CN110305272A - A kind of virus shape nano material and its Actinochemical synthesis - Google Patents

A kind of virus shape nano material and its Actinochemical synthesis Download PDF

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Publication number
CN110305272A
CN110305272A CN201910683797.2A CN201910683797A CN110305272A CN 110305272 A CN110305272 A CN 110305272A CN 201910683797 A CN201910683797 A CN 201910683797A CN 110305272 A CN110305272 A CN 110305272A
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nano material
virus
actinochemical synthesis
actinochemical
synthesis
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谭剑波
曾锐明
张力
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Guangdong University of Technology
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Guangdong University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00Living radical polymerisation
    • C08F2438/03Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Abstract

The invention belongs to technical field of polymer materials, more particularly to viral shape nano material and its Actinochemical synthesis.The present invention provides a kind of Actinochemical synthesis of viral shape nano material, it include: uniformly to mix the second block monomer, multi-functional Macro RAFT agent and photoinitiator with selective solvent, dispersin polymerization is carried out in the case where causing light source and induces self assembly, obtains diblock copolymer nano material.Wherein the second block monomer includes acrylic ester monomer.The present invention also provides a kind of viral shaped polymer nano materials.The present invention provides a kind of viral shape nano material and its Actinochemical synthesis, can effectively solve the technical issues of existing visible light polymerization induction self assembly can not synthesize viral shape pattern polymer nano material.

Description

A kind of virus shape nano material and its Actinochemical synthesis
Technical field
The invention belongs to technical field of polymer materials, more particularly to viral shape nano material and its photochemical syntheses side Method.
Background technique
The block copolymer nano material for having special appearance is always research hot topic, and polymer nano material definition is ruler It at least needs to be less than 100nm there are dimension in very little, and different-shape (spherical, vesica, tubulose, baked donut shape, sunflower shape Deng) polymer nano material biological therapy, drug conveying, catalysis, in terms of have huge potential application Value.So the method for the block polymer nano material that development can prepare specific morphology is that one of macromolecule subject grinds Study carefully emphasis.In recent years, polymerisation induced self assembly provides one newly to prepare the block polymer nano material of specific morphology Thinking.And the pattern of the common block copolymer obtained by polymerisation induced self assembly only has ball and vesica, such case The relatively restricted application field of copolymer.
It can be seen that light-initiated prepare the research hotspot that functional polymer is current macromolecule subject, there is efficiency of initiation High and low energy consumption, required temperature be low, photocontrol property and the advantages that biological friendly, has prepared different morphologies at present Block copolymer provides new method to prepare intelligent macromolecule.
In conclusion existing visible light polymerization induces the pattern of self assembly block copolymer and synthesizes disease Malicious shape pattern becomes those skilled in the art's technical problem urgently to be resolved.
Summary of the invention
The present invention provides a kind of viral shape nano material and its Actinochemical synthesis, can effectively solve existing visible light Cause the technical issues of polymerisation induced self assembly can not synthesize viral shape pattern polymer nano material.
The present invention is in view of the shortcomings of the prior art, main purpose is to provide a kind of viral shape easy to operate, that stability is high receives The Actinochemical synthesis of rice material.This method carries out tune Jie using multi-functional RAFT reagent, to design the poly- of novel pattern It closes object nano material and provides new mentality of designing.Viral shape nano material has the structure of more feelers on surface, on microcosmic Particle surface modification can be effectively carried out, also can be applied to the preparation of super hydrophobic material.
Technical scheme is as follows: under nitrogen atmosphere by acrylic ester monomer, Diacetone Acrylamide it is more Function Macro RAFT agent, photoinitiator and solvent mixing, carry out dispersion polymerization under the irradiation for causing light source, obtain The diblock copolymer nano material of viral shape;Wherein, multi-functional Macro RAFT agent is as stabilizer and the molten segment of parent, into Row RAFT light dispersin polymerization synthesizes stable viral shaped polymer nano material.
The beneficial effects of the present invention are: the present invention utilizes visible light-initiated RAFT dispersin polymerization, with poly- diacetone acrylamide Amide (PDAAM) is the structure of multi-functional Macro RAFT agent, and acrylic ester monomer is polymerized monomer, is carried out in a solvent Light initiation polymerization induction is self-assembly of viral shaped polymer nano material.Entire Macro RAFT agent be a stabilizer and Solvophilic segment, Macro RAFT agent stability is high and has said solvophilic.After common polymer is formed, monomer is added Also can not continue to increase chain extension, and the Macro RAFT agent that the present invention uses can cause again polymerization and form copolymer.Therefore, originally The Actinochemical synthesis of invention has different morphologies, particularly has viral shape pattern, can be in catalysis, super-hydrophobic, nanometer The fields such as reactor, biological medicine are with good application prospect.The light-initiated mode that the present invention takes, reaction rate is fast, only It need to can reach within one hour 90% or more monomer conversion.Present invention can also apply to the monomer polymerization with functional group, New thinking is provided for the functionalized polymer of design stability.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art To obtain other attached drawings according to these attached drawings.
Fig. 1 is transmission electron microscope (TEM) figure of the viral shaped polymer nano material of embodiment 2 provided by the invention preparation;
Fig. 2 is transmission electron microscope (SEM) figure of the viral shaped polymer nano material of embodiment 2 provided by the invention preparation;
Fig. 3 is transmission electron microscope (TEM) figure of the viral shaped polymer nano material of embodiment 3 provided by the invention preparation;
Fig. 4 is scanning electron microscope (SEM) figure of the viral shaped polymer nano material of embodiment 3 provided by the invention preparation;
Fig. 5 is transmission electron microscope (TEM) figure of the viral shaped polymer nano material of embodiment 4 provided by the invention preparation;
Fig. 6 is transmission electron microscope (SEM) figure of the viral shaped polymer nano material of embodiment 4 provided by the invention preparation;
Fig. 7 is transmission electron microscope (TEM) figure of the viral shaped polymer nano material of embodiment 5 provided by the invention preparation;
Fig. 8 is transmission electron microscope (SEM) figure of the viral shaped polymer nano material of embodiment 5 provided by the invention preparation;
Fig. 9 is nucleus magnetic hydrogen spectrum figure of the three functions small molecule RAFT reagent provided by the invention in deuterated dimethyl sulfoxide;
Figure 10 is nucleus magnetic hydrogen spectrum figure of the four functions small molecule RAFT reagent provided by the invention in deuterated chloroform.
Specific embodiment
The embodiment of the invention provides a kind of viral shape nano material and its Actinochemical synthesis, can effectively solve existing The technical issues of visible light polymerization induction self assembly can not synthesize viral shape pattern polymer nano material.
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the invention is clearly and completely described, Obviously, the embodiment described is the embodiment of part of representative of the invention, rather than whole embodiments, this field are general Other all embodiments obtained belong to protection of the invention to logical technical staff without making creative work Range.
Wherein, the raw material of following instance is commercially available or self-control;
Embodiment 1
It is specific as follows present embodiment discloses the synthetic route of Macro RAFT agent:
Synthetic macromolecule RAFT reagent, structure is as shown in Equation 2, and structural formula 2 is specific the preparation method comprises the following steps: diacetone acrylamide acyl Amine is obtained with multi-functional small molecules RAFT reagent by RAFT solution polymerization, wherein the knot of multi-functional small molecules RAFT reagent Structure formula such as formula 1:
Formula 1;
Formula 2, n are the natural number of 10-100, and m is the natural number of 2-8;CORE is central node;
The present invention provides the specific synthetic route of Macro RAFT agent, and steps are as follows:
Into the round-bottomed flask of 100mL, addition Diacetone Acrylamide (20.0000g, 118.1893mmol), three functions are small Molecule RAFT reagent (1.6812g, 1.8760mmol) or four function small molecule RAFT reagents (1.5533g, 1.4070mmol), AIBN (0.1846g, 1.1256mmol), metaformaldehyde (1.0652g, 11.8189mmol) and dioxane (46g), stirring are equal 0.5mL sample is taken after even, seals reaction system after being passed through nitrogen 20min.Round-bottomed flask is put into and is heated to 70 DEG C of oil bath pan Middle heating stirring contacts reaction system sufficiently with air and is put into ice water to carry out termination reaction after 2h, then takes 0.5mL sample Product are characterized by nucleus magnetic hydrogen spectrum, determine conversion ratio using metaformaldehyde as internal standard to determine the practical segment degree of polymerization.It is used after reaction N-hexane sedimentation, obtains yellow solid.Remaining solvent vacuum drying is removed, Macro RAFT agent is finally obtained;
Embodiment 2
The first Actinochemical synthesis of virus shaped polymer nano material provided by the invention, the specific steps are as follows:
It weighs isobornyl acrylate (IBOA, 1g, 4.8mmol), three function Macro RAFT agents (0.0716g, 0.0059mmol), photoinitiator diphenyl (2,4,6- trimethyl formamide) phosphine oxide (0.0021g, 0.0059mmol) is placed in In 25mL round-bottomed flask, adding ethanol/water mixed solvent (1.9834g/0.35g, 85:15, w/w), to be stirred well to reagent complete Fully dissolved.It keeps the nitrogen for continuing 20min to be passed through under the conditions of being protected from light, stops nitrogen and be passed through rear reaction system sealing.At 40 DEG C Heat preservation 10min is protected from light under water-bath, with LED light (405nm, 0.45mW/cm2) illumination initiation is carried out, stop reaction after 1h30min. Transmission electron microscope (TEM) figure of products therefrom and scanning electron microscope (SEM) figure are as shown shown in Figure 1 and Figure 2, are viral shape pattern.
Embodiment 3
It weighs isobornyl acrylate (IBOA, 1g, 4.8mmol), three function Macro RAFT agents (0.0708g, 0.0064mmol), photoinitiator diphenyl (2,4,6- trimethyl formamide) phosphine oxide (0.0021g, 0.0059mmol) is placed in In 25mL round-bottomed flask, adding ethanol/water mixed solvent (1.9834g/0.35g, 85:15, w/w), to be stirred well to reagent complete Fully dissolved.It keeps the nitrogen for continuing 20min to be passed through under the conditions of being protected from light, stops nitrogen and be passed through rear reaction system sealing.At 40 DEG C Heat preservation 10min is protected from light under water-bath, with LED light (405nm, 0.45mW/cm2) illumination initiation is carried out, stop reaction after 1h30min. Transmission electron microscope (TEM) figure and scanning electron microscope (SEM) figure of products therefrom are viral shape pattern as shown in attached drawing 3 and attached drawing 4.
Embodiment 4
It weighs isobornyl acrylate (IBOA, 1g, 4.8mmol), three function Macro RAFT agents (0.0466g, 0.0042mmol), photoinitiator diphenyl (2,4,6- trimethyl formamide) phosphine oxide (0.0021g, 0.0059mmol) is placed in In 25mL round-bottomed flask, adding ethanol/water mixed solvent (1.9834g/0.35g, 85:15, w/w), to be stirred well to reagent complete Fully dissolved.It keeps the nitrogen for continuing 20min to be passed through under the conditions of being protected from light, stops nitrogen and be passed through rear reaction system sealing.At 40 DEG C Heat preservation 10min is protected from light under water-bath, with LED light (405nm, 0.45mW/cm2) illumination initiation is carried out, stop reaction after 1h30min. Transmission electron microscope (TEM) figure and scanning electron microscope (SEM) figure of products therefrom are viral shape pattern as shown in attached drawing 5 and attached drawing 6.
Embodiment 5
It weighs isobornyl acrylate (IBOA, 1g, 4.8mmol), four function Macro RAFT agents (0.0676g, 0.0046mmol), photoinitiator diphenyl (2,4,6- trimethyl formamide) phosphine oxide (0.0021g, 0.0059mmol) is placed in In 25mL round-bottomed flask, adding ethanol/water mixed solvent (1.9834g/0.35g, 85:15, w/w), to be stirred well to reagent complete Fully dissolved.It keeps the nitrogen for continuing 20min to be passed through under the conditions of being protected from light, stops nitrogen and be passed through rear reaction system sealing.At 40 DEG C Heat preservation 10min is protected from light under water-bath, with LED light (405nm, 0.45mW/cm2) illumination initiation is carried out, stop reaction after 1h30min. Transmission electron microscope (TEM) figure and scanning electron microscope (SEM) figure of products therefrom are viral shape pattern as shown in attached drawing 7 and attached drawing 8.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention that claims determine, also Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by The range of claims determines.

Claims (10)

1. a kind of Actinochemical synthesis of virus shape nano material characterized by comprising
Second block monomer, multi-functional Macro RAFT agent and photoinitiator are uniformly mixed with selective solvent, caused Dispersin polymerization is carried out under light source and induces self assembly, obtains diblock copolymer nano material.Wherein the second block monomer includes third Olefin(e) acid esters monomer.
2. the Actinochemical synthesis of virus shape nano material according to claim 1, which is characterized in that described second is embedding Duan Danti is acrylic ester monomer.
3. the Actinochemical synthesis of virus shape nano material according to claim 1, which is characterized in that described multi-functional The structural formula of RAFT reagent:
4. the Actinochemical synthesis of virus shape nano material according to claim 1, which is characterized in that described light-initiated Agent include (2,4,6- trimethylbenzoyl) phenyl-phosphonic acid ethyl ester, diphenyl (2,4,6- trimethylbenzoyl) phosphine oxide, One of bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl or (2,4,6- trimethylbenzoyl) phenyl-phosphonic acid sodium.
5. the Actinochemical synthesis of virus shape nano material according to claim 1, which is characterized in that the initiation light The wavelength in source is 405-465nm.
6. the Actinochemical synthesis of virus shape nano material according to claim 1, which is characterized in that the initiation light The light intensity in source is 0.3-50mW/cm2
7. the Actinochemical synthesis of virus shape nano material according to claim 1, which is characterized in that the polymerization is single It is 10%-30% that body, which accounts for system quality ratio,.
8. the Actinochemical synthesis of virus shape nano material according to claim 1, which is characterized in that the polymerization is single The mass ratio of the material value of body and Macro RAFT agent is (50-400): 1.
9. the Actinochemical synthesis of virus shape nano material according to claim 1, which is characterized in that the macromolecular The mass ratio of the material value of RAFT reagent and the photoinitiator is (1-5): 1.
10. a kind of virus shaped polymer nano material, which is characterized in that the viral shape as described in claim 1 to 9 any one The Actinochemical synthesis of polymer nano material is prepared.
CN201910683797.2A 2019-07-26 2019-07-26 A kind of virus shape nano material and its Actinochemical synthesis Pending CN110305272A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104220471A (en) * 2012-02-03 2014-12-17 帝斯曼知识产权资产管理有限公司 Polymeric beads, process and composition
CN106279469A (en) * 2016-08-29 2017-01-04 中山大学 A kind of quick method preparing clean polymer microballoon

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104220471A (en) * 2012-02-03 2014-12-17 帝斯曼知识产权资产管理有限公司 Polymeric beads, process and composition
CN106279469A (en) * 2016-08-29 2017-01-04 中山大学 A kind of quick method preparing clean polymer microballoon

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HE, JUN,等: "Ketone-Functionalized Polymer Nano-Objects Prepared via Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA) Using a Poly(diacetone acrylamide)-Based Macro-RAFT Agent", 《MACROMOLECULAR RAPID COMMUNICATIONS 》 *
LANG, XIAOLONG,等: "Interaction and Conformation of Aqueous Poly(N-isopropylacrylamide) (PNIPAM) Star Polymers below the LCST", 《MACROMOLECULES》 *
RUIMING ZENG,等: "Uncontrolled polymerization that occurred during photoinitiated RAFT dispersion polymerization of acrylic monomers promotes the formation of uniform raspberry-like polymer particles", 《POLYMER CHEMISTRY》 *
肖俊杰: "DAAM的RAFT聚合及其在聚合物改性中的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

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