CN104892810B - A kind of method that photopolymerization prepares porous polymer particles after first assembling - Google Patents
A kind of method that photopolymerization prepares porous polymer particles after first assembling Download PDFInfo
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Abstract
The invention discloses photopolymerization after a kind of first assembling to prepare poromeric method, can prepare the porous polymer of different-shape.By the way that the organic ligand containing photopolymerization and metallic ion coordination are assembled into inorganic organic framework materials, photopolymerizable monomer polymerize in frame material and is crosslinked organic frame, after removing metal ion, obtains porous organic polymer.This method technique is simple, strong operability, can obtain different-shape and the porous polymer particles of size.
Description
Technical field
The present invention relates to the preparation process of porous polymer particles, more particularly to a kind of side using photopolymerization after first assembling
The method that method prepares porous polymer particles.
Background technology
Porous polymer particles have special dimensional effect and interfacial effect because of its loose structure, gas storage, separation,
Medicine, biomedicine, organizational project, water process, catalyst carrier, special pigment and coating etc. is carried to be widely used.It is more
Pore polymer particle has two big feature of porosity and high-crosslinking-degree.On porous polymer particles synthesis, processing, characterization with
And application study also causes extensive concern in chemical material field, and achieve significant progress.Ac.cn
With university such as national nanometer centers, the Chinese Academy of Sciences, Zhongshan University, the Central China University of Science and Technology, Jilin University, Tsinghua University, Shanghai traffic
University, Nankai University etc. have carried out the research of related fields, and achieve a series of important researchs for having international influence
Achievement.In general, porous polymer particles be using Polymer Synthesizing means prepare polymer beads, using two kinds or two kinds with
The immiscible property of upper liquid, is made, such as suspension polymerisation, dispersin polymerization, seeding polymerization using heterogeneous polymerization method.Last century
The fifties end Duesk etc. is reported first obtains porous polymer particles by suspension polymerisation, it is considered to be prepares porous polymeric
The founder of thing.The particle diameter that suspension polymerisation can generate particle can be from 50 μm to 1mm, and Size Distribution is wider, generally will be through undue
Level processing could use；Dispersin polymerization is to prepare the good method of monodisperse particle, but its be generally used to prepare it is non-crosslinked and non-
Porous polymer particle, therefore the general non-porous or only a small amount of micropore of obtained particle, are not easy to preparation and are surrounded by functional material
Particle；Seed swelling method is the good method for preparing porous polymer particles of current most study, it can prepare size
Homogeneous micro-size particles, but the preparation process being swollen repeatedly is time-consuming and laborious, and step is comparatively laborious.Therefore, a kind of operation of development
Method simplicity, mild condition, can obtain the method for preparing three-dimensional porous polymer particle of sizes pattern with very heavy
The scientific meaning and theory value wanted.
In recent years, another novel porous structure material-metal-organic framework (Metal-Organic Framework,
MOF) material has obtained extensive research.MOF is a kind of inorganic-organic hybridization nano porous material, it be it is a kind of by metal from
Son/cluster and organic ligand are by being coordinated bridging self assembly the three-dimensional porous coordination polymer that is formed.Due to the uniqueness knot of MOF
Functional, porosity and specific surface area that structure is brought are big, duct Modulatory character is strong and the characteristic such as specific diversity, are storing up
The fields such as gas, separation, catalysis, biological medicine and optics receive great attention.With metal ion and organic ligand not
Disconnected design and exploitation, the MOF material categories of current controllable synthesis are more and more, the MOF materials and special knot of thousands of kinds
The MOF of structure is synthesized, by regulating and controlling synthesis condition, as the species and concentration of solvent species, metal ion and ligand, temperature and
Preparation method etc., people can prepare the MOF particles of different crystal size and pattern, and can prepare the continuous raw of high quality
Long homogeneous flawless MOF films.The size of MOF can have spherical, octahedra from tens nanometers to several microns, its pattern
Type, rectangle, fusiformis etc.；Moreover, there is the preparation method of more MOF easier to be controllable, can such as be closed by hydro-thermal method
Into different-shape and the MOF of size.
Research in relation to being prepared three-dimensional porous polymer using the three-dimensional porous structure of MOF is had not been reported.This technology is intended
Around a series of organic ligands containing photopolymerizable monomer are designed, the MOF containing photopolymerizable monomer is prepared, using different
The different sizes and pattern feature of MOF species and MOF prepare the three-dimensional porous polymer of different chemical compositions, pattern and size
Organize work, high molecular polymerization, especially photopolymerization and metal-organic framework materials are intersected and combined, preparation structure is stable, tool
There are different-shape and the porous polymer particles of size.The porous polymer particles can be answered due to having well-regulated loose structure
For fields such as gas storage, gas separation, catalyst carrier, nano-reactor, chemical sensor, biological medicines, while by
Carboxylic acid group is rich in it, can be applied to the neck such as organic amine wastewater processing, heavy metal containing wastewater treatment, ammonia gas absorption, molecule controlled release
Domain.
The content of the invention
The defects of for existing process manufacturing cost height, complex process, the invention discloses a kind of porous polymer particles
Preparation process, it does not have or at least partly overcomes disadvantages mentioned above, and changes experiment condition, can obtain having different sizes
With the porous polymer particles particle of pattern.
Different from existing preparation method, the method the present invention relates to photopolymerization after a kind of first assembling prepares porous polymer
Particle.Position is assembled by the organic ligand containing photopolymerizable monomer and metal ion group MOF particles are made, then in illumination bar
Under part, photoinitiator resolves into free radical after absorbing photon, triggers monomer polymerization, by all organic ligands be cross-linked into one it is whole
Body, porous polymer particles are obtained after metal ion is removed by complexing agent.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of method that photopolymerization prepares porous polymer and particle after first assembling, includes the following steps：
1. organic ligand of the design synthesis containing photopolymerizable monomer；
Obtained 2. dissolving in a solvent and being uniformly mixed the organic ligand containing photopolymerizable monomer, metal salt, auxiliary agent
Reaction solution system；
3. the solution system configured is injected in reaction bulb, obtained by solvent-thermal method assembling coordination containing photopolymerization
The organic and inorganic frame material particle (Metal-Organic Framework, MOF) of monomer；
4. under the conditions of lucifuge, MOF particles, photoinitiator containing photopolymerizable monomer are distributed in solvent, in room
The lower illumination of temperature triggers monomer polymerization；
5. after the MOF particles after photopolymerization are soaked removal metal ion with complexing agent, porous polymer particles are obtained.
In step 1 and 2, organic bone of the organic ligand for containing photopolymerizable monomer as porous polymer particles
Frame.
It is as follows that design synthesizes the step of organic ligand containing photopolymerizable monomer：
(1) building-up process of the first synthetic method is：Using as the monomer M of organic ligand skeleton1It is dissolved in solvent, so
After add acid binding agent, be mixed into solution；Again using as the monomer M for introducing photopolymerizable group2It is dissolved in solvent, in ice
Bath, ice salt bath or under room temperature, with 1 second/drop~10 seconds/rate of addition of drop is instilled in above-mentioned solution, is added dropwise to complete
Afterwards, under room temperature or 30~80 DEG C of heating conditions, the reaction was continued 2h~96h, after reaction, adds 1mol/L dilute hydrochloric acid and separates out
Precipitation, precipitation are washed with water three times, and vacuum drying, weighs spare；
The building-up process of (2) second of synthetic method is：Using as the monomer M of organic ligand skeleton1, as introduce can light
The monomer M of polymer-based group3, acid binding agent be dissolved in solvent, under heated reflux condition, react 2h~96h, after reaction, add
1mol/L dilute hydrochloric acid separates out precipitation, and precipitation is washed with water three times, and vacuum drying, weighs spare；
(3) building-up process of the third synthetic method is：Under room temperature or 30~60 DEG C of heating conditions, organic match somebody with somebody will be used as
The monomer M of body skeleton1With the monomer M as introducing photopolymerizable group4Be mixed into suspension, by concentration be 98% it is dense
Sulfuric acid is added in above-mentioned suspension with the rate of addition of~5 seconds/drop of 1 second/drop, and concentrated sulfuric acid dosage is M1The 10%-15% of quality,
10min~1h, filtering are reacted, precipitation is washed with water three times, and vacuum drying, weighs spare.
Further, the monomer M described in a. as organic ligand skeleton1General formula be：
R2=OH or NH2
Wherein R1Group is following group, wherein " * " is represented and R2Tie point：
0≤m≤5
B. it is described as the monomer M for introducing photopolymerizable group2The amount of material be M11.1~3 times, M2Structural formula
For：
C. it is described as the monomer M for introducing photopolymerizable group3The amount of material be M11.1~3 times, M3Structural formula
For：
D. it is described as the monomer M for introducing photopolymerizable group4The amount of material be M11.1~3 times, M4Structural formula
For：
E. the reaction expression for synthesizing the organic ligand containing photopolymerizable monomer is：
The reaction expression of the first synthetic method is：
Wherein R4=HCl；
Wherein R3Group is following group, wherein " * " is represented and R1Tie point：
The reaction expression of second of synthetic method is：
Wherein R6=HBr；
Wherein R5Group is following group, wherein " * " is represented and R1Tie point：
The reaction expression of the third synthetic method is：
Wherein R7Group is following group, wherein " * " is represented and R1Tie point：
F. acid binding agent includes triethylamine, sodium hydroxide, pyridine, potassium carbonate or sodium carbonate, and the amount of the material of acid binding agent is M1
2.2~5 times；
G. solvent includes water, tetrahydrofuran, water and carbon tetrachloride mixed system, dioxane or water and tetrahydrofuran mixing
System.
In step 2, tie point of the metal salt as porous polymer particles, including copper, cobalt, nickel, iron, zinc, zirconates；
Including copper nitrate, copper chloride, aluminium chloride, cobalt nitrate, cobalt chloride, nickel nitrate, iron chloride, zinc nitrate, zirconium chloride.
The ratio of organic ligand and metal salt containing photopolymerizable monomer is (the amount ratio of material) 1:1~1:5.Work as metal
When salt dosage is too low, reaction is incomplete, reaction speed is slow；When amount of metal salts is excessive, metal salt is caused to waste, and be added to
This.
Auxiliary agent is acid or amine substance.Acid includes acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, benzoic acid.The amine
Matter includes ammonium hydroxide, triethylamine, monoethanolamine, diethanol amine, triethanolamine, triethylenediamine, triethylene tetramine, diethylentriamine.
The volume ratio of organic ligand and auxiliary agent containing photopolymerizable monomer is 1:0.5~1:2.
Carrier of the solvent as reaction, can dissolve the organic ligand containing photopolymerizable monomer, metal salt and help
Agent.One kind in the preferred water of the solvent, alcohols solvent, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO)
It is or several.Wherein alcohols solvent is methanol, ethanol, ethylene glycol, propyl alcohol, propane diols, glycerine, 1,2-PD, butanol, fourth two
One or more in alcohol.
Step 3 carries out in reaction bulb, easy to operate.Directly the above-mentioned reaction solution prepared is injected in reaction bulb, in room
Reaction is heated in temperature or baking oven.There is different reaction temperatures, reaction temperature model to the different MOF containing photopolymerizable monomer
Enclose be room temperature to 95 DEG C, reaction time range for 2 it is small when by one week.
Under light illumination, photoinitiator triggers the monomer photopolymerization in MOF particles to step 4, and organic ligand is cross-linked into one
It is overall.Photoinitiator is cracking type free radical photo-initiation, hydrogen-abstraction free radical photo-initiation or cationic photoinitiator.Institute
Stating cracking type free radical photo-initiation includes benzoin and its derivative, benzil derivatives, dialkyl group epoxide acetophenone, α-hydroxyl
Alkyl phenones, α-amine alkyl phenones, the hydrogen-abstraction free radical photo-initiation include benzophenone/tertiary amine, anthraquinone/tertiary amine, sulphur
Miscellaneous anthrone/tertiary amine, camphorquinone/tertiary amine, the cationic photoinitiator include aryl diazonium salts, diaryl group iodized salt, three virtues
Base sulfosalt, iron arene complexes.The dosage of photoinitiator is the 0.1%~5% of MOF mass particles.Light source include mercury lamp, xenon lamp,
UV-LED lamps, plate burning light or Iodine gallium light, light application time 60-600s, light intensity 10-100mW/cm2。
Step 5 is complexed the metal ion in MOF particles with complexing agent, so that metal ion be removed, is left organic backbone,
As porous polymer particles.The complexing agent is can be with the material of complexing of metal ion, including aqueous slkali and acid solution.Alkali soluble
Liquid includes ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution；Acid solution includes hydrochloric acid solution, sulfuric acid solution, ethylenediamine tetra-acetic acid
(EDTA)。
The present invention technological principle be：Based on the porous organic frameworks of MOF, organic containing photopolymerizable monomer is matched somebody with somebody
Body is introduced into MOF frames, since monomer is not involved in being coordinated in MOF is prepared, and the pore passage structure having due to MOF so that can
Photo polymerization monomer can polymerize in the duct of MOF, so that the organic ligand of MOF particles is cross-linked into an entirety.And metal
Assembled between ion and organic ligand by coordinate bond, coordinate bond is unstable, metal ion easily with other complexing agents be complexed and
It is removed, and remaining Porous-Organic frame, so as to fulfill the purpose of porous polymer particles is prepared.
Preparation process of the present invention is simple, and the porous polymer particles appearance and size for preparing gained is controllable.
Brief description of the drawings
Fig. 1 press the nuclear-magnetism figure of the organic ligand containing photopolymerizable monomer prepared by embodiment 1；
Fig. 2 porous polymer TEM as prepared by embodiment 2 scheme；
Fig. 3 press the nuclear-magnetism figure of the organic ligand containing photopolymerizable monomer prepared by embodiment 4；
Fig. 4 porous polymer SEM as prepared by embodiment 5 scheme；
Fig. 5 porous polymer SEM as prepared by embodiment 8 scheme；
Fig. 6 porous polymer SEM as prepared by embodiment 9 scheme；
Fig. 7 press the nuclear-magnetism figure of the organic ligand containing photopolymerizable monomer prepared by embodiment 10；
Fig. 8 porous polymer TEM as prepared by embodiment 11 scheme；
Fig. 9 porous polymer SEM as prepared by embodiment 12 scheme；
Figure 10 press the nuclear-magnetism figure of the organic ligand containing photopolymerizable monomer prepared by embodiment 13；
Figure 11 porous polymer SEM as prepared by embodiment 14 scheme；
Figure 12 porous polymer TEM as prepared by embodiment 15 scheme；
Figure 13 press the nuclear-magnetism figure of the organic ligand containing photopolymerizable monomer prepared by embodiment 16；
Figure 14 porous polymer SEM as prepared by embodiment 18 scheme.
Embodiment
Technical scheme is described further below by preferred embodiment, but should not be construed as to this
The limitation of invention protection domain.
Embodiment 1：
1.98g (0.01mol) 2,5-Dihydroxyterephthalic acid is dissolved in 120ml tetrahydrofurans, 0~5 DEG C of ice bath, to
6.1g (0.05mol) triethylamine is added in system, is mixed into solution；2.7g (0.03mol) acryloyl chloride is dissolved in 20ml tetra-
In hydrogen furans, instilled with the rate of addition of 8 seconds/drop in above-mentioned solution.After being added dropwise to complete, ice bath is removed, is reacted at room temperature
24h.After reaction, 1mol/L dilute hydrochloric acid is added to neutralize, it is 2,5- diacrylate terephthalic acid (TPA)s to separate out precipitation, is washed with water
Wash three times, vacuum drying, weighs, yield 75.8%.
Embodiment 2：
By 25mmol/L 2,5- diacrylate terephthalic acid (TPA)s, the DMF solution of the zirconium chloride of 50mmol/L, according to
1:3 volume ratio configuration solution, then glacial acetic acid is added into above-mentioned system, dosage is molten with 2,5- diacrylate terephthalic acid (TPA)s
The volume ratio of liquid is 3:4, sealing, when reaction 70 is small under 90 degree, obtain particle diameter has containing for octahedral structure for 100nm or so
There is the MOF of photopolymerizable monomer.After the MOF is cleaned with DMF solution, it is distributed in methanol, adds 1% (relative to MOF particles
Quality) photoinitiator 1173 (2- hydroxy-2-methyl -1- phenyl -1- acetone) in light intensity is 60mW/cm2Mercury lamp under illumination 2
Minute, the crosslinked MOF of internal organic ligand is made.Carried out clearly with the sodium hydroxide solution of 1mol/L and the hydrochloric acid solution of 1mol/L
Wash, you can obtaining particle diameter has the porous polymer of class shape of octahedron for 100nm or so.
Embodiment 3：
By 25mmol/L 2,5- diacrylate terephthalic acid (TPA)s, the DMF solution of the cobalt nitrate of 25mmol/L, according to 1:2
Volume ratio configuration solution, 60 degree reaction 8 it is small when, obtain particle diameter for 2 μm or so have class rectangular parallelepiped structure containing can light
The MOF of polymerized monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 2% (relative to the matter of MOF particles
Amount) photoinitiator 2959 (2- hydroxyls -4- (2- hydroxy ethoxies) -2- methyl phenyl ketones) in light intensity is 50mW/cm2Mercury lamp under light
According to 3 minutes, the crosslinked MOF of internal organic ligand is obtained.With the sodium hydroxide solution of 1mol/L and the hydrochloric acid solution of 1mol/L into
Row cleaning, you can obtain particle diameter as 2 μm or so the porous polymers with class rectangular parallelepiped structure pattern.
Embodiment 4：
1.96g (0.01mol) 2,6- diaminourea terephthalic acid (TPA)s are dissolved in 150ml dioxane, -20 DEG C of ice salt baths,
2g (0.02.5mol) pyridines are added into system into solution；1.6g (0.015mol) methacrylic chloride is dissolved in 20ml dioxies six
In ring, instilled with the rate of addition of 5 seconds/drop in above-mentioned solution.After being added dropwise to complete, ice salt bath is removed, reacts at room temperature 16h.
After reaction, 1mol/L dilute hydrochloric acid is added to neutralize, it is product to separate out precipitation, is washed with water three times, and vacuum drying, weighs, and is produced
Rate 70.6%.
Embodiment 5：
By 25mmol/L 2,6- dimethacrylamide terephthalic acid (TPA)s, the DMF solution of the copper nitrate of 25mmol/L, is pressed
According to 1:2 volume ratio configuration solution, when 60 degree of reactions 8 are small, obtain particle diameter has containing for octahedral structure can for 200nm or so
The MOF of photo polymerization monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 1% (relative to the matter of MOF particles
Amount) photoinitiator 369 (2- phenyl benzyl -2- dimethyl amines -1- (4- morpholine benzyls phenyl) butanone) in light intensity is 80mW/cm2Mercury
Illumination 3 minutes under lamp, obtain the crosslinked MOF of internal organic ligand.With the sodium hydroxide solution of 1mol/L and the hydrochloric acid of 1mol/L
Solution is cleaned, you can obtains the porous polymer with class octahedral structure pattern.
Embodiment 6：
By 25mmol/L 2,6- dimethacrylamide terephthalic acid (TPA)s, the DMF solution of the zirconium chloride of 50mmol/L,
According to 2:3 volume ratio configuration solution, then glacial acetic acid is added into above-mentioned system, dosage is and 2,5- diacrylate terephthaldehydes
The volume ratio of acid solution is 3:4, sealing, when reaction 48 is small under 80 degree, obtain particle diameter has octahedral structure for 300nm or so
The MOF containing photopolymerizable monomer.After the MOF is cleaned with DMF solution, it is distributed in methanol, adds 1% (relative to MOF
The quality of particle) photoinitiator 1173 (2- hydroxy-2-methyl -1- phenyl -1- acetone) in light intensity is 40mW/cm2LED light under
Illumination 5 minutes, is made the crosslinked MOF of internal organic ligand.With the sodium hydroxide solution of 1mol/L and the hydrochloric acid solution of 1mol/L
Cleaned, you can obtaining particle diameter has the porous polymer of class shape of octahedron for 300nm or so.
Embodiment 7：
0.99g (0.005mol) 2,5- dihydric para-phthalic acids and excess methyl acrylic anhydride 3.7g's (0.024mol)
Suspension is heated to 50 DEG C, adds 10 drop concentration as 98% concentrated sulfuric acid using the rate of addition of 5 seconds/drop, reacts 15min, filter,
Precipitation is washed with water three times, vacuum drying, weighs, yield 56.7%.
Embodiment 8：
By 25mmol/L 2,5- dimethylacrylate terephthalic acid (TPA)s, the DMF solution of the cobalt nitrate of 25mmol/L, is pressed
According to 1:2 volume ratio configuration solution, when 60 degree of reactions 8 are small, obtain particle diameter has containing for octahedral structure for 200nm or so
The MOF of photopolymerizable monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 2% (relative to MOF particles
Quality) photoinitiator 907 (2- methyl isophthalic acids-(4- methyl mercaptos phenyl) -2- morpholine -1- acetone) in light intensity is 60mW/cm2Mercury lamp
Lower illumination 3 minutes, obtains the crosslinked MOF of internal organic ligand.It is molten with the sodium hydroxide solution of 1mol/L and the hydrochloric acid of 1mol/L
Liquid is cleaned, you can obtaining particle diameter has the porous polymer of class octahedral structure pattern for 200nm or so.
Embodiment 9：
By 25mmol/L 2,5- dimethylacrylate terephthalic acid (TPA)s, the DMF solution of the iron chloride of 25mmol/L, is pressed
According to 1:2 volume ratio configuration solution, when 50 degree of reactions 18 are small, obtain particle diameter has containing for fusiformis structure can for 2 μm or so
The MOF of photo polymerization monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 1% (relative to the matter of MOF particles
Amount) photoinitiator 651 (a, a- dimethoxy-a- phenyl acetophenones) in light intensity is 70mW/cm2Mercury lamp under illumination 3 minutes, obtain
To the crosslinked MOF of internal organic ligand.Cleaned with the sodium hydroxide solution of 1mol/L and the hydrochloric acid solution of 1mol/L, you can
Particle diameter is obtained as 2 μm or so the porous polymers with class fusiformis structure and morphology.
Embodiment 10：
3.3g (0.01mol) 3,3'- dihydroxy ethyl -4,4'- biphenyl dicarboxylic acids are dissolved in the sodium hydroxide water of 100ml 2M
In solution, 0.02g tetrabutylammonium bromide is added into system, is mixed into solution, 2.7g (0.03mol) acryloyl chloride is dissolved in
In carbon tetrachloride, instilled with the rate of addition of 10 seconds/drop in above-mentioned solution.After being added dropwise to complete, ice salt bath is removed, room temperature is anti-
Answer 48h.After reaction, the neutralization of 1mol/L dilute hydrochloric acid is added, it is product to separate out precipitation, and dilute hydrochloric acid and water alternately wash three times,
Vacuum drying, weighs, yield 67%.
Embodiment 11：
By 25mmol/L 3,3'- ethyl diacrylate -4,4'- biphenyl dicarboxylic acids, the DMF of the zirconium chloride of 25mmol/L
Solution, according to 1:2 volume ratio configuration solution, then glacial acetic acid is added into above-mentioned system, dosage is and 2,5- diacrylates pair
The volume ratio of terephthalic acid solution is 2:3, sealing, when 85 degree of reactions 70 are small, obtain particle diameter has octahedra knot for 100nm or so
The MOF containing photopolymerizable monomer of structure.After the MOF is cleaned with DMF solution, it is distributed in ethanol, it is (opposite adds 1%
In the quality of MOF particles) photoinitiator TPO (2,4,6- trimethylbenzoy-diphenies phosphine oxide) in light intensity is 60mW/
cm2LED light under illumination 3 minutes, obtain the crosslinked MOF of internal organic ligand.With the sodium hydroxide solution and 1mol/ of 1mol/L
The hydrochloric acid solution of L is cleaned, you can obtaining particle diameter has the porous polymer of class octahedral structure pattern for 100nm or so.
Embodiment 12：
25mmol/L 3,3'- ethyl diacrylate -4,4'- biphenyl dicarboxylic acids, the DMF of the zinc nitrate of 50mmol/L is molten
Liquid, according to 1:1 volume ratio configuration solution, and add 5% (relative to the quality of 2,5- diacrylate terephthalic acid (TPA)s)
Triethylamine is into above-mentioned solution, when 60 degree of reactions 8 are small, obtain particle diameter for 10 μm or so have cube structure containing phtotpolymerizable
Close the MOF of monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 1% (relative to the quality of MOF particles)
Photoinitiator 1173 (2- hydroxy-2-methyl -1- phenyl -1- acetone) is 40mW/cm in light intensity2LED light under illumination 5 minutes,
Obtain the crosslinked MOF of internal organic ligand.Cleaned with the sodium hydroxide solution of 1mol/L and the hydrochloric acid solution of 1mol/L, i.e.,
Particle diameter be can obtain as 10 μm or so the porous polymers with class cube structure pattern.
Embodiment 13：
1.98g (0.01mol) 2,5-Dihydroxyterephthalic acid is dissolved in 120ml tetrahydrofurans, 0~5 DEG C of ice bath, to
6.1g (0.05mol) triethylamine is added in system, is mixed into solution；4.5g (0.03mol) trimethyl epoxy chloroacetic chloride is molten
In 20ml tetrahydrofurans, instilled with the rate of addition of 6 seconds/drop in above-mentioned solution.After being added dropwise to complete, ice bath, room are removed
Temperature reaction 50h.After reaction, 1mol/L dilute hydrochloric acid is added to neutralize, it is product to separate out precipitation, is washed with water three times, vacuum is done
It is dry, weigh, yield 68%.
Embodiment 14：
By 25mmol/L 2,5- bis- (trimethyl epoxy acetate groups) terephthalic acid (TPA), the DMF of the zinc nitrate of 50mmol/L
Solution, according to 1:3 volume ratio configuration solution, and add 5% (relative to the quality of 2,5- diacrylate terephthalic acid (TPA)s)
Triethylenediamine into above-mentioned solution, when room temperature reaction 2 is small, obtaining particle diameter for 10 μm or so there is rectangular parallelepiped structure to contain
There is the MOF of photopolymerizable monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 1% (relative to MOF particles
Quality) photoinitiator 184 (1- hydroxycyclohexyl phenyl ketones) in light intensity is 60mW/cm2Mercury lamp under illumination 3 minutes, obtain
To the crosslinked MOF of internal organic ligand.Cleaned with the sodium hydroxide solution of 1mol/L and the hydrochloric acid solution of 1mol/L, you can
Particle diameter is obtained as 10 μm or so the porous polymers with class rectangular parallelepiped structure pattern.
Embodiment 15：
By 25mmol/L 2,5- bis- (trimethyl epoxy acetate groups) terephthalic acid (TPA), the DMF of the copper nitrate of 75mmol/L
Solution, according to 1:2 volume ratio configuration solution, when 40 degree of reactions 8 are small, obtain particle diameter has octahedral structure for 100nm or so
The MOF containing photopolymerizable monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 1% (relative to MOF
The quality of particle) cation light initiator (triaryl sulfonium salts) in light intensity is 40mW/cm2Mercury lamp under illumination 3 minutes, obtain
The internal crosslinked MOF of organic ligand.Cleaned with the sodium hydroxide solution of 1mol/L and the hydrochloric acid solution of 1mol/L, you can
There is the porous polymer of class octahedral structure pattern to particle diameter for 100nm or so.
Embodiment 16：
By 1.98g (0.01mol) 2,5- dihydric para-phthalic acids, 0.69g (0.01mol) potassium carbonate, 3.6g
(0.03mol) propylene bromine is dissolved in 150ml tetrahydrofurans, is heated to reflux 96h, is cooled to room temperature, and adds 1mol/L dilute hydrochloric acid precipitateds
As product, is washed with water three times, and vacuum drying, weighs, yield 80%.
Embodiment 17：
By 25mmol/L 2,5- bis- (vinyl ether group) terephthalic acid (TPA), the DMF solution of the zinc nitrate of 50mmol/L, is pressed
According to 1:1 volume ratio configuration solution, and add the triethylene of 8% (relative to the quality of 2,5- diacrylate terephthalic acid (TPA)s)
Tetramine is into above-mentioned solution, when 60 degree of reactions 8 are small, obtain particle diameter and contains photopolymerization with rectangular parallelepiped structure for 10 μm or so
The MOF of monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 1% (relative to the quality of MOF particles) light
Initiator 2959 (2- hydroxyls -4- (2- hydroxy ethoxies) -2- methyl phenyl ketones) is 50mW/cm in light intensity2Mercury lamp under illumination 3 divide
Clock, obtains the crosslinked MOF of internal organic ligand.Carried out clearly with the sodium hydroxide solution of 1mol/L and the hydrochloric acid solution of 1mol/L
Wash, you can obtain particle diameter as 10 μm or so the porous polymers with class rectangular parallelepiped structure pattern.
Embodiment 18：
By 25mmol/L 2,5- bis- (vinyl ether group) terephthalic acid (TPA), the DMF solution of the cobalt nitrate of 50mmol/L, is pressed
According to 1:4 volume ratio configuration solution, when 50 degree of reactions 16 are small, obtain particle diameter has containing for octahedral structure for 150nm or so
There is the MOF of photopolymerizable monomer.After the MOF is cleaned with DMF solution, it is distributed in ethanol, adds 1% (relative to MOF particles
Quality) 261 (η of cation light initiator6- isopropylbenzene cyclopentadienyl iron (II) hexafluorophosphate) in light intensity it is 80mW/cm2Solidification case
Middle illumination 3 minutes, obtains the crosslinked MOF of internal organic ligand.It is molten with the sodium hydroxide solution of 1mol/L and the hydrochloric acid of 1mol/L
Liquid is cleaned, you can obtaining particle diameter has the porous polymer of class octahedral structure pattern for 150nm or so.
Claims (1)
1. a kind of method that photopolymerization prepares the porous polymer particles of different morphologies after first assembling, includes the following steps：
(1) organic ligand of the design synthesis containing photopolymerizable monomer；
(2) organic ligand containing photopolymerizable monomer, metal salt, auxiliary agent are dissolved in a solvent and be uniformly mixed and reacted
Solution system；
(3) solution system configured is injected in reaction bulb, is obtained by solvent-thermal method assembling coordination containing photopolymerization list
The organic and inorganic frame material particle of body, hereinafter referred to as MOF；
(4) under the conditions of lucifuge, MOF particles, photoinitiator containing photopolymerizable monomer are distributed in solvent, at room temperature
Illumination triggers monomer polymerization；
(5) the MOF particles after photopolymerization are soaked with complexing agent after removing metal ion, obtains porous polymer particles；
Wherein, the step of design synthesizes the organic ligand containing photopolymerizable monomer is as follows：
The building-up process of the first synthetic method is：Using as the monomer M of organic ligand skeleton1It is dissolved in solvent, then adds and tie up
Sour agent, is mixed into solution；Again using as the monomer M for introducing photopolymerizable group2It is dissolved in solvent, in ice bath, ice salt bath
Or under room temperature, instilled with the rate of addition of~10 seconds/drop of 1 second/drop in above-mentioned solution, after being added dropwise to complete, in room temperature
Or under 30~80 DEG C of heating conditions, the reaction was continued 2h~96h, after reaction, adds 1mol/L dilute hydrochloric acid and separates out precipitation, precipitation
It is washed with water three times, vacuum drying, weighs spare.
The building-up process of second of synthetic method is：Using as the monomer M of organic ligand skeleton1, as introduce photopolymerizable group
Monomer M3, acid binding agent be dissolved in solvent, under heated reflux condition, react 2h~96h, after reaction, add 1mol/L it is dilute
Hydrochloric acid separates out precipitation, and precipitation is washed with water three times, and vacuum drying, weighs spare.
The building-up process of the third synthetic method is：Under room temperature or 30~60 DEG C of heating conditions, organic ligand skeleton will be used as
Monomer M1With the monomer M as introducing photopolymerizable group4Be mixed into suspension, by concentration be 98% the concentrated sulfuric acid with 1
The rate of addition of second/drop~5 second/drop is added in above-mentioned suspension, and concentrated sulfuric acid dosage is M1The 10%-15% of quality, reaction
10min~1h, filtering, precipitation are washed with water three times, and vacuum drying, weighs spare；
A. the monomer M as organic ligand skeleton1General formula be：
R2=OH or NH2
Wherein R1Group is following group, wherein " * " is represented and R2Tie point：
B. it is described as the monomer M for introducing photopolymerizable group2The amount of material be M11.1~3 times, M2Structural formula be：
C. it is described as the monomer M for introducing photopolymerizable group3The amount of material be M11.1~3 times, M3Structural formula be：
D. it is described as the monomer M for introducing photopolymerizable group4The amount of material be M11.1~3 times, M4Structural formula be：
E. the reaction expression for synthesizing the organic ligand containing photopolymerizable monomer is：
The reaction expression of the first synthetic method is：
Wherein R4=HCl；
Wherein R3Group is following group, wherein " * " is represented and R1Tie point：
The reaction expression of second of synthetic method is：
Wherein R6=HBr；
Wherein R5Group is following group, wherein " * " is represented and R1Tie point：
The reaction expression of the third synthetic method is：
Wherein
Wherein R7Group is following group, wherein " * " is represented and R1Tie point：
F. acid binding agent includes triethylamine, sodium hydroxide, pyridine, potassium carbonate or sodium carbonate, and the amount of the material of acid binding agent is M12.2
~5 times；
G. solvent includes water, tetrahydrofuran, water and carbon tetrachloride mixed system, dioxane or water and tetrahydrofuran mixture
System.
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