CN110003507A - The hollow organic porous nano ball skeleton of carboxylic acid functional and its synthesis and application - Google Patents
The hollow organic porous nano ball skeleton of carboxylic acid functional and its synthesis and application Download PDFInfo
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Abstract
The invention discloses a kind of hollow organic porous nano ball skeleton of carboxylic acid functional and the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional and its synthetic methods.In the present invention, the first hollow organic porous nano ball macromolecular presoma of synthesis of carboxylic acid functionalization, then the super cross-linking reaction of friedel-craft, the hollow organic porous nano ball framework material of synthesis of carboxylic acid functionalization are carried out to macromolecular presoma under the action of catalyst.Using the hollow organic porous nano ball skeleton of the carboxylic acid functional as carrier, Carboxylic acid ligand is anchor point in skeleton, noble silver is complexed in skeleton, the hollow organic porous nano ball skeleton adulteration silver catalyst of synthesis of carboxylic acid functionalization.The method of the present invention has the characteristics that synthesis is simple, structure regulating is various.The invention also discloses the applications in the reduction reaction of methylene blue and nitro-aromatic compound, mercaptan coupling reaction, the reaction of selective oxidation styrene respectively of the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional.
Description
Technical field
The invention belongs to polymer-supported noble metal silver catalyst technical fields, are related to the hollow organic micropore of carboxylic acid functional
Nanosphere skeleton and its carried silver catalyst and its synthesis and application.
Background technique
Porous polymer is because it is with good porosity, biggish specific surface area and easy processing type, by increasingly
More concerns.In addition, stronger covalent bridging key assigns the higher thermal stability of porous polymer.Therefore, porous polymer can
It stores and separates for gas, can be used as the carrier of drug controlled release, itself can also be used as catalyst or catalyst
Carrier, can be used as the carrier of biological micromolecule or cell, filtering and separating film, proton exchange membrane, energy storage
Electrode material.
Poromeric microstructure can usually determine its performance and application.That is, having special appearance special
The porous polymer of point can often show more superior performance.In the structure that these have been designed, micro- Porous hollow is organic
Nanosphere has been received more and more attention as a kind of novel 3 D stereo material, this also has benefited from it with porous shell
Layer, controllable hollow structure and biggish specific surface area, unique structure is but also micro- Porous hollow organic nano ball exists
Absorption separates, catalysis, the fields extensive application such as nano-reactor and drug loading release.Synthesize at present it is micro- it is porous in
The method for having machine nanosphere in vain mainly has hard template, three kinds of modes of soft template and self-template.During typical hard template, gather
It closes object and is coated on the template ball surface prepared first, these balls can be SiO2, Fe3O4Deng then these template balls are gone
It removes, to obtain hollow nanospheres.Such as silicon ball table of the Wu et al. by the method in situ for causing free radical polymerization after modification
Bread covers a strata styrene chain, then is crosslinked to obtain the super crosslinking shell of the polystyrene with rigid structure by the way that a step is super,
Sol-gel finally, which is got rid of, using HF obtains micro- Porous hollow organic nano ball.Similar, Son seminar utilizes
Sonogashira coupling reaction coats one layer of microporous polymer containing alkynyl in silicon ball surface, then gets rid of intermediate silicon ball mould
Plate obtains the hollow organic nano ball that shell contains alkynyl.However, hard template method often has surface modification, complicated templated synthesis
Step and subsequent the problems such as removing the toxic reagent used needed for removing template, these problems also cause hard template method repetitive rate it is low,
It is at high cost.Opposite, soft template rule eliminates the step of last template removes, and substantially reduces synthesis step, reduces most
Synthesis cost afterwards.Most of all, soft template method can relatively simply adjust the structure of the ectonexine shell of hollow nanospheres
And property.For example it is that can sacrifice template one-step synthesis nanometer that Wang et al., which is reported with the degradable cross linked polyacrylate of multiform looks,
The new method of grade conjugation microporous polymer micro-capsule glue.No matter for hard template or soft template, the two requires to spend additionally
Time and at synthesizing necessary sacrifice template originally, and these templates tend not to be transformed into final hollow structure.With
From the point of view of this, self-template rule is synthesis hollow structure economy the most simply method, because it does not need additional template.They
Synthesis mechanism mainly include Ostwald curing, Kirkendall effect, electrochemical displacement and surface protection etching etc..So
And self-template methods are generally only used for synthesizing the inorganic hollow structure of some metals or metal oxide-type.Recently, Baneriee
Et al. successfully synthesize a kind of hollow sphere that shell contains meso-hole structure using Ostwald maturing process and be conjugated organic frame
(COF).However the COF ball size that this method synthesizes is larger (0.5-4 μm), and size distributing inhomogeneity.So seeking a kind of letter
Micro- Porous hollow organic nano ball that single, economical and effective method is used to synthesize size uniformity is one quite significant and fill
The work of full challenge.
The methylene blue and nitryl aromatic race chemicals reduction reaction of silver catalysis are considered as sanitary sewage disposal all the time
One of effective ways.In actual production, selection is more economical, is easier to the catalyst obtained to handle sanitary sewage, to work
Industry production has very important significance.Further investigation with people to precious metal supported catalyst, researchers
Trial loads to metal-organic solution deposition on the carrier of high-specific surface area, to integrate homogeneous catalyst high activity and non-equal catalyst
Mutually segregative advantage.But general carrying method metal-organic solution deposition load capacity is few, distribution is not easy to control, also results in
The reduction of catalytic activity.Therefore, the heterogeneous catalysis controllable with high-specific surface area, organic ligand load capacity, distribution is developed
Agent will very important meaning.
Summary of the invention
In order to overcome the drawbacks described above of the prior art, the invention proposes a kind of hollow organic porous nanos of carboxylic acid functional
Ball skeleton and its synthetic method.Wherein, the micropore of the hollow organic porous nano ball skeleton of the carboxylic acid functional, mesoporous ratio,
The concentration of Carboxylic acid ligand and its distribution can be carried out Effective Regulation, while have big specific surface area, excellent chemical stabilization
Property.
The invention also provides prepared in carboxylic acid functional by the hollow organic porous nano ball skeleton of the carboxylic acid functional
The synthetic method for having machine porous nano ball skeleton adulteration silver catalyst in vain, by the hollow organic porous nano ball of the carboxylic acid functional
The hollow organic porous nano ball skeleton adulteration silver catalyst of the carboxylic acid functional is formed after skeleton adulteration silver, the catalyst is used
It is anti-in reduction reaction, mercaptan coupling reaction, selective oxidation styrene of catalysis methylene blue and nitro-aromatic compound etc.
It answers, shows excellent catalytic performance, compared with poromerics carried silver catalyst in the prior art, homogeneous silver catalyst,
The hollow organic porous nano ball skeleton adulteration silver catalyst of new catalyst carboxylic acid functional proposed by the present invention possesses higher
Rate of catalysis reaction, more cycle-index (10-16), preferable stability.
A kind of synthetic method of the hollow organic porous nano ball skeleton of carboxylic acid functional proposed by the present invention, first synthesis of carboxylic acid
The hollow organic porous nano ball macromolecular presoma (triblock copolymer PLA-b-PtBA-b-PS) of functionalization, then in catalyst
Under effect to macromolecular presoma carry out the super cross-linking reaction of friedel-craft, the hollow organic porous nano ball skeleton of synthesis of carboxylic acid functionalization,
The following steps are included:
Step (1): synthesis is as before the hollow organic porous nano ball skeleton macromolecular of carboxylic acid functional shown in following formula (I)
Drive body；
Step (2): aforementioned obtained presoma and crosslinking agent carbon tetrachloride, catalyst ferric trichloride are subjected to the super friendship of a step
Connection method, that is, super the cross-linking reaction of friedel-craft obtains the hollow organic porous nano ball skeleton of the carboxylic acid functional；
Wherein, m=150-300；N=100-200；1=5-20.
Preferably, m=250；N=150；L=11.
The synthetic method of the hollow organic porous nano ball skeleton of a kind of carboxylic acid functional proposed by the present invention, using three block
Copolymer polylactic acid-b- polyacrylic acid the tert-butyl ester-b- polystyrene (PLA-b-PtBA-b-PS) soft template prepares carboxylic acid functional
Hollow organic porous nano ball skeleton.
Wherein, the hollow organic porous nano ball skeleton macromolecular presoma (triblock copolymer of the carboxylic acid functional
PLA-b-PtBA-b-PS synthesis), comprising the following steps:
(a) synthesis of polylactic acid (PLA)
Under the high temperature conditions, under the effect of the catalyst, using benzyl alcohol as initiator, by D, L- lactide and benzyl alcohol into
Row ring-opening polymerization obtains polylactic acid (PLA) polymer.That is, the polylactic acid is to polymerize to obtain by racemic form lactide.
Shown in reaction process such as following formula (A):
Wherein, n=100-200；Preferably, n=150.
In step (a), the high temperature is 120-140 DEG C；It preferably, is 140 DEG C.
In step (a), the temperature of the ring-opening polymerization is 120 DEG C -130 DEG C；It preferably, is 130 DEG C.
In step (a), the time of the ring-opening polymerization is 0.5-3 hours；Preferably, it is 1 hour.
In step (a), the catalyst is selected from stannous octoate and/or triethyl aluminum；It preferably, is stannous octoate.
In step (a), the effect of the catalyst is catalysis D, and ring-opening reaction occurs for L- lactide.
In step (a), the D, the molar ratio of L- lactide, catalyst and benzyl alcohol is (60-100): 0.5: 1；It is preferred that
Ground is 100: 0.5: 1.
In step (a), the D, the effect of L- lactide is to obtain polylactic acid through ring-opening polymerisation as main reaction substrate.
In a specific embodiment, in step (a), the synthesis step of the polylactic acid (PLA) includes: by benzyl alcohol
(10 μ l), D, L- lactide (1.3g), stannous octoate (19mg) are added in reaction tube, 130 DEG C tube sealing reaction 3 hours.Reaction
After with 20ml methylene chloride dissolve, precipitate in methyl alcohol, collect sediment simultaneously be dissolved in methylene chloride, precipitate again
In methyl alcohol, it is repeated in three times.The white product finally obtained hollow drying 24 hours at room temperature, obtain polylactic acid
(PLA) polymer, the PLA degree of polymerization is 156 to nuclear-magnetism as the result is shown.
(b) synthesis of PLA-TC
In a solvent, three monothioester of dodecyl (TC) and acylating agent, PLA carry out acylation reaction, esterification, obtain institute
State the PLA, i.e. PLA-TC of end modified three monothioester of chain transfer agents dodecyl (TC).
Wherein, shown in three monothioester of dodecyl (TC) structure such as following formula (II):
Shown in the reaction process such as following formula (B) for synthesizing PLA-TC:
Wherein, n=100-200；Preferably, n=150.
In step (b), the solvent is selected from methylene chloride, chloroform, tetrahydrofuran, and one in Isosorbide-5-Nitrae-dioxane etc.
Kind is a variety of；It preferably, is methylene chloride；It is further preferred that for dry methylene chloride.
In step (b), it is preferable that three monothioester of dodecyl (TC) and acylating agent first carry out acylation reaction, then again with
PLA carries out esterification.
In step (b), the temperature of the acylation reaction is 0-40 DEG C；It preferably, is 25 DEG C.
In step (b), the time of the acylation reaction is 1-6 hours；Preferably, it is 2 hours.
In step (b), the temperature of the esterification is 0-40 DEG C；It preferably, is 25 DEG C.
In step (b), the time of the esterification is 24-48 hours；Preferably, it is 24 hours.
In step (b), three monothioester of dodecyl (TC), acylating agent, PLA molar ratio be (1-2): (5-10):
(50-100)；It preferably, is 1: 5: 100.
In step (b), the effect of three monothioester of dodecyl (TC) is the initiation group as next step.
In step (b), the effect of the acylating agent is to improve the reactivity of TC；The acylating agent is selected from oxalyl chloride, two
One of chlorine sulfoxide, phosgene etc. are a variety of；It preferably, is oxalyl chloride, wherein the structure of the oxalyl chloride such as following formula
(III) shown in:
(c) synthesis of di-block copolymer polylactic acid-b- polyacrylic acid tert-butyl ester PLA-b-PtBA
The PLA-TC and tert-butyl acrylate synthesized under the action of initiator, in the step (b) passes through reversible addition-
It is broken chain transfer polymerization reaction, PLA-TC is made to connect the polyacrylic acid tert-butyl ester, it is poly- to obtain the di-block copolymer polylactic acid-b-
Tert-butyl acrylate PLA-b-PtBA.
In step (c), the temperature of the reversible addion-fragmentation chain transfer polymerization reaction is 50-70 DEG C；It preferably, is 70
℃。
In step (c), the time of the reversible addion-fragmentation chain transfer polymerization reaction is 6-12 hours；It preferably, is 12
Hour.
In step (c), the reversible addion-fragmentation chain transfer polymerization reaction carries out under nitrogen atmosphere.
In step (c), the effect of the initiator is to cause reversible addion-fragmentation chain transfer polymerization reaction；The initiation
Agent is selected from AIBN and/or benzoyl peroxide (BPO)；It preferably, is AIBN.
In step (c), the PLA-TC, initiator, tert-butyl acrylate ratio are (1-2): (0.1-0.5): (10-30)；
It preferably, is 1: 0.1: 20.
(d) conjunction of the triblock copolymer polylactic acid-b- polyacrylic acid tert-butyl ester-b- polystyrene PLA-b-PtBA-b-PS
At
Under the action of initiator, the PLA-b-PtBA and styrene synthesized in the step (c) is disconnected by reversible addition-
Chain transfer polymerization reaction is split, so that PLA-b-PtBA is connected polystyrene, obtains the hollow organic porous nano of the carboxylic acid functional
The ball skeleton macromolecular presoma, that is, triblock copolymer polylactic acid-b- polyacrylic acid tert-butyl ester-b- polystyrene PLA-b-PtBA-
b-PS。
Shown in reaction process such as following formula (C):
Wherein, m=150-300；N=100-200；L=5-20.
Preferably, m=250；N=150；L=11.
In step (d), the temperature of the reversible addion-fragmentation chain transfer polymerization reaction is 50-70 DEG C；It preferably, is 70
℃。
In step (d), the time of the reversible addion-fragmentation chain transfer polymerization reaction is 6-12 hours；It preferably, is 12
Hour.
In step (d), the reversible addion-fragmentation chain transfer polymerization reaction carries out under nitrogen atmosphere.
In step (d), the PLA-b-PtBA, initiator, styrene molar ratio be (1-2): (0.1-0.5): (400-
2000)；It preferably, is 1: 0.1: 2000.
In step (d), the effect of the initiator is to cause reversible addion-fragmentation chain transfer polymerization reaction；The initiation
Agent is selected from AIBN and/or benzoyl peroxide (BPO)；It preferably, is AIBN.
In a specific embodiment, the synthetic method of the triblock copolymer (PLA-b-PtBA-b-PS) includes
Following steps:
(a) synthesis of PLA
By benzyl alcohol (10 μ l), D, L- lactide (1.3g), stannous octoate (19mg) is added in reaction tube, 130 DEG C of envelopes
Tube reaction 1 hour.It is dissolved with 20ml methylene chloride, is precipitated in methyl alcohol after reaction, collect sediment and be dissolved in two
In chloromethanes, precipitates in methyl alcohol, be repeated in three times again.Hollow drying 24 is small at room temperature for the white product finally obtained
When, polylactic acid (PLA) polymer is obtained, the PLA degree of polymerization is 156 to nuclear-magnetism as the result is shown.
(b) synthesis of PLA-TC
Three monothioester of dodecyl (TC, 400mg) is added in dry flask, 4ml is then added by syringe
Dry methylene chloride.After TC is completely dissolved, 0.9ml oxalyl chloride is added dropwise in above-mentioned solution by syringe, together
When connect bubbler.After reaction 2 hours, extra oxalyl chloride and solvent is removed in vacuum.The PLA that will be synthesized in step (a)
(2.5g) is dissolved in the dry methylene chloride of 15ml, is then added in above-mentioned reaction tube by syringe.After reaction 24 hours,
It precipitates in methyl alcohol, methylene chloride dissolution.Dissolution precipitating obtains the PLA that end has chain transfer agents TC in triplicate, i.e.,
PLA-TC, upper TC group is successfully modified in the end PLA to nuclear-magnetism as the result is shown.
(c) synthesis of PLA-b-PtBA
The PLA-TC (500mg) that will be synthesized in step (b), AIBN (0.7mg) and tert-butyl acrylate (0.3ml) are added to
In reaction tube, after nitrogen deoxygenation, the reaction tube after sealing is placed in 70 DEG C of oil bath pan and is stirred to react 12 hours.Reaction terminates
Afterwards, it opens bottle cap and is passed through air and terminates and react, and precipitate in methyl alcohol.Obtain block polymer PLA-b-PtBA.
(d) synthesis of PLA-b-PtBA-b-PS
The PLA-b-PtBA (500mg) that will be synthesized in step (c), AIBN (0.7mg) and styrene (9.7ml) are added to instead
Ying Guanzhong after nitrogen deoxygenation, the reaction tube after sealing is placed in 70 DEG C of oil bath pan and is stirred to react 5 hours.After reaction,
It opens bottle cap and is passed through air and terminates and react, and precipitate in methyl alcohol.Obtain block polymer PLA-b-PtBA-b-PS.
One of the method for the present invention sharpest edges are, point of every section of homopolymer can be effectively controlled by adjusting reaction condition
Son amount (length) such as at that same temperature can improve molecular weight by extending the reaction time；In the identical reaction time
It is interior, molecular weight can be improved by improving temperature；Under the equality of temperature same reaction time, it can be improved point by improving monomer concentration
Son amount.
The invention also provides the hollow organic porous nano ball skeleton macromolecular presoma (three blocks of the carboxylic acid functional
Copolymer p LA-b-PtBA-b-PS) in the application for preparing the hollow organic porous nano ball skeleton of carboxylic acid functional.
In the present invention, the hollow organic porous nano ball skeleton of carboxylic acid functional is by PLA-b-PtBA-b-PS triblock copolymer
Object is obtained through the super crosslinking of a step.
In the step (2), in organic solvent, the invention also provides the triblock copolymer (PLA-b-PtBA-
B-PS) under the action of catalyst ferric trichloride, by step friedel-craft (Friedel-Crafts) super cross-linking reaction, institute is obtained
State the hollow organic porous nano ball skeleton of carboxylic acid functional.In the process, polylactic acid PLA can be hydrolyzed fragment into oligomer or
Lactic acid monomer.
The super cross-linking reaction of friedel-craft in the step (2) specifically: by being crosslinked to polystyrene for aforementioned obtained presoma
Layer carries out the super super cross-linking reaction of cross-linking method, that is, friedel-craft of a step with crosslinking agent carbon tetrachloride, catalyst ferric trichloride.
Wherein, the organic solvent is carbon tetrachloride, and the carbon tetrachloride is also used as crosslinking agent simultaneously.
Wherein, the temperature of the super cross-linking reaction of the friedel-craft (Friedel-Crafts) is 75-90 DEG C；It preferably, is 90
℃。
Wherein, the time of the super cross-linking reaction of the friedel-craft (Friedel-Crafts) is 12-24 hours；It preferably, is 24
Hour.
Wherein, the concentration of the triblock copolymer (PLA-b-PtBA-b-PS) in a solvent is between 1~10mg/ml；
It preferably, is 10mg/ml.
Wherein, phenyl ring in the triblock copolymer (PLA-b-PtBA-b-PS), ferric trichloride molar ratio be 1: (2-
4)；It preferably, is 1: 4.
Wherein, the super cross-linking reaction of the friedel-craft (Friedel-Crafts) preferably carries out under capping.
Wherein, the effect of the ferric trichloride is the catalysis super cross-linking reaction of friedel-craft.
Wherein, the hollow organic porous nano ball skeleton of the carboxylic acid functional being prepared is by hollow nanospheres as structure list
Member, which is cross-linked with each other, accumulates composition；The spherical shell of the hollow nanospheres is by the polystyrene in triblock polymer through super crosslinking structure
At；The diameter of hollow nanospheres is 30-40nm, and shell thickness is 6-7nm；The hollow organic porous nano ball skeleton of carboxylic acid functional
Structure is uniform, and has porosity and high-specific surface area, and specific surface area is 490~806m2g-1, micropore area is 92~212m2g-1, total pore volume is 0.98~1.28m3g-1。
In a specific embodiment, the synthetic method of the hollow organic porous nano ball skeleton of the carboxylic acid functional,
Include: that the triblock copolymer is directly dissolved in carbon tetrachloride, catalyst anhydrous ferric trichloride, temperature control is then added
System is at 90 DEG C, in closed container for 24 hours by friedel-craft (Friedel-Crafts) super cross-linking reaction, after reaction, respectively
Purify obtained solid with mixed solution, the methanol of 95% second alcohol and water (4: 1), last normal-temperature vacuum drying obtains carboxylic for 24 hours
The hollow organic porous nano ball skeleton of acid functionalization.
The invention also provides the hollow organic porous nano ball skeleton of carboxylic acid functional prepared by the above method,
In, the hollow organic porous nano ball skeleton structure of carboxylic acid functional is controllable, and Carboxylic acid ligand, net are contained in micropore hole wall
Network skeleton is made of styrene crosslinking, and micropore is present in polystyrene backbone gap, and specific surface area is 490~806m2/ g, hole
0.98~1.28cm of volume3/g。
The invention also provides a kind of hollow organic porous nano ball skeleton of carboxylic acid functional, the carboxylic acid functional is hollow
Organic porous nano ball skeleton structure is controllable, and Carboxylic acid ligand is contained in micropore hole wall, and network skeleton is crosslinked group by styrene
At micropore is present in polystyrene backbone gap, and specific surface area is 490~806m2/ g, 0.98~1.28cm of pore volume3/g。
Wherein, the hollow organic porous nano ball skeleton of the carboxylic acid functional is prepared according to the method described above.
The invention also provides the synthetic method of the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional,
Using the hollow organic porous nano ball skeleton of the carboxylic acid functional as carrier, Carboxylic acid ligand is anchor point in skeleton, by your gold
Belong to silver to be complexed in skeleton, the hollow organic porous nano ball skeleton adulteration silver catalyst of synthesis of carboxylic acid functionalization.
In the synthetic method of the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional of the present invention, with
Precious metal salt silver nitrate is that silver-colored ligand complex is carried on the hollow organic micropore of the carboxylic acid functional in a solvent by source metal
Nanosphere skeleton hole inner wall obtains the hollow organic porous nano ball skeleton adulteration silver catalyst of the carboxylic acid functional comprising
Following steps:
(1) synthesis of the hollow organic porous nano ball skeleton macromolecular presoma of carboxylic acid functional
(a) synthesis of polylactic acid PLA
Under the high temperature conditions, under the effect of the catalyst, using benzyl alcohol as initiator, by D, L- lactide and benzyl alcohol into
Row ring-opening polymerization obtains polylactic acid PLA polymer；
(b) synthesis of PLA-TC
In a solvent, three monothioester TC of dodecyl is reacted with acylating agent, PLA, is obtained the end modified chain and is turned
Move the PLA, i.e. PLA-TC of three monothioester TC of reagent dodecyl；
(c) synthesis of di-block copolymer polylactic acid-b- polyacrylic acid tert-butyl ester PLA-b-PtBA
The PLA-TC and tert-butyl acrylate synthesized under the action of initiator, in step (b) passes through reversible addition-fracture
Chain transfer polymerization reaction, makes PLA-TC connect the polyacrylic acid tert-butyl ester, obtains the di-block copolymer polylactic acid-b- polypropylene
Tert-butyl acrylate PLA-b-PtBA；
(d) conjunction of the triblock copolymer polylactic acid-b- polyacrylic acid tert-butyl ester-b- polystyrene PLA-b-PtBA-b-PS
At
The PLA-b-PtBA and styrene synthesized under the action of initiator, in step (c) passes through reversible addition-fracture chain
Transfer polymerization reaction, makes PLA-b-PtBA connect polystyrene, obtains the triblock copolymer polylactic acid-b- polyacrylic acid uncle
Butyl ester-b- polystyrene PLA-b-PtBA-b-PS.
Finally, the hollow organic porous nano ball skeleton macromolecular presoma of carboxylic acid functional, process such as above formula (C) are obtained
It is shown.
(2) the hollow organic porous nano ball skeleton of the super cross-linking reaction synthesis of carboxylic acid functionalization of friedel-craft
The presoma crosslinking agent of the hollow organic porous nano ball skeleton macromolecular of the carboxylic acid functional that step (1) is obtained
Carbon tetrachloride and catalyst ferric trichloride carry out the super cross-linking reaction of friedel-craft to polystyrene cross-linked layer；
(3) synthesis of the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional
Using precious metal salt silver nitrate as source metal, silver-colored ligand complex is carried on micropore organic nano ball skeleton hole inner wall,
The hollow organic porous nano ball skeleton adulteration silver catalyst of the carboxylic acid functional is obtained, the reaction is as shown in formula (D):
In the step (1), for the hollow organic porous nano ball skeleton adulteration silver catalyst of synthesis of carboxylic acid functionalization
The method of presoma is reversible addition-cracking-chain tra nsfer (RAFT) polymerization and from main chain Graft Method (graft from).
Wherein, in step (a), the high temperature is 120-140 DEG C；It preferably, is 140 DEG C.
Wherein, in step (a), the temperature of the ring-opening polymerization is 120 DEG C -130 DEG C；It preferably, is 130 DEG C.
Wherein, in step (a), the time of the ring-opening polymerization is 0.5-3 hours；Preferably, it is 1 hour.
Wherein, in step (a), the catalyst is selected from stannous octoate and/or triethyl aluminum；It preferably, is stannous octoate.
The effect of the catalyst is catalysis D, and ring-opening reaction occurs for L- lactide.
Wherein, in step (a), the D, the molar ratio of L- lactide, catalyst and benzyl alcohol is (60-100): 0.5: 1；
It preferably, is 100: 0.5: 1.
Wherein, in step (a), the D, the effect of L- lactide is to obtain poly- cream through ring-opening polymerisation as main reaction substrate
Acid.
Wherein, in step (b), the solvent is selected from methylene chloride, chloroform, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane etc.
One of or it is a variety of；It preferably, is methylene chloride；It is further preferred that for dry methylene chloride.
Wherein, in step (b), it is preferable that three monothioester of dodecyl (TC) and acylating agent first carry out acylation reaction, then
Esterification is carried out with PLA again.
Wherein, in step (b), the temperature of the acylation reaction is 0-40 DEG C；It preferably, is 25 DEG C.
Wherein, in step (b), the time of the acylation reaction is 1-6 hours；Preferably, it is 2 hours.
Wherein, in step (b), the temperature of the esterification is 0-40 DEG C；It preferably, is 25 DEG C.
Wherein, in step (b), the time of the esterification is 24-48 hours；Preferably, it is 24 hours.
Wherein, in step (b), three monothioester of dodecyl (TC), acylating agent, PLA molar ratio be (1-2): (5-
10):(50-100)；It preferably, is 1: 5: 100.
Wherein, in step (b), the effect of three monothioester of dodecyl (TC) is the initiation group as next step.
Wherein, in step (b), the effect of the acylating agent is to improve the reactivity of TC；The acylating agent is selected from oxalyl
One of chlorine, thionyl chloride, phosgene etc. are a variety of；It preferably, is oxalyl chloride.
Wherein, in step (c), the temperature of the reversible addion-fragmentation chain transfer polymerization reaction is 50-70 DEG C；Preferably,
It is 70 DEG C.
Wherein, in step (c), the time of the reversible addion-fragmentation chain transfer polymerization reaction is 6-12 hours；It is preferred that
Ground is 12 hours.
Wherein, in step (c), the reversible addion-fragmentation chain transfer polymerization reaction carries out under nitrogen atmosphere.
Wherein, in step (c), the PLA-TC, initiator, tert-butyl acrylate molar ratio be (1-2): (0.1-
0.5):(10-30)；It preferably, is 1: 0.1: 20.
Wherein, in step (c), the effect of the initiator is to cause reversible addion-fragmentation chain transfer polymerization reaction；It is described
Initiator is selected from one of AIBN, benzoyl peroxide (BPO) etc. or a variety of；It preferably, is AIBN.
Wherein, in step (d), the temperature of the reversible addion-fragmentation chain transfer polymerization reaction is 50-70 DEG C；Preferably,
It is 70 DEG C.
Wherein, in step (d), the time of the reversible addion-fragmentation chain transfer polymerization reaction is 6-12 hours；It is preferred that
Ground is 12 hours.
Wherein, in step (d), the reversible addion-fragmentation chain transfer polymerization reaction carries out under nitrogen atmosphere.
Wherein, in step (d), the PLA-b-PtBA, initiator, styrene molar ratio be (1-2): (0.1-0.5):
(400-2000)；It preferably, is 1: 0.1: 2000.
Wherein, in step (d), the effect of the initiator is to cause reversible addion-fragmentation chain transfer polymerization reaction；It is described
Initiator is selected from AIBN and/or benzoyl peroxide (BPO)；It preferably, is AIBN.
In the step (2), the crosslinking agent for being crosslinked triblock copolymer PLA-b-PtBA-b-PS is carbon tetrachloride.
In the step (2), the catalyst for being crosslinked triblock copolymer PLA-b-PtBA-b-PS is ferric trichloride.
In the step (2), for being crosslinked the crosslinking agent of triblock copolymer PLA-b-PtBA-b-PS, catalyst and three
The molar ratio of phenyl ring is 4: 4: 1 in block copolymer (PLA-b-PtBA-b-PS).
In the step (2), the reaction dissolvent is carbon tetrachloride, and the carbon tetrachloride is also used as crosslinking agent simultaneously.
In the step (2), the temperature of the reaction is 75-90 DEG C；It preferably, is 90 DEG C.
In the step (2), the time of the reaction is 12-24 hours；Preferably, for for 24 hours.
In the step (3), the mass ratio of silver-colored source silver nitrate and the hollow organic porous nano ball skeleton of carboxylic acid functional is
0.1∶1。
In the step (3), the reaction dissolvent is preferably the mixed solvent of methanol and water.
In the step (3), dipping is preferably stirred at room temperature 12 hours in the reaction, is most gone back in situ through sodium borohydride afterwards
It is former.
In a specific embodiment, using the hollow organic porous nano ball skeleton of the carboxylic acid functional as carrier,
Carboxylic acid ligand is that noble silver is complexed in skeleton by anchor point in the in the mixed solvent of methanol and water in skeleton, synthesis of carboxylic acid function
The hollow organic porous nano ball skeleton adulteration silver catalyst of energyization, specific reaction is as shown in following formula (E):
Wherein, m=150-300；N=100-200；1=5-20.
Preferably, m=250；N=150；L=11.
It is negative that the invention also provides the hollow organic porous nano ball skeletons of carboxylic acid functional prepared by the above method
Carry silver catalyst, including the hollow organic porous nano ball skeleton of carboxylic acid functional and precious metal catalyst functional group, microscopic appearance
Above it belongs to a kind of organic micro- mesoporous material with hollow microporous organic nano ball reticular structure.Carboxylic acid functional is hollow organic
Porous nano ball skeleton structure is controllable, Carboxylic acid ligand is contained in micropore hole wall, network skeleton is made of styrene crosslinking, micro-
Hole is primarily present in polystyrene backbone gap, and structure composition is represented by PS.The precious metal catalyst functional group comes
Source is precious metal salt silver nitrate, is carried in the hollow hole wall of micropore organic nano ball skeleton with Carboxylic acid ligand complexing；It is described
The specific surface area of the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional is 430~491m2/ g, pore volume
0.77~1.28cm3/g；
The main collection of micropore size distribution of the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional
In in 1.3nm, mesoporous pore size distribution is concentrated mainly on 5.1nm by the degree of polymerization of regulation polylactic acid stratum nucleare.
The invention also provides a kind of hollow organic porous nano ball skeleton adulteration silver catalysts of carboxylic acid functional comprising
The hollow organic porous nano ball skeleton of carboxylic acid functional and precious metal catalyst functional group, wherein the precious metal catalyst function
Radical sources are precious metal salt silver nitrate, are carried on the hollow organic porous nano of the carboxylic acid functional with Carboxylic acid ligand complexing
In the hollow ball wall of ball skeleton.
Wherein, the pattern of the catalyst be hollow organic porous nano ball cross-linked network, specific surface area be 430~
491m2/ g, 0.77~1.28cm of pore volume3/g。
The hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional of the present invention is repeatable to be recycled repeatedly
And catalytic activity is basically unchanged.
The invention also provides the hollow organic porous nano ball skeleton of the carboxylic acid functional, and/or, in carboxylic acid functional
Have application of the machine porous nano ball skeleton adulteration silver catalyst in catalysis methylene blue reduction reaction in vain；Specifically propose carboxylic acid
Application of the hollow organic porous nano ball skeleton adulteration silver catalyst of functionalization in catalysis methylene blue reduction reaction, it is described to answer
With the step of include: to disperse aqueous solvent for the hollow organic porous nano ball skeleton catalyst of the carboxylic acid functional of negative Ag-bearing,
Catalysis substrate methylene blue and sodium borohydride is added；Under nitrogen protection, 3min is reacted at room temperature, and reaction carries out complete；Reaction
System is recycled solid catalyst by centrifugation；Repetitive cycling 16 times, catalytic activity is held essentially constant.
The invention also provides the hollow organic porous nano ball skeleton of the carboxylic acid functional, and/or, in carboxylic acid functional
Have application of the machine porous nano ball skeleton adulteration silver catalyst in catalysis nitro-aromatic compound reduction reaction in vain；Specifically mention
It is anti-in catalysis nitro-aromatic compound reduction the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional has been gone out
The step of application in answering, the application includes: to urge the hollow organic porous nano ball skeleton of the carboxylic acid functional of negative Ag-bearing
Agent is scattered in aqueous solvent, and catalysis substrate nitro-aromatic compound and sodium borohydride is added；Under nitrogen protection, at room temperature instead
20min is answered, reacts basic and carries out completely；Reaction system is recycled solid catalyst by centrifugation；Repetitive cycling 10
Secondary, catalytic activity is held essentially constant；Its result such as the following table 1.
The hollow organic porous nano ball skeleton adulteration silver catalyst catalysis different substituents nitrobenzene of 1 carboxylic acid functional of table with
The reduction reaction of sodium borohydride.
The invention also provides the hollow organic porous nano ball skeleton of the carboxylic acid functional, and/or, in carboxylic acid functional
Have application of the machine porous nano ball skeleton adulteration silver catalyst in catalysis mercaptan coupling reaction in vain；Specifically propose carboxylic acid function
Change application of the hollow organic porous nano ball skeleton adulteration silver catalyst in catalysis mercaptan coupling reaction, the step of the application
It include: to disperse acetonitrile solvent for the hollow organic porous nano ball skeleton catalyst of the carboxylic acid functional of negative Ag-bearing, addition is urged
Change substrate mercaptan and hydrogen peroxide urea；Under nitrogen protection, 6min is reacted at room temperature, and reaction conversion ratio is more managed with yield
Think；Reaction system is recycled solid catalyst by centrifugation；Repetitive cycling 10 times, catalytic activity is kept not substantially
Become；Its result such as the following table 2.
The hollow organic porous nano ball skeleton adulteration silver catalyst catalysis different substituents mercaptan of 2 carboxylic acid functional of table and mistake
Aoxidize the coupling reaction of urea hydrogen.
The invention also provides the hollow organic porous nano ball skeleton of the carboxylic acid functional, and/or, in carboxylic acid functional
Have application of the machine porous nano ball skeleton adulteration silver catalyst in the reaction of catalytic selectivity styrene oxide in vain；Specifically propose
The hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional answering in the reaction of catalytic selectivity styrene oxide
It include: by the hollow organic porous nano ball skeleton catalyst dispersion of the carboxylic acid functional of negative Ag-bearing with the step of, application
In acetonitrile solvent, catalysis substrate styrene and tert-butyl hydroperoxide is added；Under nitrogen protection, 12h is reacted at 80 DEG C, react
Conversion ratio is fine with selection rate；Reaction system is recycled solid catalyst by centrifugation；Grope differential responses condition,
Catalytic activity is fine；Its result such as the following table 3.
Benzene second under the conditions of the hollow organic porous nano ball skeleton adulteration silver catalyst catalysis differential responses of 3 carboxylic acid functional of table
The selective oxidation reaction of alkene and tert-butyl hydroperoxide.
The hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional proposed by the present invention and its synthetic method,
(triblock copolymer polylactic acid-b- is poly- for the hollow organic porous nano ball skeleton macromolecular presoma of synthesis of carboxylic acid functionalization first
Tert-butyl acrylate-b- polystyrene PLA-b-PtBA-b-PS), then using carbon tetrachloride as solvent and crosslinking agent, anhydrous trichlorine
Change iron as catalyst and the super cross-linking reaction of friedel-craft is carried out to macromolecular presoma, it is hollow organic that one-step synthesis goes out carboxylic acid functional
Porous nano ball framework material.In the present invention, as control measures, big point can be regulated and controled by changing the feed ratio of different monomers
The degree of polymerization of each block component in sub- presoma, so come regulate and control the hollow organic porous nano ball skeleton of carboxylic acid functional it is micro-,
The relative scale of mesopore volume, the content and its distribution of Carboxylic acid ligand.
The method of the present invention has many advantages, such as that synthesis is simple, structure regulating is various, has good prospects for commercial application.Herein
On the basis of, the hollow organic porous nano ball skeleton large specific surface area of carboxylic acid functional proposed by the invention has and answers well
Use prospect.Compared with existing supported catalyst, the hollow organic porous nano ball skeleton adulteration silver catalysis of carboxylic acid functional of the present invention
Agent is hollow microporous organic nano net network carried silver catalyst, has and separates simple and quick, high catalytic efficiency, is recycled multiple
The features such as use.The hollow organic porous nano ball skeleton of carboxylic acid functional proposed by the invention, synthetic method is simple, and structure can
Control, large specific surface area have a good application prospect, and have and separate simple and quick, high catalytic efficiency, recyclable to be used for multiple times
Good characteristics.
The hollow organic porous nano ball framework material of novel carboxylic acid functionalization proposed by the present invention and its preparation and it is negative
The research for carrying silver catalyst and preparation, can not only widen the research field of organic porous material, but also industry can be pushed to urge
Change field is further developed, to abundant porous material loading catalysis research, make its towards functionalization, stabilisation, diversification,
Industrialized direction, which is developed, to have great importance.
Detailed description of the invention
Fig. 1 is the nuclear magnetic spectrum of PLA polymer prepared by the embodiment of the present invention 1.
Fig. 2 is the nuclear magnetic spectrum of PLA-TC polymer prepared by the embodiment of the present invention 1.
Fig. 3 is the nuclear magnetic spectrum of triblock copolymer PLA-b-PtBA-b-PS prepared by the embodiment of the present invention 1.
Fig. 4 is the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional prepared by the embodiment of the present invention 3
TEM figure.
Fig. 5 is the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional prepared by the embodiment of the present invention 3
Nitrogen adsorption desorption curve figure and graph of pore diameter distribution.
Specific embodiment
In conjunction with following specific embodiments and attached drawing, the present invention is described in further detail, protection content of the invention
It is not limited to following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that change
Change and advantage is all included in the present invention, and using appended claims as protection scope.Implement process of the invention,
Condition, reagent, experimental method etc. are among the general principles and common general knowledge in the art in addition to what is specifically mentioned below,
There are no special restrictions to content by the present invention.
The synthesis of the hollow organic porous nano ball skeleton presoma of 1 carboxylic acid functional of embodiment
First by ring-opening polymerization method synthesizing polylactic acid, then in the end modified upper chain transfer agents of polylactic acid, finally
The polyacrylic acid tert-butyl ester and polystyrene are connected by reversible addion-fragmentation chain transfer polymerization, obtains triblock copolymer
PLA-b-PtBA-b-PS。
Shown in its synthesis process such as following formula (C):
Wherein, n=156, m=200, l=11.
Specifically includes the following steps:
(a-1) synthesis of PLA
By benzyl alcohol (10 μ l), D, L- lactide (1.3g), stannous octoate (19mg) is added in reaction tube, 130 DEG C of envelopes
Tube reaction 1 hour.It is dissolved with 20ml methylene chloride, is precipitated in methyl alcohol after reaction, collect sediment and be dissolved in two
In chloromethanes, precipitates in methyl alcohol, be repeated in three times again.Hollow drying 24 is small at room temperature for the white product finally obtained
When, polylactic acid (PLA) polymer is obtained, the PLA degree of polymerization is 156 to nuclear-magnetism as the result is shown.See Fig. 1.The peak a is polylactic acid end in Fig. 1
The characteristic peak for the secondary methylene being connected with hydroxyl is held, the peak b is then the characteristic peak of time methylene in polylactic acid chain.The peak at the peak b and the peak a
Area ratio is then the degree of polymerization of polylactic acid.
(b-1) synthesis of PLA-TC
Three monothioester of dodecyl (TC, 400mg) is added in dry flask, 4ml is then added by syringe
Dry methylene chloride.After TC is completely dissolved, 0.9ml oxalyl chloride is added dropwise in above-mentioned solution by syringe, together
When connect bubbler.After reaction 2 hours, extra oxalyl chloride and solvent is removed in vacuum.The PLA that will be synthesized in step (a)
(2.5g) is dissolved in the dry methylene chloride of 15ml, is then added in above-mentioned reaction tube by syringe.After reaction 24 hours,
It precipitates in methyl alcohol, methylene chloride dissolution.Dissolution precipitating obtains the PLA that end has chain transfer agents TC in triplicate, i.e.,
PLA-TC, upper TC group is successfully modified in the end PLA to nuclear-magnetism as the result is shown.See Fig. 2.The peak a is to close on three sulfide linkages on TC in Fig. 2
The characteristic peak of methylene, the peak b are the characteristic peak of time methylene in polylactic acid chain.It is not seen in the place that chemical shift is 3.2ppm
The characteristic peak for observing the secondary methylene that polylactic acid end is connected with hydroxyl illustrates that terminal hydroxyl modifies upper TC group completely.
(c-1) synthesis of PLA-b-PtBA-b-PS
The PLA-TC (500mg) that will be synthesized in step (b), AIBN (0.7mg), tert-butyl acrylate (0.3ml) and benzene second
Alkene (9.7ml) is added in reaction tube, after nitrogen deoxygenation, the reaction tube after sealing is placed in 70 DEG C of oil bath pan and is stirred to react
12 hours.After reaction, it opens bottle cap and is passed through air and terminates and react, and precipitate in methyl alcohol.Obtain block polymer PLA-
b-PtBA-b-PS.PtBA block chain polymerization degree is 11, PS block chain polymerization degree to nuclear-magnetism as the result is shown is 200.See Fig. 3.A in Fig. 3
Peak is the characteristic peak that the methylene of three sulfide linkages is closed on TC, and the peak b is the characteristic peak of time methylene in polylactic acid chain.The peak c, the peak d and e
Peak is the resultant peak of five protons on phenyl ring in polystyrene, and the peak f is the characteristic peak of the methylene in tert-butyl acrylate.Pass through
The ratio for calculating the group peak area and b peak area at the peak c, d, e, converts the degree of polymerization D of available polystyrene through following formula.
D=0.4 × Sb+c+d
D is the degree of polymerization of polystyrene；S is the group peak area at the peak b+c+d.
The synthesis of the hollow organic porous nano ball skeleton of 2 carboxylic acid functional of embodiment
The triblock copolymer PLA-b-PtBA-b-PS that the embodiment of the present invention 1 synthesizes is dissolved in carbon tetrachloride, is then added
Enter quantitative anhydrous ferric trichloride, in closed container 90 DEG C of standing reactions for 24 hours, after reaction, respectively with 95% ethyl alcohol with
Mixed solution, the methanol of water (4: 1) clean three times obtained solid, and last normal-temperature vacuum is dry for 24 hours, obtains the carboxylic acid
The hollow organic porous nano ball skeleton of functionalization.Specifically includes the following steps:
Triblock copolymer PLA-b-PtBA-b-PS (700mg) is dissolved in 7ml carbon tetrachloride, after being completely dissolved, is added
Enter 2.9g anhydrous ferric trichloride.Stirring after five minutes, screws closed with covers reactor, moves it into 90 DEG C of oil bath pans, stands anti-
It answers 24 hours.After reaction solution is cooled to room temperature, lid is opened, the mixed solution of 95% second alcohol and water (4: 1) of 100ml is added
It is stirred overnight, after filtering, gained filter residue obtains the hollow organic micropore of final product carboxylic acid functional after methanol cleans three times and receives
Rice ball skeleton.
TEM test result such as Fig. 4, it can be found that each structural unit is that hollow structure, silver nanoparticle is presented from Fig. 4
Particle distribution is inside hollow ball, and outer shell thickness is about 7nm, and hollow parts diameter is about 12nm.
Nitrogen adsorption desorption test result such as Fig. 5, Cong Tuzhong it can be found that adsorption isothermal curve in low pressure range
For (0-0.1) nitrogen adsorption curve almost at vertical ascent state, this shows hollow organic porous nano ball cross-linked network tool
There is a large amount of microcellular structure.In addition, nitrogen desorption curve has an apparent hysteresis loop in the pressure range of 0.5-1, this
It shows hollow organic porous nano ball cross-linked network while also there is meso-hole structure abundant.Graph of pore diameter distribution is also intuitive
It is 1.9nm and 5.8nm that ground, which embodies hollow organic porous nano ball cross-linked network major bore,.
The synthesis of the hollow organic porous nano ball skeleton adulteration silver catalyst of 3 carboxylic acid functional of embodiment
The hollow organic porous nano ball skeleton of carboxylic acid functional that the embodiment of the present invention 2 synthesizes is dissolved in the mixed of first alcohol and water
In bonding solvent, silver-colored source nitric acid silver salt solution is then added, dipping 12h is stirred at room temperature, after reaction, with sodium borohydride water
It is reduction that solution carries out metal originally, and last normal-temperature vacuum is dry for 24 hours, obtains the hollow organic porous nano ball of the carboxylic acid functional
Skeleton adulteration silver catalyst.
The hollow organic porous nano ball skeleton adulteration silver catalyst catalysis methylene blue reduction of 4 carboxylic acid functional of embodiment is anti-
It answers
Aqueous solvent is dispersed by the hollow organic porous nano ball skeleton catalyst of the carboxylic acid functional of negative Ag-bearing, addition is urged
Change substrate methylene blue and sodium borohydride；Under nitrogen protection, 3min is reacted at room temperature, and reaction carries out complete；Reaction system is logical
Centrifugation is crossed to recycle solid catalyst；Repetitive cycling 16 times, catalytic activity is held essentially constant.
The hollow organic porous nano ball skeleton adulteration silver catalyst of 5 carboxylic acid functional of embodiment is catalyzed nitryl aromatic race chemical combination
Object reduction reaction
Aqueous solvent is dispersed by the hollow organic porous nano ball skeleton catalyst of the carboxylic acid functional of negative Ag-bearing, addition is urged
Change substrate nitro aromatic compound and sodium borohydride；Under nitrogen protection, 20min is reacted at room temperature, and reaction has carried out substantially
Entirely；Reaction system is recycled solid catalyst by centrifugation；Repetitive cycling 10 times, catalytic activity is kept not substantially
Become.
The hollow organic porous nano ball skeleton adulteration silver catalyst of 6 carboxylic acid functional of embodiment is catalyzed mercaptan coupling reaction
Acetonitrile solvent is dispersed by the hollow organic porous nano ball skeleton catalyst of the carboxylic acid functional of negative Ag-bearing, is added
Catalysis substrate mercaptan and hydrogen peroxide urea；Under nitrogen protection, 6min is reacted at room temperature, and reaction conversion ratio and yield are more
It is ideal；Reaction system is recycled solid catalyst by centrifugation；Repetitive cycling 10 times, catalytic activity is kept not substantially
Become.
The hollow organic porous nano ball skeleton adulteration silver catalyst catalytic selectivity Oxybenzene second of 7 carboxylic acid functional of embodiment
Alkene reaction
Acetonitrile solvent is dispersed by the hollow organic porous nano ball skeleton catalyst of the carboxylic acid functional of negative Ag-bearing, is added
Catalysis substrate styrene and tert-butyl hydroperoxide；Under nitrogen protection, 12h, reaction conversion ratio and selection rate are reacted at 80 DEG C
Still；Reaction system is recycled solid catalyst by centrifugation；Grope differential responses condition, catalytic activity is still
It can.
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally
Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect
Protect range.
Claims (12)
1. a kind of synthetic method of the hollow organic porous nano ball skeleton of carboxylic acid functional, which comprises the following steps:
Step (1): synthesis is such as the hollow organic porous nano ball skeleton macromolecular forerunner of carboxylic acid functional shown in following formula (I)
Body；
Step (2): aforementioned obtained presoma and crosslinking agent carbon tetrachloride, catalyst ferric trichloride are subjected to the super cross-linking method of a step
That is the super cross-linking reaction of friedel-craft obtains the hollow organic porous nano ball skeleton of the carboxylic acid functional；
Wherein, m=150-300；N=100-200；L=5-20；
Wherein, the synthesis of the hollow organic porous nano ball skeleton macromolecular presoma of the carboxylic acid functional, comprising the following steps:
(a) synthesis of polylactic acid PLA；
Under the effect of the catalyst, using benzyl alcohol as initiator, by D, L- lactide and benzyl alcohol carry out ring-opening polymerization, obtain
To polylactic acid PLA；
(b) synthesis of PLA-TC；
In a solvent, the polylactic acid PLA that three monothioester TC of dodecyl and acylating agent, step (a) obtain carries out acylation reaction, ester
Change reaction, obtains the PLA, i.e. PLA-TC of end modified three monothioester TC of chain transfer agents dodecyl；
(c) synthesis of di-block copolymer polylactic acid-b- polyacrylic acid tert-butyl ester PLA-b-PtBA；
The PLA-TC and tert-butyl acrylate synthesized under the action of initiator, in the step (b) passes through reversible addition-fracture
Chain transfer polymerization reaction, makes PLA-TC connect the polyacrylic acid tert-butyl ester, obtains the di-block copolymer polylactic acid-b- polypropylene
Tert-butyl acrylate PLA-b-PtBA；
(d) synthesis of the triblock copolymer polylactic acid-b- polyacrylic acid tert-butyl ester-b- polystyrene PLA-b-PtBA-b-PS；
The PLA-b-PtBA and styrene synthesized under the action of initiator, in the step (c) passes through reversible addition-fracture chain
Transfer polymerization reaction, makes PLA-b-PtBA connect polystyrene, obtains the hollow organic porous nano ball bone of the carboxylic acid functional
The frame macromolecular presoma, that is, triblock copolymer polylactic acid-b- polyacrylic acid tert-butyl ester-b- polystyrene PLA-b-PtBA-b-
PS。
2. synthetic method as described in claim 1, which is characterized in that in the step (1),
In the step (a): the temperature of the ring-opening polymerization is 120 DEG C -130 DEG C；And/or the ring-opening polymerization
Time be 0.5-3 hours；And/or the catalyst is selected from stannous octoate and triethyl aluminum；And/or the D, L- third is handed over
The molar ratio of ester, catalyst and benzyl alcohol is (60-100): 0.5: 1；
In the step (b): the solvent is selected from one of methylene chloride, chloroform, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane
Or it is a variety of；And/or the temperature of the acylation reaction is 0-40 DEG C；And/or the time of the acylation reaction is 1-6 hours；With/
Or, the temperature of the esterification is 0-40 DEG C；And/or the time of the esterification is 24-48 hours；And/or it is described
Three monothioester of dodecyl (TC), acylating agent, PLA molar ratio be (1-2): (5-10): (50-100)；And/or the acylation
Agent is selected from oxalyl chloride；
In the step (c): the temperature of the reversible addion-fragmentation chain transfer polymerization reaction is 50-70 DEG C；And/or it is described can
Inverse addition-fracture chain transfer polymerization reaction time is 6-12 hours；And/or the reversible addion-fragmentation chain transfer polymerization is instead
It should carry out under nitrogen atmosphere；And/or the molar ratio of the PLA-TC, initiator, tert-butyl acrylate is (1-2): (0.1-
0.5):(10-30)；And/or the initiator is selected from AIBN；
In the step (d): the temperature of the reversible addion-fragmentation chain transfer polymerization reaction is 50-70 DEG C；And/or it is described can
Inverse addition-fracture chain transfer polymerization reaction time is 6-12 hours；And/or the reversible addion-fragmentation chain transfer polymerization is instead
It should carry out under nitrogen atmosphere；And/or the molar ratio of the PLA-b-PtBA, initiator, styrene is (1-2): (0.1-
0.5):(400-2000)；And/or the initiator is selected from AIBN.
3. synthetic method as described in claim 1, which is characterized in that in the step (2), the carbon tetrachloride had both been used as molten
Agent is also used as crosslinking agent simultaneously；And/or the temperature of the super cross-linking reaction of friedel-craft is 75-90 DEG C；And/or the friedel-craft is super
The time of cross-linking reaction is 12-24 hours.
4. a kind of hollow organic porous nano ball skeleton of carboxylic acid functional, which is characterized in that it presses claim 1 the method system
It is standby to obtain.
5. a kind of hollow organic porous nano ball skeleton of carboxylic acid functional, which is characterized in that the carboxylic acid functional is hollow organic
Porous nano ball skeleton structure is controllable, Carboxylic acid ligand is contained in micropore hole wall, network skeleton is made of styrene crosslinking, micro-
Hole is present in polystyrene backbone gap, and specific surface area is 490~806m2/ g, 0.98~1.28cm of pore volume3/g。
6. a kind of synthetic method of the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional, which is characterized in that
In the method, using precious metal salt silver nitrate as source metal, in a solvent, silver-colored ligand complex is carried on such as claim 4 or 5
The hole inner wall of the hollow organic porous nano ball skeleton of the carboxylic acid functional, obtains the hollow organic micropore of the carboxylic acid functional
Nanosphere skeleton adulteration silver catalyst.
7. synthetic method as claimed in claim 6, which is characterized in that in the method, the mixed solution with first alcohol and water is
Solvent is silver-colored source with silver nitrate, at room temperature stirring dipping 12 hours, most afterwards through sodium borohydride in-situ reducing.
8. synthetic method as claimed in claim 6, which is characterized in that in the method, the silver source silver nitrate and carboxylic acid function
The mass ratio of the hollow organic porous nano ball skeleton of energyization is 0.1: 1.
9. a kind of hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional, which is characterized in that it is wanted by right
6 the methods are asked to be prepared.
10. a kind of hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional, which is characterized in that the catalyst
Pattern be hollow organic porous nano ball cross-linked network, specific surface area be 430~491m2/ g, 0.77~1.28cm of pore volume3/
g；The catalyst includes the hollow organic porous nano ball skeleton of carboxylic acid functional as described in claim 4 or 5 and your gold
Belong to catalysis group；Wherein, precious metal catalyst functional group source is precious metal salt silver nitrate, with Carboxylic acid ligand network
Conjunction is carried in the hollow ball wall of the hollow organic porous nano ball skeleton of the carboxylic acid functional.
11. the hollow organic porous nano ball skeleton of carboxylic acid functional as described in claim 4 or 5 is in preparing carboxylic acid functional
Have the application in machine porous nano ball skeleton adulteration silver catalyst in vain.
12. the hollow organic porous nano ball skeleton adulteration silver catalyst of carboxylic acid functional as described in claim 9 or 10 is being urged
Change organic reaction in, catalysis methylene blue reduction reaction in, catalysis nitro-aromatic compound reduction reaction in, be catalyzed
Application in mercaptan coupling reaction, and/or in the reaction of catalytic selectivity styrene oxide.
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| CN110586182A (en) * | 2019-08-26 | 2019-12-20 | 华东师范大学 | Hollow porous polymer nanosphere composite material packaged by noble metal nanoparticles and synthesis and application thereof |
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