CN103948546A - Method for preparing antioxidant coated polymer nano-vesicle - Google Patents
Method for preparing antioxidant coated polymer nano-vesicle Download PDFInfo
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Abstract
The invention discloses a method for preparing an anti-oxidant coated polymer nano-vesicle. The method comprises the following steps: mixing bromo-polyoxyethylene, pentamethyldiethylenetriamine, dimethylaminoethyl methacrylate and a solvent in water-free and oxygen-free condition, adding cuprous bromide or cuprous chloride, and performing atom transfer radical polymerization in argon or nitrogen protection at 20-80 DEG C for 6-20 hours; dissolving styrene in anhydrous paraxylene, deoxidizing, and adding into the atom transfer radical polymerization to react at 40-130 DEG C for 12-72 hours; evaporating and dissolving the prepared polymer, passing the prepared through a neutral alumina column, precipitating, filtering and drying in vacuum to obtain an amphiphilic block copolymer PEO-b-PDMA-b-PS; dissolving the PEO-b-PDMA-b-PS and an antioxidant in THF (tetrahydrofuran), dripping deionized water or methanol which is 3-10 times of the THF at a speed of 1-60d/min under intense stirring; dialyzing in deionized water, and drying to obtain the product. The product obtained by the method can play a good health-care effect on skin, and can be used for delaying skin aging.
Description
Technical field
The invention belongs to skin beauty health-care chemicals technical field, relate to a kind of effectively preparation method of the skin-care product of delay skin aging, be specifically related to a kind of preparation method of polymer nano vesicle of coated antioxidant.
Background technology
Along with the carrying out of industrial age, various toxic gas are discharged in atmosphere, and the environmental problem causing thus highlights day by day; Be exactly wherein very distinct issues for the destruction of ozone layer.See through atmosphere because the destruction of ozone layer makes a large amount of ultraviolet, shine directly on human body skin.Excessive ultraviolet radiation not only causes very large injury for people's skin, more can greatly increase the probability of suffering from skin carcinoma.Therefore sunscreen product on the market emerges in an endless stream, and these products mainly absorb or shielding of ultraviolet radiation by some active component wherein, thereby reaches the object of ultraviolet radiation preventing.Existing sunscreen product, is that organic products or inorganic product all exist significant deficiency, often harmful; Inorganic product comprises that titanium dioxide and zinc oxide or some other heavy metallic oxides all have very strong photo-catalysis capability, and these active component can cause catalytic reaction at human body skin, produces free radical, thereby human body skin is damaged.In addition, these products have only played the ultraviolet effect of eliminating, and skin are not played the effect of health care, and they are at a complete loss as to what to do for the elimination of free radical; And free radical is a key factor that causes skin aging.
Antioxidant is a kind of chemical substance that can efficiently eliminate free radical.The kind of antioxidant has a lot, and every kind has different effects, but they have a general character, and that is exactly to eliminate free radical by redox reaction well.Taking ferulic acid as example, it is a kind of conventional antioxidant, and the content in the Chinese crude drugs such as Resina Ferulae, Radix Angelicae Sinensis, Rhizoma Chuanxiong, Rhizoma Cimicifugae, Semen Ziziphi Spinosae is higher, is one of the effective elements of the medicine in these, as one of quality index of Chinese patent medicine.In raw-food material, in coffee, rice husk, chinese cymbidium bean, Testa Tritici, Testa oryzae, ferulaic acid content is also higher.Pharmacological action and the biological activity of many ferulic acids and derivant found in research aspect pharmacological effect in recent years, and toxicity is lower, thereby has purposes widely at aspects such as medicine, health product, cosmetic material and food additive.Remove these good drug effects, as a kind of conventional antioxidant, ferulic acid has efficient antioxidant effect, therefore Trapped free radical efficiently.
Nanometer polymer vesicle is subject to extensive concern in recent years as pharmaceutical carrier, it is a kind of double membrane structure with cavity, the cavity of the inside can be used for wrapping medicine carrying thing, therefore also can be used for being coated antioxidant, and the hydrophilic polymer chains that outside disperses can make it stable existence in water.If the surface of polymer vesicle is hydrophilic polyoxyethylene chain (PEO is also called polyglycol chain PEG), just can change the physicochemical properties on vesicle surface, make it have good water solublity and stability, there is good biocompatibility simultaneously.In sum, a kind of like this product that can effectively remove free radical on skin and can play fine health-care effect to skin of preparation has important practical significance.
Summary of the invention
For the defect of prior art, the object of this invention is to provide a kind of preparation method of polymer nano vesicle of coated antioxidant, the product being obtained by the method can play a role in health care to skin well, delay skin aging.
To achieve these goals, the present invention has adopted following technical scheme:
The preparation method that the invention provides a kind of polymer nano vesicle of coated antioxidant, comprises the following steps:
By macromole evocating agent bromo polyoxyethylene (PEO-Br), catalyst ligand pentamethyl-diethylenetriamine (PMDETA) and monomer dimethylaminoethyl methacrylate (DMA) mix under the condition of anhydrous and oxygen-free with solvent, add catalyst cuprous bromide or Cu-lyt. (CuBr, CuCl), under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), polymerization temperature is 20～80 DEG C, time is 6～20 hours, styrene is dissolved in anhydrous xylol, after deoxygenation, join in above-mentioned reaction, polymerization temperature is 40～130 DEG C, time is 12～72 hours, the polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO-b-PDMA-b-PS,
Amphipathic nature block polymer PEO-b-PDMA-b-PS and antioxidant are dissolved in THF, under strong agitation, drip 3～10 times of deionized waters to THF or methanol with the speed of 1～60d/min; After stirring, in deionized water, dialyse, after being dried, obtain the polymer nano vesicle of coated antioxidant.
The mol ratio of described macromole evocating agent bromo polyoxyethylene (PEO-Br), catalyst ligand pentamethyl-diethylenetriamine (PMDETA) and monomer dimethylaminoethyl methacrylate (DMA) is 1:(1～5): (20～100).
The addition of described catalyst cuprous bromide or Cu-lyt. (CuBr, CuCl) is identical with the polyoxyethylated molal quantity of macromole evocating agent bromo.
The polyoxyethylated mol ratio of described styrene and bromo is (100～400): 1.
The molecular weight of described amphipathic nature block polymer PEO-b-PDMA-b-PS is 4000～60000.
Described solvent is one or more in toluene, dichloromethane, oxolane, methanol, ethanol, dimethyl sulfoxide or dimethyl formamide.
The concentration that described amphipathic nature block polymer PEO-b-PDMA-b-PS is dissolved in THF is 1～20mg/ml.
Described antioxidant is one or more in ferulic acid, glutathion, vitamin E, carotenoid or ascorbic acid.The concentration that described antioxidant is dissolved in THF is 0.1～100mg/ml.
The diameter of the polymer nano vesicle of described coated antioxidant is 100～800 nanometers (nm).
The present invention compared with the existing technology, has the following advantages and beneficial effect:
1, the synthetic triblock polymer of the present invention, in assembling process, can, by controlling the ratio adjusting size of initial concentration, drop rate and deionized water, obtain disperseing the polymer nano vesicle of homogeneous.
2, in the synthetic polymer nano vesicle of the present invention, contain amine structure, this structure can with the effect of multiple antioxidant generation non-covalent bond, thereby can efficiently be coated multiple antioxidant.
3, the synthetic product of the present invention can play the effect of health care in anti-ultraviolet, has efficient removing ability for free radical, therefore benefits for delay skin aging.
4, in the synthetic polymer architecture of the present invention, contain a large amount of phenyl ring, the vesicle itself that therefore assembling forms just has efficient uvioresistant performance, and the cavity that vesicle has can be coated a large amount of different types of antioxidants; Tertiary amine structure in polymer can occur to interact with some antioxidants and greatly increase bag carrying capacity; The polymer vesicle Stability Analysis of Structures of coated antioxidant, preparation method is simple, has good biocompatibility, and not Diazolidinyl Urea has the ability of very high removing free radical, therefore has good effect for delay skin aging; The antioxidant carrying due to bag has various pharmacological function, therefore can be used as a kind of health product and uses.
Brief description of the drawings
Fig. 1 is macromole evocating agent PEO
43-Br(A) with amphipathic nature block polymer PEO-b-PDMA-b-PS(B) nuclear-magnetism spectrum comparison diagram.
Fig. 2 is dynamic light scattering (DLS) figure of the polymer nano vesicle of self assembly formation.
Fig. 3 is the transmission electron microscope figure of polymer nano vesicle, and wherein: the scale of C is 200nm, the scale of D is 100nm.
Fig. 4 is the antioxidant effect figure of the polymer nano vesicle of coated ferulic acid.
Detailed description of the invention
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is further detailed explanation.
Embodiment 1
By 0.5g macromole evocating agent PEO
43-Br, 0.08g catalyst ligand PMDETA, 0.8g monomer DMA and 2ml absolute methanol add in round-bottomed flask, macromole evocating agent PEO
43the mol ratio of-Br, catalyst ligand PMDETA and monomer DMA is 1:1:20; Under the condition of anhydrous and oxygen-free, add 0.08g Catalysts Cu Br; The addition of catalyst cuprous bromide and macromole evocating agent PEO
43the molal quantity of-Br is identical.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 25 DEG C, and the response time is 8 hours.After reaction finishes, 3.9g monomer styrene is dissolved in 10ml xylol, joins in flask after deoxygenation, reaction temperature is 60 DEG C, and the response time is 50 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO
43-b-PDMA
20-b-PS
110; Wherein the polyoxyethylated mol ratio of styrene and bromo is 110:1; The amphipathic nature block polymer PEO obtaining
43-b-PDMA
20-b-PS
110molecular weight be 16000.
By the amphipathic nature block polymer PEO making
43-b-PDMA
20-b-PS
110be dissolved in THF with antioxidant ferulic acid, make amphipathic nature block polymer PEO
43-b-PDMA
20-b-PS
110be respectively 2mg/ml and 1mg/ml with the ultimate density of ferulic acid.Under strong agitation, speed with 10d/min is added drop-wise to the deionized water that is three times in THF volume in above-mentioned solution, in deionized water, organic solvent and free ferulic acid are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated ferulic acid turning white, after being dried, obtain the polymer nano vesicle powder that diameter is the coated ferulic acid of 300 nanometers.As shown in Fig. 1～4, Fig. 1 is macromole evocating agent PEO
43-Br(A) with amphipathic nature block polymer PEO-b-PDMA-b-PS(B) nuclear-magnetism spectrum comparison diagram, illustrate that two kinds of polymer have successfully been synthesized; Fig. 2 is dynamic light scattering (DLS) figure of the polymer nano vesicle of self assembly formation, can see that its particle diameter is 303nm, and polydispersity coefficient is 0.048, illustrates that it has good dispersibility; Fig. 3 is the transmission electron microscope figure of polymer nano vesicle, and wherein: the scale of C is 200nm, the scale of D is 100nm, in figure, can obviously see hollow-core construction; Fig. 4 is the antioxidant effect figure of the polymer nano vesicle of coated ferulic acid, can see that working as ferulic acid concentration is 2 in figure
μwhen g/ml, just can remove more than 80% free radical, its efficient antioxidant effect is described.Embodiment 2
By 0.5g macromole evocating agent PEO
43-Br, 0.24g catalyst ligand PMDETA, 2.4g monomer DMA and 2ml absolute methanol add in round-bottomed flask, macromole evocating agent PEO
43the mol ratio of-Br, catalyst ligand PMDETA and monomer DMA is 1:3:60; Under the condition of anhydrous and oxygen-free, add 0.08g Catalysts Cu Br; The addition of catalyst cuprous bromide and macromole evocating agent PEO
43the molal quantity of-Br is identical.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 40 DEG C, and the response time is 13 hours.After reaction finishes, 7.8g monomer styrene is dissolved in 10ml xylol, joins in flask after deoxygenation, reaction temperature is 80 DEG C, and the response time is 60 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO
43-b-PDMA
60-b-PS
220; Wherein the polyoxyethylated mol ratio of styrene and bromo is 220:1; The amphipathic nature block polymer PEO obtaining
43-b-PDMA
20-b-PS
220molecular weight be 34000.
By the amphipathic nature block polymer PEO making
43-b-PDMA
60-b-PS
220be dissolved in THF with antioxidant glutathion, make amphipathic nature block polymer PEO
43-b-PDMA
60-b-PS
220be respectively 5mg/ml and 3mg/ml with the ultimate density of glutathion.Under strong agitation, speed with 15d/min is added drop-wise to the deionized water that is three times in THF volume in above-mentioned solution, in deionized water, organic solvent and free glutathion are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated glutathion turning white, after being dried, obtain the polymer nano vesicle powder that diameter is the coated glutathion of 200 nanometers.
Embodiment 3
By 0.5g macromole evocating agent PEO
43-Br, 0.4g catalyst ligand PMDETA, 3.2g monomer DMA and 3ml absolute methanol add in round-bottomed flask, macromole evocating agent PEO
43the mol ratio of-Br, catalyst ligand PMDETA and monomer DMA is 1:4:80; Under the condition of anhydrous and oxygen-free, add 0.08g Catalysts Cu Br; The addition of catalyst cuprous bromide and macromole evocating agent PEO
43the molal quantity of-Br is identical.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 50 DEG C, and the response time is 18 hours.After reaction finishes, 11.7g monomer styrene is dissolved in 15ml xylol, joins in flask after deoxygenation, reaction temperature is 130 DEG C, and the response time is 12 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO
43-b-PDMA
80-b-PS
340; Wherein the polyoxyethylated mol ratio of styrene and bromo is 340:1; The amphipathic nature block polymer PEO obtaining
43-b-PDMA
80-b-PS
340molecular weight be 50000.
By the amphipathic nature block polymer PEO making
43-b-PDMA
80-b-PS
340be dissolved in THF with antioxidant vitamin E, make amphipathic nature block polymer PEO
43-b-PDMA
80-b-PS
340be respectively 4mg/ml and 2mg/ml with the ultimate density of vitamin E.Under strong agitation, speed with 17d/min is added drop-wise to the deionized water that is three times in THF volume in above-mentioned solution, in deionized water, organic solvent and free vitamin E are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated vitamin E turning white, after being dried, obtain the polymer nano vesicle powder that diameter is 200 nanometer coated vitamin Es.
Embodiment 4
By macromole evocating agent PEO-Br, catalyst ligand PMDETA, monomer DMA and 2ml toluene add in round-bottomed flask, and the mol ratio of macromole evocating agent PEO-Br, catalyst ligand PMDETA and monomer DMA is 1:1:20; Under the condition of anhydrous and oxygen-free, add catalyst Cu-lyt.; The addition of catalyst Cu-lyt. is identical with the molal quantity of macromole evocating agent PEO-Br.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 20 DEG C, and the response time is 20 hours.After reaction finishes, monomer styrene is dissolved in 10ml xylol, joins in flask after deoxygenation, reaction temperature is 40 DEG C, and the response time is 72 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO-b-PDMA-b-PS; Wherein the polyoxyethylated mol ratio of styrene and bromo is 100:1; The molecular weight of the amphipathic nature block polymer PEO-b-PDMA-b-PS obtaining is 15000.The amphipathic nature block polymer PEO-b-PDMA-b-PS making and antioxidant carotenoid are dissolved in THF, make the ultimate density of amphipathic nature block polymer PEO-b-PDMA-b-PS and carotenoid be respectively 1mg/ml and 0.1mg/ml.Under strong agitation, speed with 1d/min is added drop-wise to 10 times of methanol to THF volume in above-mentioned solution, in deionized water, organic solvent and free carotenoid are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated carotenoid turning white, after being dried, obtain the polymer nano vesicle powder that diameter is the coated carotenoid of 100 nanometers.
Embodiment 5
By macromole evocating agent PEO-Br, catalyst ligand PMDETA, monomer DMA and 2ml dichloromethane add in round-bottomed flask, and the mol ratio of macromole evocating agent PEO-Br, catalyst ligand PMDETA and monomer DMA is 1:5:100; Under the condition of anhydrous and oxygen-free, add catalyst cuprous bromide; The addition of catalyst cuprous bromide is identical with the molal quantity of macromole evocating agent PEO-Br.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 80 DEG C, and the response time is 6 hours.After reaction finishes, monomer styrene is dissolved in 10ml xylol, joins in flask after deoxygenation, reaction temperature is 100 DEG C, and the response time is 45 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO-b-PDMA-b-PS; Wherein the polyoxyethylated mol ratio of styrene and bromo is 400:1; The molecular weight of the amphipathic nature block polymer PEO-b-PDMA-b-PS obtaining is 60000.
The amphipathic nature block polymer PEO-b-PDMA-b-PS making and antioxidants ascorbic acid are dissolved in THF, make the ultimate density of amphipathic nature block polymer PEO-b-PDMA-b-PS and ascorbic acid be respectively 20mg/ml and 100mg/ml.Under strong agitation, speed with 60d/min is added drop-wise to 5 times of deionized waters to THF volume in above-mentioned solution, in deionized water, organic solvent and free ascorbic acid are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated ascorbic acid turning white, after being dried, obtain the polymer nano vesicle powder that diameter is the coated ascorbic acid of 800 nanometers.
Embodiment 6
By macromole evocating agent PEO-Br, catalyst ligand PMDETA, monomer DMA and 2ml oxolane add in round-bottomed flask, and the mol ratio of macromole evocating agent PEO-Br, catalyst ligand PMDETA and monomer DMA is 1:2.5:60; Under the condition of anhydrous and oxygen-free, add catalyst cuprous bromide; The addition of catalyst cuprous bromide is identical with the molal quantity of macromole evocating agent PEO-Br.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 70 DEG C, and the response time is 7 hours.After reaction finishes, monomer styrene is dissolved in 10ml xylol, joins in flask after deoxygenation, reaction temperature is 120 DEG C, and the response time is 35 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO-b-PDMA-b-PS; Wherein the polyoxyethylated mol ratio of styrene and bromo is 200:1; The molecular weight of the amphipathic nature block polymer PEO-b-PDMA-b-PS obtaining is 32000.
The amphipathic nature block polymer PEO-b-PDMA-b-PS making and antioxidant ferulic acid are dissolved in THF, make the ultimate density of amphipathic nature block polymer PEO-b-PDMA-b-PS and ferulic acid be respectively 10mg/ml and 50mg/ml.Under strong agitation, speed with 30d/min is added drop-wise to 4 times of deionized waters to THF volume in above-mentioned solution, in deionized water, organic solvent and free ferulic acid are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated ferulic acid turning white, after being dried, obtain the polymer nano vesicle powder that diameter is the coated ferulic acid of 500 nanometers.
Embodiment 7
By macromole evocating agent PEO-Br, catalyst ligand PMDETA, monomer DMA and 2ml ethanol add in round-bottomed flask, and the mol ratio of macromole evocating agent PEO-Br, catalyst ligand PMDETA and monomer DMA is 1:2:40; Under the condition of anhydrous and oxygen-free, add catalyst cuprous bromide; The addition of catalyst cuprous bromide is identical with the molal quantity of macromole evocating agent PEO-Br.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 30 DEG C, and the response time is 18 hours.After reaction finishes, monomer styrene is dissolved in 10ml xylol, joins in flask after deoxygenation, reaction temperature is 50 DEG C, and the response time is 65 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO-b-PDMA-b-PS; Wherein the polyoxyethylated mol ratio of styrene and bromo is 300:1; The molecular weight of the amphipathic nature block polymer PEO-b-PDMA-b-PS obtaining is 37000.
The amphipathic nature block polymer PEO-b-PDMA-b-PS making and antioxidant ferulic acid are dissolved in THF, make the ultimate density of amphipathic nature block polymer PEO-b-PDMA-b-PS and ferulic acid be respectively 8mg/ml and 40mg/ml.Under strong agitation, speed with 20d/min is added drop-wise to 6 times of deionized waters to THF volume in above-mentioned solution, in deionized water, organic solvent and free ferulic acid are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated ferulic acid turning white, after being dried, obtain the polymer nano vesicle powder that diameter is the coated ferulic acid of 200 nanometers.
Embodiment 8
By macromole evocating agent PEO-Br, catalyst ligand PMDETA, monomer DMA and 2ml dimethyl sulfoxide add in round-bottomed flask, and the mol ratio of macromole evocating agent PEO-Br, catalyst ligand PMDETA and monomer DMA is 1:3:80; Under the condition of anhydrous and oxygen-free, add catalyst cuprous bromide; The addition of catalyst cuprous bromide is identical with the molal quantity of macromole evocating agent PEO-Br.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 60 DEG C, and the response time is 13 hours.After reaction finishes, monomer styrene is dissolved in 10ml xylol, joins in flask after deoxygenation, reaction temperature is 80 DEG C, and the response time is 42 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO-b-PDMA-b-PS; Wherein the polyoxyethylated mol ratio of styrene and bromo is 150:1; The molecular weight of the amphipathic nature block polymer PEO-b-PDMA-b-PS obtaining is 30000.
The amphipathic nature block polymer PEO-b-PDMA-b-PS making and antioxidant ferulic acid are dissolved in THF, make the ultimate density of amphipathic nature block polymer PEO-b-PDMA-b-PS and ferulic acid be respectively 15mg/ml and 80mg/ml.Under strong agitation, speed with 40d/min is added drop-wise to 7 times of deionized waters to THF volume in above-mentioned solution, in deionized water, organic solvent and free ferulic acid are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated ferulic acid turning white, after being dried, obtain the polymer nano vesicle powder that diameter is the coated ferulic acid of 400 nanometers.
Embodiment 9
By macromole evocating agent PEO-Br, catalyst ligand PMDETA, monomer DMA and 2ml dimethyl formamide add in round-bottomed flask, and the mol ratio of macromole evocating agent PEO-Br, catalyst ligand PMDETA and monomer DMA is 1:4:50; Under the condition of anhydrous and oxygen-free, add catalyst cuprous bromide; The addition of catalyst cuprous bromide is identical with the molal quantity of macromole evocating agent PEO-Br.Under argon or nitrogen protection, carry out atom transfer radical polymerization (ATRP), reaction temperature is 55 DEG C, and the response time is 15 hours.After reaction finishes, monomer styrene is dissolved in 10ml xylol, joins in flask after deoxygenation, reaction temperature is 90 DEG C, and the response time is 40 hours.The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO-b-PDMA-b-PS; Wherein the polyoxyethylated mol ratio of styrene and bromo is 250:1; The molecular weight of the amphipathic nature block polymer PEO-b-PDMA-b-PS obtaining is 36000.
The amphipathic nature block polymer PEO-b-PDMA-b-PS making and antioxidant ferulic acid are dissolved in THF, make the ultimate density of amphipathic nature block polymer PEO-b-PDMA-b-PS and ferulic acid be respectively 18mg/ml and 5mg/ml.Under strong agitation, speed with 50d/min is added drop-wise to 8 times of deionized waters to THF volume in above-mentioned solution, in deionized water, organic solvent and free ferulic acid are removed in dialysis, finally obtain the polymer nano vesicle solution of the light blue coated ferulic acid turning white, after being dried, obtain the polymer nano vesicle powder that diameter is the coated ferulic acid of 600 nanometers.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various amendments to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from improvement and the amendment that category of the present invention makes all should be within protection scope of the present invention.
Claims (10)
1. a preparation method for the polymer nano vesicle of coated antioxidant, is characterized in that: comprise the following steps:
Macromole evocating agent bromo polyoxyethylene, catalyst ligand pentamethyl-diethylenetriamine and monomer dimethylaminoethyl methacrylate are mixed under the condition of anhydrous and oxygen-free with solvent, add catalyst cuprous bromide or Cu-lyt., under argon or nitrogen protection, carry out atom transfer radical polymerization, polymerization temperature is 20～80 DEG C, time is 6～20 hours, styrene is dissolved in anhydrous xylol, after deoxygenation, join in above-mentioned reaction, polymerization temperature is 40～130 DEG C, and the time is 12～72 hours; The polymer making is revolved to steaming, dissolving, crosses neutral alumina pillar, precipitation, filtration, vacuum drying, obtain amphipathic nature block polymer PEO-b-PDMA-b-PS; Amphipathic nature block polymer PEO-b-PDMA-b-PS and antioxidant are dissolved in THF, under strong agitation, drip 3～10 times of deionized waters to THF or methanol with the speed of 1～60d/min; After stirring, in deionized water, dialyse, after being dried, obtain the polymer nano vesicle of coated antioxidant.
2. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: the mol ratio of described macromole evocating agent bromo polyoxyethylene, catalyst ligand pentamethyl-diethylenetriamine and monomer dimethylaminoethyl methacrylate is 1:(1～5): (20～100).
3. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: the addition of described catalyst cuprous bromide or Cu-lyt. is identical with the polyoxyethylated molal quantity of macromole evocating agent bromo.
4. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: the polyoxyethylated mol ratio of described styrene and bromo is (100～400): 1.
5. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: the molecular weight of described amphipathic nature block polymer PEO-b-PDMA-b-PS is 4000～60000.
6. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: described solvent is one or more in toluene, dichloromethane, oxolane, methanol, ethanol, dimethyl sulfoxide or dimethyl formamide.
7. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: the concentration that described amphipathic nature block polymer PEO-b-PDMA-b-PS is dissolved in THF is 1～20mg/ml.
8. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: described antioxidant is one or more in ferulic acid, glutathion, vitamin E, carotenoid or ascorbic acid.
9. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: the concentration that described antioxidant is dissolved in THF is 0.1～100mg/ml.
10. the preparation method of the polymer nano vesicle of coated antioxidant according to claim 1, is characterized in that: the diameter of the polymer nano vesicle of described coated antioxidant is 100～800 nanometers.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861129A (en) * | 2015-04-27 | 2015-08-26 | 中国科学院长春应用化学研究所 | Polymer giant vesicle preparation method and device |
| CN108084462A (en) * | 2017-12-29 | 2018-05-29 | 安徽宏实光机电高科有限公司 | A kind of preparation method of polymer vesicle coating modification nylon powder |
| CN109513460A (en) * | 2018-11-20 | 2019-03-26 | 扬州大学 | A kind of synthetic method of beta carotene degradation catalyst |
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| CN102631951A (en) * | 2012-04-10 | 2012-08-15 | 同济大学 | Method for preparing organic-inorganic hybrid nano-titania hollow ball with high catalytic performance |
| CN102675568A (en) * | 2012-06-01 | 2012-09-19 | 同济大学 | Preparation method for organic-inorganic hybrid skin-friendly efficient sunscreen product |
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| CN102631951A (en) * | 2012-04-10 | 2012-08-15 | 同济大学 | Method for preparing organic-inorganic hybrid nano-titania hollow ball with high catalytic performance |
| CN102675568A (en) * | 2012-06-01 | 2012-09-19 | 同济大学 | Preparation method for organic-inorganic hybrid skin-friendly efficient sunscreen product |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861129A (en) * | 2015-04-27 | 2015-08-26 | 中国科学院长春应用化学研究所 | Polymer giant vesicle preparation method and device |
| CN104861129B (en) * | 2015-04-27 | 2017-07-25 | 中国科学院长春应用化学研究所 | The preparation method and device of polymer Giant Vesicles |
| CN108084462A (en) * | 2017-12-29 | 2018-05-29 | 安徽宏实光机电高科有限公司 | A kind of preparation method of polymer vesicle coating modification nylon powder |
| CN109513460A (en) * | 2018-11-20 | 2019-03-26 | 扬州大学 | A kind of synthetic method of beta carotene degradation catalyst |
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| CN103948546B (en) | 2016-04-06 |
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