CN106750058B - A kind of polymer is single-stranded/and the Janus material of Nanocomposites structure and its cation cause double-bond polymerization preparation method - Google Patents
A kind of polymer is single-stranded/and the Janus material of Nanocomposites structure and its cation cause double-bond polymerization preparation method Download PDFInfo
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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Abstract
The present invention provide a kind of polymer it is single-stranded/the Janus material of Nanocomposites structure and its cation cause double-bond polymerization preparation method.The Janus nano material is caused by cation containing double bond monomer polymerization preparation, and it wherein at least includes a spherical structure that structural model, which can be selected from chain, and order of connection any combination of spherical structure unit arranges；The single-stranded chemical composition of polymer, the degree of polymerization is adjustable；Nanoparticle chemistry composition, size are controllable.The present invention can be realized the Janus material with multiple latent functionality that quick, mass prepares the Nomenclature Composition and Structure of Complexes accuracy controlling, this material combines the single-stranded excellent properties with nanoparticle of polymer, has great importance in the fields such as catalysis, water-oil separating, water body purification and cell recognition.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to and a kind of polymer is single-stranded/Nanocomposites structure
Janus material and its cation cause double-bond polymerization preparation method.
Background technique
Janus originates from the two-sided mind of ancient Roman's mythology.1991, de Gennes was put forward for the first time mono- word of Janus, to
Those particle (the de Gennes, P.G.Soft in structure or composition with double properties are described
Matter.Science.1992,256(5056),495-497).Janus material with double properties is a kind of with uniqueness
Micro-structure and functional new material, it is with important application prospects in numerous areas.The existing method for preparing Janus material is still
So there are problems.Most common interface Protection Code (Wang, B.Amphiphilic Janus Gold Nanoparticles
via Combining“Solid-State Grafting-to”and“Grafting-from”Methods.Journal of
The American Chemical Society.2008,130 (35), 11594-11595.) though it is able to achieve to Janus material knot
The accurate control of structure, but it is difficult to mass production.Microfluid method (Kim, S.-H.Optofluidic Synthesis of
Electroresponsive Photonic Janus Balls with Isotropic Structural
Colors.Advanced Materials.2008,20 (21), 4129-4134) preparation Janus material composition strict partition and
Form of diverse, but size is larger, can not obtain the sub-micron even material of nanoscale.Phase separation method is easy to mass production
(Tanaka,T.Preparation of“Mushroom-like”Janus Particles by Site-Selective
Surface-Initiated Atom Transfer Radical Polymerization in Aqueous Dispersed
Systems.Langmuir.2010,26(11),7843-7847.；Tanaka,T.Dual Stimuli-Responsive
“Mushroom-like”Janus Polymer Particles as Particulate
Surfactants.Langmuir.2010,26 (14), 11732-11736.), but be difficult to realize chemical composition strict partition and
The precise controlling of micro-structure.Especially, polymer it is single-stranded/Nanocomposites Janus material, mainly by block copolymer friendship
Join and prepares (Cheng, L.；Hou,G.L.；Miao,J.J.；Chen,D.Y.Efficient Synthesis of
Unimolecular Polymeric Janus Nanoparticles and Their Unique Self-Assembly
Behavior in a Common Solvent.Macromolecules.2008,41,8159-8166.；Zhou,F.；Xie,
M.X.；Chen,D.Y.Structure and Ultrasonic Sensitivity of the Superparticles
Formed by Self-Assembly of Single Chain Janus Nanoparticles.Macromolecules.2
014,47,365-372；Xu,F.G.；Fang,Z.H.；Yang,D.G.；Gao,Y.；Li,H.M.；Chen,D.Y.Water in
Oil Emulsion Stabilized by Tadpole-like Single Chain Polymer Nanoparticles
and Its Application in Biphase Reaction.ACS AppliedMaterials&Interfaces.2014,
6,6717-6723), i.e., to obtain the Janus that nanoparticle and macromolecular single-chain coexist by intramolecular crosslinking some block compound
Material.But intermolecular cross-linking, process must carry out this method at extremely low solid content (≤1%) in order to prevent.Still lacking can be real
Existing the Nomenclature Composition and Structure of Complexes accuracy controlling, size the function and service Janus material of nanoscale controllable and high solids content mass
Preparation.
Summary of the invention
Based on the problems of above-mentioned existing preparation method, the object of the present invention is to provide a kind of quick, mass systems
It is standby to have both the single-stranded method with the Janus material of Nanocomposites structure of polymer, that is, pass through cationic polymerization process and prepares
Chain/ball unit any combination is prepared by contiguous segmentation living polymerization mode with chain/spherical structure Janus high molecular material
Made of Janus material.
To achieve the goals above, the cationic polymerization that the present invention provides a kind of quickly intimate 100% conversion ratio prepares simultaneous
The standby single-stranded method with the Janus material of Nanocomposites structure of polymer.The method has quick, simplicity, solid content height etc.
Advantage.There is the Janus material of the method preparation chain and nanoparticle chemistry to form adjustable, the single-stranded degree of polymerization and nano-particles size
Controllably, single-stranded and nanoparticle the order of connection, that is, controllable feature of material structure/composition.
It is provided by the present invention by polymer is single-stranded and the molecular Janus nano material of nanoparticle, it is Janus nanometers described
Material is caused by cation containing double bond monomer polymerization preparation, and structural model can be selected from the order of connection of chain Yu spherical structure unit
Any combination arrangement (such as ball, ball/ball, chain/ball, chain/ball/chain, ball/chain/ball, chain/ball/chain/ball/chain, ball/chain/ball/chain/
Ball), it wherein at least include a spherical structure；The single-stranded chemical composition of polymer, the degree of polymerization is adjustable；Nanoparticle chemistry composition, ruler
It is very little controllable.
The polymer single stranded portion degree of polymerization is 10-10000, preferably 30-3000, more preferably 50-1000；Nanoparticle
Having a size of 1-20nm, preferably 2-10nm.
Janus material structure/composition prepared by the present invention is controllable, and connection structure can be chain/ball order of connection any combination
Arrangement, as (polymer of connected ball is single-stranded very short, can be with for ball (polymer is single-stranded very short at this time, can ignore), ball/ball
Ignore), chain/ball, chain/ball/chain, ball/chain/ball, chain/ball/chain/ball/chain, the nanoparticles such as ball/chain/ball/chain/ball and single-stranded company
Connect any one in the model of sequence any combination arrangement；The single-stranded chemical composition of polymer, the degree of polymerization is adjustable；Nanoparticle chemistry
Composition, size are controllable.
The method that preparation provided by the invention has spherical model Janus material, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain polymer chain A；
2) monomer B and crosslinking agent are mixed to join in the reaction system of step 1), cation, which gathers, to be closed, in polymer chain
The end group of A connects upper nanoparticle, obtains the Janus material with single spherical model.
In the above method, the total volume of the monomer B and crosslinking agent that form nanoparticle are much larger than the list for forming polymer chain A
The volume of body A, the polymer chain of formation is shorter for the ball shape structure that next step is formed, and does not influence to be subsequently formed
Ball shape structure is also a ball shape structure on the whole.
Specifically, the ratio of the total volume of the volume of the monomer A and monomer B and crosslinking agent can be 1:10-50.
Preparation provided by the invention has ball/spherical model Janus material method, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain polymer chain A；
2) monomer B and crosslinking agent are mixed to join in the reaction system of step 1), cationic polymerization, in polymer chain A
End group connect upper nanoparticle, obtain the Janus material with single spherical model；
3) monomer C is added in the reaction system of step 2), cationic polymerization, in the Janus material with single spherical model
Polymer chain C is formed on material；
4) monomer D and crosslinker mixture, cationic polymerization, in polymer chain C are added into the reaction system of step 3)
End group connect upper nanoparticle, obtain that there is ball/spherical structure Janus material.
In the above method, the total volume of the monomer B and crosslinking agent that form nanoparticle are much larger than the list for forming polymer chain A
The polymer chain A of the volume of body A, formation is shorter for the ball shape structure that next step is formed, and does not influence to be subsequently formed
Ball shape structure；And the total volume for the monomer D and crosslinking agent for forming nanoparticle is much larger than the monomer C's for forming polymer chain C
The polymer chain C of volume, formation is shorter for the ball shape structure that next step is formed, and does not influence the ball-type being subsequently formed
Structure, therefore obtained with ball/spherical structure Janus material.
Specifically, the volume of monomer A, the total volume of monomer B and crosslinking agent, the volume of monomer C, monomer D and crosslinking agent
The ratio of total volume can be 1:10-50:1:10-50.
Preparation provided by the invention has chain/spherical model Janus material method, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain first segment polymer chain A；
2) it after mixing monomer B and crosslinking agent, is added in the reaction system of step 1), cationic polymerization, in polymer
The end group of chain A connects upper nanoparticle, obtains having chain/spherical model Janus material.
In the above method, the monomer B of nanoparticle and the total volume of crosslinking agent and the monomer A for forming polymer chain A are formed
Volume it is suitable, the polymer chain A of formation be not for the ball shape structure that next step is formed it is very short, generally form one
Kind chain/ball shape structure, rather than ball shape structure.
Specifically, the ratio of the total volume of the volume of monomer A and monomer B and crosslinking agent can be 1:0.1-5, concretely 1:1.
Preparation provided by the invention has chain/ball/chain model Janus material method, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain first segment polymer chain A；
2) it after mixing monomer B and crosslinking agent, is added in the reaction system of step 1), cationic polymerization, in polymer
The end group of chain A connects upper nanoparticle, obtains having chain/spherical model Janus material；
3) monomer C is added to the reaction system of step 2), cationic polymerization, it is friendship that obtain both ends, which be the single-stranded centre of polymer,
Connection nanoparticle has chain/ball/chain model Janus material.
In the above method, the monomer B of nanoparticle and the total volume of crosslinking agent and the monomer A for forming polymer chain A are formed
Volume it is suitable, the polymer chain A of formation be not for the ball shape structure that next step is formed it is very short, generally form one
Kind chain/ball shape structure；And formed nanoparticle monomer B and crosslinking agent total volume it is suitable with the volume of monomer C, formation it is poly-
Closing object chain C is not very short for the ball shape structure that previous step is formed, thus generally forms a kind of chain/ball/chain knot
Structure
Specifically, the volume of monomer A, the volume of the total volume of monomer B and crosslinking agent, monomer C ratio be 1:0.1-5:
0.1-5, concretely 1:1:1.
Preparation provided by the invention has ball/chain/spherical model Janus material method, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain polymer chain A；
2) it after mixing monomer B and crosslinking agent, is added in reaction system described in step 1), cationic polymerization is polymerizeing
The end group of object chain A connects upper nanoparticle；
3) monomer C is added in reaction system described in step 2), cationic polymerization, is connected in the end group of nanoparticle
Polymer chain C is to get to ball/chain model Janus material；
4) after mixing monomer D and crosslinking agent, reaction system described in step 3), cationic polymerization, in polymer is added
The end group of chain C connects upper nanoparticle, and it is that polymer is single-stranded i.e. with ball/chain/ball that obtain both ends, which be among cross-linking nanoparticles,
The Janus material of model.
In the above method, the total volume of the monomer B and crosslinking agent that form nanoparticle are much larger than the list for forming polymer chain A
The polymer chain A of the volume of body A, formation is shorter for the ball shape structure that next step is formed, and does not influence to be subsequently formed
Ball shape structure；Form the volume and the total volume phase of the monomer B and crosslinking agent that form nanoparticle of the monomer C of polymer chain C
When, the polymer chain C of formation be not for the ball shape structure that previous step is formed it is very short, generally formed ball/chain
Structure；And formed nanoparticle monomer D and crosslinking agent total volume with formed the volume of monomer C of polymer chain C it is suitable, gather
Close object chain C relative to next step formed ball shape structure for be not it is very short, generally formed ball/chain/ball shape structure.
Specifically, the volume of monomer A, the total volume of monomer B and crosslinking agent, monomer C, monomer D and crosslinking agent total volume
Than that can be 1:10-50:10-50:10-50.
In the above method, monomer A, B, C and D are the monomer of cationically polymerizable, including vinyl benzene class, vinyl ethers
The conjugate class monomer and vinyl coupling agent of class, vinyl, can be selected from styrene, p- methyl styrene, α-methylstyrene, p-
Methoxy styrene, p- chlorostyrene, 4- t-butyl styrene, 4- 1-chloro-4-methyl-benzene, 3- aldehyde radical styrene, divinyl
Benzene；Vinyl ethers, methyl vinyl ether, isobutyl vinyl ether, tert-Butyl vinyl ether, octadecyl vinyl ether, 12
Alkyl vinyl ether；Isoprene, butadiene, N- vinyl carbazole, vinyl pyrrolidone；Styrene ethyl trimethoxy silicon
Alkane, methyl styrene silane, vinyl methyl dimethoxysilane, vinyltrimethoxysilane, vinyl triethoxyl silicon
Alkane, octane oxygroup three (methacryloxy) zirconate, octane oxygroup three (acryloxy) zirconate, diisopropoxy second
One kind or any of ethyl acetoacetic acid oleic acid ester group Aluminate, two oleic acid acyloxy of isopropoxy (dioctyl phosphoric acid acyloxy) titanate esters
Combination.
The initiator of the cationic polymerization is selected from the Bronsted acid such as concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid, fluorine sulphur
Acid, trichloroacetic acid, trifluoroacetic acid, trifluoromethane sulfonic acid；Lewis acid such as boron trifluoride, alchlor, titanium tetrachloride, four
Stannic chloride, zinc chloride, antimony chloride；Iodine, oxonium ion and more stable cationic salts such as perchlorate, trityl group salt
With one of cycloheptatriene salt or any combination thereof.Wherein the dosage of the initiator is to be added the volume basis of monomer A amount
Than being calculated as 0.05-5%, preferably 0.1-3%, more preferably 0.3-1%.
The cationic polymerization carries out in organic solvent, and the organic solvent can be selected from benzene, toluene, low polarity halogen
For one of alkane such as chloromethanes, methylene chloride, dichloroethanes, chloroform, carbon tetrachloride, monochloro-benzene, dichloro-benzenes or its
Meaning combination.
The reaction system is with volume percentage, total monomer (all monomers in entire all steps of method) solid content
For 0.1-40%, preferably 1-30%.
In above method either step, reaction temperature is -100 DEG C -60 DEG C, and preferably -20 DEG C -40 DEG C, polymerization time is equal
For 5-60min, preferably 15-30min.
In the above method, crosslinking agent can be selected from one of divinylbenzene, butadiene, isoprene or its any group
It closes, content is added so that the volume percentage of monomer (monomer for the formation nanoparticle being added together with crosslinking agent) amount is added
For 1-40%, preferably 5%-20%.
Above-mentioned preparation has in chain/spherical model Janus material method, the volume of monomer A and monomer B and crosslinking agent it is total
The ratio of volume can be 1:0.1-5, concretely 1:1.
Above-mentioned preparation has in chain/ball/chain model Janus material method, the volume of monomer A, monomer B and crosslinking agent
The ratio of the volume of total volume, monomer C is 1:0.1-5:0.1-5, concretely 1:1:1.
Above-mentioned preparation has in ball/chain/spherical model Janus material method, the volume of monomer A, monomer B and crosslinking agent
Total volume, monomer C, monomer D and crosslinking agent total volume ratio be 1:10-50:10-50:10-50.
The present invention can be realized quickly, mass prepare the Nomenclature Composition and Structure of Complexes accuracy controlling with multiple latent functionality
Janus material, this material combines the single-stranded excellent properties with nanoparticle of polymer, in catalysis, water-oil separating, water body purification
Have great importance in the fields such as cell recognition.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo that the polystyrene spheres being prepared in example 2 are reacted in the embodiment of the present invention one.
Fig. 2 is surveyed by the dynamic light scattering for reacting the polystyrene spheres being prepared in example 2 in the embodiment of the present invention one
Particle diameter distribution.
Fig. 3 is surveyed by the dynamic light scattering for reacting the hammer chain structure being prepared in example 1 in the embodiment of the present invention four
Particle diameter distribution.
Fig. 4 is the nuclear magnetic spectrogram that the hammer chain structure being prepared in example 1 is reacted in the embodiment of the present invention four.
Fig. 5 is the transmission electron microscope photo that the hammer chain structure being prepared in example 1 is reacted in the embodiment of the present invention four.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
The preparation of one spherical model Janus material of embodiment
React example 1
Boron trifluoride ether solution (25 μ l) is added in methylene chloride (5ml), styrene monomer is added after mixing
After being stirred to react 15min under room temperature, the volume ratio that has been pre-mixed is added into the reaction system as the 3- of 9:1 in (0.05ml)
Aldehyde radical styrene, divinylbenzene monomers (0.5ml), after room temperature the reaction was continued 15min, reaction solution dehydrated alcohol is terminated,
Precipitating, washing, sample freeze-drying.Solid content 11%.There is about 2nm nanoparticle in transmission electron microscope display；Dynamic light scattering characterization is deposited
At unimodal (about 5nm).
React example 2
Boron trifluoride ether solution (25 μ l) is added in methylene chloride (5ml), p- methyl styrene is added after mixing
Monomer (0.05ml), after being stirred to react 15min under room temperature, it is 9:1 that the volume ratio being pre-mixed is added into the reaction system
Styrene, divinylbenzene monomers (1.0ml), after room temperature the reaction was continued 15min, reaction solution dehydrated alcohol is terminated, is heavy
It forms sediment, washing, sample freeze-drying.Solid content 21%.There is about 2nm nanoparticle in transmission electron microscope (Fig. 1) display；Dynamic light scattering (figure
2) there are unimodal (about 5nm) for characterization；Infrared spectrum shows the characteristic peak for polystyrene occurred.
The preparation of two balls of embodiment/spherical model Janus material
React example 1
Boron trifluoride ether solution (25 μ l) is added in methylene chloride (5ml), styrene monomer is added after mixing
(0.05ml) after stirring at normal temperature reacts 15min, the 4- (chlorine that the volume ratio being pre-mixed is 9:1 is added into the reaction system
Methyl) styrene, divinylbenzene monomers (0.5ml), after room temperature the reaction was continued 15min, continuously add styrene monomer
(0.05ml), stirring at normal temperature react 15min, and the 4- (chloromethane that the volume ratio being pre-mixed is 9:1 is added into the reaction system
Base) styrene, divinylbenzene monomers (0.5ml), after room temperature the reaction was continued 15min, reaction solution dehydrated alcohol is terminated, is heavy
It forms sediment, washing, sample freeze-drying.Solid content 22%.There are about 4nm worm-like particles in transmission electron microscope display；Dynamic light scattering shows grain
Sub- diameter increases to 7nm by 4nm in ball to ball/ball polymerization process；Nuclear magnetic resonance spectroscopy and infrared spectrum have poly- benzyl chlorobenzene
The characteristic peak of ethylene.
React example 2
Boron trifluoride ether solution (25 μ l) is added in methylene chloride (5ml), styrene monomer is added after mixing
(0.05ml) after stirring at normal temperature reacts 15min, the 4- (chlorine that the volume ratio being pre-mixed is 9:1 is added into the reaction system
Methyl) styrene, divinylbenzene monomers (0.5ml), after room temperature the reaction was continued 15min, continuously add styrene monomer
(0.05ml), stirring at normal temperature react 15min, then are added to be dissolved in methylene chloride (5ml) into the reaction system and be pre-mixed
Volume ratio be 9:1 4- (chloromethyl) styrene, divinylbenzene monomers (0.5ml) will after room temperature the reaction was continued 15min
Reaction solution is terminated with dehydrated alcohol, precipitating, is washed, sample freeze-drying.Solid content 11%.It is compacted that transmission electron microscope shows that there are 4nm or so
Worm shape particle；Dynamic light scattering shows that particle diameter increases to 7nm by 4nm in ball to ball/ball polymerization process.
The preparation of three chains of embodiment/spherical model Janus material
React example 1
Trifluoro etherificate boron second solution (25 μ l) is added in methylene chloride (5ml), 3- aldehyde radical styrene is added after mixing
After normal-temperature reaction 15min, the volume ratio that has been pre-mixed is added into the reaction system as the 4- (chlorine of 9:1 in monomer (0.5ml)
Methyl) styrene, divinylbenzene monomers (0.5ml), after room temperature the reaction was continued 15min, reaction solution dehydrated alcohol is terminated,
Precipitating, washing, sample freeze-drying.Solid content 20%.There is about 2nm nanoparticle in transmission electron microscope display；Nuclear magnetic resonance spectroscopy is shown
Occur the characteristic peak of poly- benzyl chlorostyrene in chain/ball spectrogram, the single-stranded spectrogram of individual polymer does not have but, it was confirmed that
Chain/spherical structure.
React example 2
Hydroiodic acid/zinc iodide (molar ratio 1:1) is added in methylene chloride (5ml), vinyl ethers list is added after mixing
After stirring at normal temperature reacts 15min, the 4- that the volume ratio being pre-mixed is 9:1 is added into the reaction system for body (0.75ml)
(chloromethyl) styrene, divinylbenzene monomers (0.5ml), after room temperature the reaction was continued 15min, by reaction solution with dehydrated alcohol end
Only, it precipitates, wash, sample freeze-drying.Solid content 25%.There is about 2nm nanoparticle in transmission electron microscope display；Nuclear magnetic resonance spectroscopy is aobvious
Show occur the characteristic peak of poly- benzyl chlorostyrene in chain/ball spectrogram, the single-stranded spectrogram of individual polymer does not have but, shows
Successfully nanoparticle has been gone up in polymer chain termination；Infrared spectrum shows in chain/ball spectrogram poly- benzyl chlorobenzene second occur
The characteristic peak of alkene, and individually the single-stranded spectrogram of polymer does not have, it was confirmed that chain/spherical structure.
The preparation of example IV chain/ball/chain model Janus material
React example 1
Boron trifluoride ether solution (50 μ l) is added in methylene chloride (5ml), p- methyl styrene is added after mixing
After stirring at normal temperature reacts 20min, the benzene that the volume ratio being pre-mixed is 9:1 is added into the reaction system for monomer (0.5ml)
After room temperature the reaction was continued 20min, 4- (chloromethyl) styrene monomer is added to it in ethylene, divinylbenzene monomers (0.5ml)
(0.5ml) after the same terms react 20min, reaction solution dehydrated alcohol is terminated, precipitating, washing, sample freeze-drying.Solid content
30%.There is about 2nm nanoparticle in transmission electron microscope (Fig. 5) display；Nuclear magnetic resonance spectroscopy (Fig. 4) display only has chain/ball/chain spectrum
The characteristic peak that just will appear poly- benzyl chlorostyrene in figure shows successfully to have synthesized second segment polymer single-stranded；Dynamic optical dissipates
It penetrates (Fig. 3) and shows that particle diameter increases to 10nm by 6nm during chain, chain/ball, chain/ball/chain polymerization and eventually becomes 15nm, demonstrate,prove
Real chain/ball/chain structure.
React example 2
Boron trifluoride ether solution (25 μ l) is added in methylene chloride (5ml), styrene monomer is added after mixing
(0.25ml) after stirring at normal temperature reacts 20min, the benzene second that the volume ratio being pre-mixed is 9:1 is added into the reaction system
After room temperature the reaction was continued 20min, 4- (chloromethane is added to it in alkene ethyl trimethoxy silane, divinylbenzene monomers (0.25ml)
Base) styrene monomer (0.25ml), reaction solution dehydrated alcohol terminates after reaction, is heavy by identical anti-conditioned response 20min
It forms sediment, washing, sample freeze-drying.Solid content 15%.There is about 2nm nanoparticle in transmission electron microscope display；Nuclear magnetic resonance spectroscopy is shown only
There is the characteristic peak that just will appear poly- benzyl chlorostyrene in chain/ball/chain spectrogram, shows successfully to have synthesized second segment polymer
It is single-stranded；Dynamic light scattering shows that particle diameter increases to 6nm by 4nm during chain, chain/ball, chain/ball/chain polymerization and eventually becomes
9nm, it was confirmed that chain/ball/chain structure.
The preparation of five balls of embodiment/chain/spherical model Janus material
React example 1
Boron trifluoride ether solution (20 μ l) is added in (5ml) in methylene chloride, and styrene monomer is added after mixing
(0.05ml) after stirring at normal temperature reacts 15min, the benzene second that the volume ratio being pre-mixed is 19:1 is added into the reaction system
4- (chloromethyl) benzene is added into reaction system after 25 DEG C of ultrasonic reaction 15min for alkene, divinylbenzene monomers (0.25ml)
Vinyl monomer (0.25ml) after the same terms react 15min, continues that the volume ratio being pre-mixed is added into the reaction system
P- methyl styrene, divinylbenzene monomers (0.25ml) for 19:1, the same terms react 20min, react after reaction
Liquid is terminated with dehydrated alcohol, precipitating, is washed, sample freeze-drying.Solid content 15%.There is about 2nm nanoparticle in transmission electron microscope display
It is right；Nuclear magnetic resonance spectroscopy shows in ball/chain spectrogram the characteristic peak of poly- benzyl chlorostyrene occur；Dynamic light scattering shows grain
Sub- diameter increases to 8nm by 5nm in ball, ball/chain, ball/chain/ball polymerization process and eventually becomes 11nm, it was demonstrated that ball/chain/chou
Structure.
React example 2
Boron trifluoride ether solution (20 μ l) is added in (5ml) in methylene chloride, and 4- (chloromethyl) benzene is added after mixing
Vinyl monomer (0.05ml), after stirring at normal temperature reacts 15min, the volume ratio being pre-mixed, which is added, into the reaction system is
Styrene ethyl trimethoxy silane, the divinylbenzene monomers (0.25ml) of 19:1, after 25 DEG C of ultrasonic reaction 15min, to
P- methyl styrene monomer (0.5ml) is added in reaction system, continues to add into the reaction system after the same terms reaction 15min
Enter 4- (chloromethyl) styrene monomer (0.25ml) that the volume ratio being pre-mixed is 19:1, after the same terms react 20min,
Reaction solution is terminated with dehydrated alcohol, precipitating, is washed, sample freeze-drying.Solid content 20%.Transmission electron microscope display has about 2nm nanometers
Particle pair；Nuclear magnetic resonance spectroscopy shows the characteristic peak that just will appear poly- benzyl chlorostyrene in only ball/chain/ball spectrogram；It is dynamic
State light scattering display particle diameter increases to 8nm by 5nm in ball, ball/chain, ball/chain/ball polymerization process and eventually becomes 11nm, demonstrate,proves
Real ball/chain/spherical structure.
According to above embodiments show quick cationic polymerization through the invention preparation simultaneously have both polymer it is single-stranded with
The Janus material of the method preparation of the Janus material of nanoparticle, structure accurately control, polymer single chain lengths and nanometer
Particle size is adjustable, and reaction is simple, and preparation reaction solid content height is, it can be achieved that mass industrial production.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
Depending on protection scope of the present invention.
Claims (12)
1. a kind of method prepared with spherical model Janus material, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain polymer chain A；
2) monomer B and crosslinking agent are mixed to join in the reaction system of step 1), cationic polymerization, at the end of polymer chain A
Base connects upper nanoparticle, obtains the Janus material with single spherical model.
2. according to the method described in claim 1, it is characterized by: forming the monomer B of nanoparticle and the total volume of crosslinking agent
Much larger than the volume for the monomer A for forming polymer chain A,
The ratio of the total volume of the volume and monomer B and crosslinking agent of the monomer A is 1:10-50.
3. a kind of prepare with ball/spherical model Janus material method, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain polymer chain A；
2) monomer B and crosslinking agent are mixed to join in the reaction system of step 1), cationic polymerization, at the end of polymer chain A
Base connects upper nanoparticle, obtains the Janus material with single spherical model；
3) monomer C is added in the reaction system of step 2), cationic polymerization, on the Janus material with single spherical model
Form polymer chain C；
4) monomer D and crosslinker mixture, cationic polymerization, at the end of polymer chain C are added into the reaction system of step 3)
Base connects upper nanoparticle, obtains having ball/spherical structure Janus material.
4. according to the method described in claim 3, it is characterized by: forming the monomer B of nanoparticle and the total volume of crosslinking agent
Much larger than the volume for the monomer A for forming polymer chain A, and the total volume for the monomer D and crosslinking agent for forming nanoparticle is much larger than
Form the volume of the monomer C of polymer chain C；
The volume of monomer A, the total volume of monomer B and crosslinking agent, the volume of monomer C, monomer D and crosslinking agent the ratio of total volume be
1:10-50:1:10-50.
5. a kind of prepare with chain/spherical model Janus material method, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain first segment polymer chain A；
2) it after mixing monomer B and crosslinking agent, is added in the reaction system of step 1), cationic polymerization, in the single-stranded A of polymer
End group connect upper nanoparticle, obtain that there is chain/spherical model Janus material.
6. according to the method described in claim 5, it is characterized by: forming the monomer B of nanoparticle and the total volume of crosslinking agent
It is suitable with the volume of monomer A of polymer chain A is formed；
The ratio of the total volume of the volume and monomer B and crosslinking agent of monomer A is 1:0.1-5.
7. a kind of prepare with chain/ball/chain model Janus material method, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain first segment polymer chain A；
2) it after mixing monomer B and crosslinking agent, is added in the reaction system of step 1), cationic polymerization, polymer chain A's
End group connects upper nanoparticle, obtains having chain/spherical model Janus material；
3) by monomer C be added step 2) reaction system, cationic polymerization, obtain both ends be the single-stranded centre of polymer be crosslinking receive
Rice corpuscles has chain/ball/chain model Janus material.
8. according to the method described in claim 7, it is characterized by: forming the monomer B of nanoparticle and the total volume of crosslinking agent
It is suitable with the volume of monomer A of polymer chain A is formed, and form the monomer B of nanoparticle and the total volume of crosslinking agent and monomer C
Volume it is suitable；
The volume of monomer A, the volume of the total volume of monomer B and crosslinking agent, monomer C ratio be 1:0.1-5:0.1-5.
9. a kind of prepare with ball/chain/spherical model Janus material method, comprising the following steps:
1) under initiator effect, so that monomer A is carried out cationic polymerization, obtain polymer chain A；
2) it after mixing monomer B and crosslinking agent, is added in reaction system described in step 1), cationic polymerization, in polymer chain A
End group connect upper nanoparticle；
3) monomer C is added in reaction system described in step 2), cationic polymerization, connects polymerization in the end group of nanoparticle
Object chain C is to get to ball/chain model Janus material；
4) after mixing monomer D and crosslinking agent, reaction system described in step 3), cationic polymerization, polymer chain C's is added
End group connects upper nanoparticle, and it is that polymer is single-stranded i.e. with ball/chain/spherical model that obtain both ends, which be among cross-linking nanoparticles,
Janus material.
10. according to the method described in claim 9, it is characterized by: forming the monomer B of nanoparticle and the total volume of crosslinking agent
Much larger than the volume for the monomer A for forming polymer chain A；It forms the volume of the monomer C of polymer chain C and forms the list of nanoparticle
The total volume of body B and crosslinking agent is suitable；And it forms the monomer D of nanoparticle and the total volume of crosslinking agent and forms polymer chain C
Monomer C volume it is suitable；
The volume of monomer A, the total volume of monomer B and crosslinking agent, monomer C, monomer D and crosslinking agent total volume ratio be 1:10-50:
10-50:10-50.
11. according to claim 1, method described in any one of 3,5,7 or 9, it is characterised in that: monomer A, B, C and D are can
The monomer of cationic polymerization, including vinyl benzene class, vinyl ethers, vinyl conjugate class monomer and vinyl coupling agent,
Selected from styrene, p- methyl styrene, α-methylstyrene, p- methoxy styrene, p- chlorostyrene, 4- tert-butyl benzene second
Alkene, 4- 1-chloro-4-methyl-benzene, 3- aldehyde radical styrene, divinylbenzene；Vinyl ethers, methyl vinyl ether, isobutyl vinyl ether-glycidyl
Ether, tert-Butyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl；Isoprene, butadiene, N- vinyl
Carbazole, vinyl pyrrolidone；Styrene ethyl trimethoxy silane, methyl styrene silane, vinyl methyl dimethoxy
Silane, vinyltrimethoxysilane, vinyltriethoxysilane, octane oxygroup three (methacryloxy) zirconate,
The one of octane oxygroup three (acryloxy) zirconate, two oleic acid acyloxy of isopropoxy (dioctyl phosphoric acid acyloxy) titanate esters
Kind or any combination；
The initiator of the cationic polymerization is in Bronsted acid, lewis acid, iodine, oxonium ion and cationic salts
One kind or any combination thereof；
The additional amount of the initiator is calculated as 0.05-5% with the percent by volume that monomer A amount is added；
Crosslinking agent is selected from one of divinylbenzene, butadiene, isoprene or any combination thereof, and additional amount is with same with it
When the percent by volume of the amount of monomer that is added be calculated as 1-40%；
The cationic polymerization carries out in organic solvent, and the organic solvent is selected from benzene, toluene, low polarity alkyl halide；
For the reaction system with volume percentage, total monomer solid content is 0.1-40%；
In either step, reaction temperature is -100 DEG C -60 DEG C, and polymerization time is 5-60min.
12. according to the method for claim 11, it is characterised in that: the low polarity alkyl halide are as follows: chloromethanes, dichloromethane
One of alkane, dichloroethanes, chloroform, carbon tetrachloride, monochloro-benzene, dichloro-benzenes or any combination thereof.
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