slowly add 0.5 mL dioxane that chain-transfer agent is dissolved, and then add 5 mL ice deionized waters.After all substances in sample bottle are all dissolved; this mixing solutions is poured in reaction flask; 0 ℃ of logical nitrogen 30 min, in 80 ℃ of reaction 6 h, is cooled to room temperature by reaction flask while finishing reaction under magnetic agitation nitrogen protection; contact with air; in the deionized water that is 6-7 at pH by product, dialyse 3 days, revolve steaming, 25 ℃ of vacuum-drying 48 h; obtain a kind of macromolecular chain transfer agent polymethyl acrylic acid diformazan ammonia ethyl ester, productive rate is 90%.
By the above-mentioned macromolecular chain transfer agent of 1 g polymethyl acrylic acid diformazan ammonia ethyl ester, 0.4 g monomer NIPA, 5 mg normal-temperature water dissolubility azo-initiator azo two isobutyl imidazoline salt hydrochlorates, 4 mL deionized waters add in reaction flask, logical nitrogen 30 min, under the nitrogen protection of normal temperature magnetic agitation, react 6 h, while finishing reaction, make reaction flask lead to atmosphere, product is dialysed in deionized water 3 days, revolve steaming, 25 ℃ of vacuum-drying 48 h, obtain block polymer polymethyl acrylic acid diformazan ammonia ethyl ester-b-N-N-isopropylacrylamide, its number-average molecular weight is 9699, productive rate is 88%.
By the above-mentioned block polymer polymethyl acrylic acid of 0.1 g diformazan ammonia ethyl ester-b-N-N-isopropylacrylamide and 20 mg linking agents 1, two (the 2-iodo oxyethyl group) ethane of 2-, 2 mL deionized water normal temperature lower magnetic force stirring reaction 3 days, product is dialysed in deionized water 3 days, revolve steaming, 25 ℃ of vacuum-drying 48 h, obtain the crosslinked block polymer of shell.
The above-mentioned block polymer of 0.1 g is dissolved in 2 mL deionized waters and 0.2 g silane coupling agent γ-(methacryloxypropyl) propyl trimethoxy silicane normal temperature lower magnetic force stirring reaction, 20 min, product is dialysed in deionized water 3 days, obtain silicon coated polymer nanoparticle.
The hydrogen nuclear magnetic spectrogram of this polymethyl acrylic acid diformazan ammonia ethyl ester-b-N-N-isopropylacrylamide as shown in Figure 1, Fig. 2 and Fig. 3 are respectively the change of size of block polymer micelle when differing temps, pH, and Fig. 4 is the transmission electron microscope picture of the silicon clad nano particle that under normal atmosphere temperature neutral, block polymer micelle is template.
Identical with embodiment 1, but dioxane solvent changes tetrahydrofuran (THF) into, and the volume ratio of itself and water keeps 1:5 ~ 1:10.
Identical with embodiment 1, but the molar ratio of dimethylaminoethyl acrylate methyl ammonia ethyl ester and NIPA becomes 60:30.
Embodiment 4
Identical with embodiment 1, but the molar ratio of dimethylaminoethyl acrylate methyl ammonia ethyl ester and NIPA becomes 70:40.
Identical with embodiment 1, but the molar ratio of dimethylaminoethyl acrylate methyl ammonia ethyl ester and NIPA becomes 80:50.
Embodiment 6
Identical with embodiment 1, but the molar ratio of dimethylaminoethyl acrylate methyl ammonia ethyl ester and NIPA becomes 20:110.
Embodiment 7
Identical with embodiment 1, but the molar ratio of dimethylaminoethyl acrylate methyl ammonia ethyl ester and NIPA becomes 30:100.
Embodiment 8
Identical with embodiment 1, but the molar ratio of dimethylaminoethyl acrylate methyl ammonia ethyl ester and NIPA becomes 40:90.
Identical with embodiment 1, but the molar ratio of dimethylaminoethyl acrylate methyl ammonia ethyl ester and NIPA becomes 50:80.
The block polymer obtaining in embodiment 2-9 and embodiment 1 have similar narrow distribution, the block polymer of embodiment 3,4,5 and embodiment 1 preparation forms the micella of different-grain diameter under the stimulation of extraneous environmental change, and the block polymer of embodiment 6,7,8,9 preparations forms the capsule of different-grain diameter under the stimulation of extraneous environmental change.
Claims (4)
1. an aqueous phase preparation method for silicon coated polymer nanoparticle, is characterized in that concrete steps are as follows:
(1) 1-2 g pH sensitive monomer is added in 25 mL reaction flasks, concentrated hydrochloric acid regulates pH to 5-6, at 0 ℃, preserves; In another sample bottle, add 19-20 mg chain-transfer agent and 4-5 mg water soluble starter, slowly add 0.5-1 mL solvent that chain-transfer agent is dissolved, then add 4-5 mL deionized water; After all substances in sample bottle are all dissolved, this mixing solutions is poured in reaction flask into 0 ℃ of logical nitrogen 30 min; under magnetic agitation nitrogen protection, in 75-80 ℃, react 3-6 h; while finishing reaction, reaction flask is cooled to room temperature, logical atmosphere, dialyses in the deionized water that is 6-7 3 days by product at pH; revolve steaming; 25 ℃ of vacuum-drying 12-48 h, obtain a kind of macromolecular chain transfer agent, wherein: chain-transfer agent is four cyano valeric acid dithiobenzoic acid; water soluble starter is 4,4
,-azo-4-cyanopentanoic acid; Described pH sensitive monomer be in vinylformic acid, dimethylaminoethyl acrylate methyl ammonia ethyl ester or dimethylaminoethyl acrylate methyl ammonia methyl esters any;
(2) by the prepared macromolecular chain transfer agent of 1-1.5g step (1), 0.5-2 g temperature sensitivity monomer, 5-15 mg water-soluble azo class initiator and 2-8 mL deionized water add in reaction flask, logical nitrogen 30 min, under the nitrogen protection of normal temperature magnetic agitation, react 6-8 h, while finishing reaction, make reaction flask lead to atmosphere, product is dialysed in deionized water 3 days, revolve steaming, 25 ℃ of vacuum-drying 12-48 h, obtain block polymer, wherein: water-soluble azo class initiator is azo two isobutyl imidazoline salt hydrochlorates; Described temperature sensitivity monomer is the acrylamide being replaced by N;
(3) by the prepared block polymer of 0.1-0.2 g step (2), 20-30 mg linking agent and 2-3 mL deionized water normal temperature lower magnetic force stirring reaction 3 days, product is dialysed in deionized water 3 days, revolve steaming, 25 ℃ of vacuum-drying 12-48 h, obtain the crosslinked block polymer of shell; Wherein: described linking agent is two (the 2-iodo oxyethyl group) ethane of 1,2-;
(4) the crosslinked block polymer of the prepared shell of 0.1-0.2g step (3) is dissolved in 2 mL deionized waters and 0.2-0.4 g silane coupling agent normal temperature lower magnetic force stirring reaction 20 min, product is dialysed in deionized water 3 days, obtain silicon coated polymer nanoparticle.
2. the aqueous phase preparation method of silicon coated polymer nanoparticle according to claim 1, it is characterized in that described in step (1), solvent is the mixing solutions of dioxane, water and dioxane, the mixing solutions of the mixing solutions of the mixing solutions of water and tetrahydrofuran (THF), water and methyl alcohol or water and dimethyl formamide.
3. the aqueous phase preparation method of silicon coated polymer nanoparticle according to claim 1, it is characterized in that silane coupling agent described in step (4) be in aminopropyl triethoxysilane, 3-glycidyl ether oxygen base propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane or tetraethoxy any.
4. the aqueous phase preparation method of silicon coated polymer nanoparticle according to claim 1, is characterized in that the described reaction of step (4) is that steaming is revolved in dialysis while finishing after-treatment products, or dialysis postlyophilization, or dry after precipitation agent precipitation.
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