CN107501487B - The hollow organic porous nano ball cross-linked network of one kind and its synthetic method and application - Google Patents
The hollow organic porous nano ball cross-linked network of one kind and its synthetic method and application Download PDFInfo
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- CN107501487B CN107501487B CN201710540298.9A CN201710540298A CN107501487B CN 107501487 B CN107501487 B CN 107501487B CN 201710540298 A CN201710540298 A CN 201710540298A CN 107501487 B CN107501487 B CN 107501487B
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- 239000011807 nanoball Substances 0.000 title claims abstract description 61
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 229920001400 block copolymer Polymers 0.000 claims abstract description 45
- 239000004793 Polystyrene Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- 229920002223 polystyrene Polymers 0.000 claims abstract description 18
- 239000002077 nanosphere Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000009825 accumulation Methods 0.000 claims abstract description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000013467 fragmentation Methods 0.000 abstract description 13
- 238000006062 fragmentation reaction Methods 0.000 abstract description 13
- 230000002441 reversible effect Effects 0.000 abstract description 13
- 238000012711 chain transfer polymerization Methods 0.000 abstract description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000004626 polylactic acid Substances 0.000 description 58
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 229920000747 poly(lactic acid) Polymers 0.000 description 39
- 238000003786 synthesis reaction Methods 0.000 description 34
- 230000015572 biosynthetic process Effects 0.000 description 31
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 21
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical group ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 10
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 9
- 239000011805 ball Substances 0.000 description 9
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 7
- 235000019445 benzyl alcohol Nutrition 0.000 description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 7
- 230000005311 nuclear magnetism Effects 0.000 description 7
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- 238000005886 esterification reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000005917 acylation reaction Methods 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- 238000007789 sealing Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
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- 229910052801 chlorine Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- -1 Chlorine sulfoxide Chemical class 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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Abstract
The invention discloses a kind of di-block copolymer and its synthetic methods, synthesize di-block copolymer by ring-opening polymerisation and reversible addion-fragmentation chain transfer polymerization.The invention also discloses the methods for preparing hollow organic porous nano ball cross-linked network by the di-block copolymer, under the effect of the catalyst by di-block copolymer, prepare the cross-linked network by Fu Kechao cross-linking reaction.The cross-linked network being prepared is made of hollow nanospheres as the structural unit accumulation that is cross-linked with each other；The spherical shell of the hollow nanospheres is made of super crosslinked polystyrene；The diameter of the hollow nanospheres is 30~40nm, and shell thickness is 6~7nm；The specific surface area of hollow organic porous nano ball cross-linked network is 582~806m2g‑1, micropore area is 102~217m2g‑1, total pore volume is 0.77~1.28m3g‑1.Method of the invention has the characteristics that easy to operate, reaction condition is mild, participates in without noble metal, low cost, obtained hollow organic porous nano ball cross-linked network size uniformity, controllable, specific surface area height.
Description
Technical field
The invention belongs to Polymer Synthesizing fields and porous polymer material field, and in particular to a kind of hollow organic micropore
Nanosphere cross-linked network and its synthetic method and application.
Background technique
Porous polymer has been subjected to getting over since it is with good porosity, biggish specific surface area and easy processing type
Carry out higher concern.In addition, stronger covalent bridging key assigns the higher chemistry of porous polymer and thermal stability.Just because such as
This, porous polymer can be used for gas storage and separation, can be used as the carrier of drug controlled release, itself can also make
For catalyst, perhaps catalyst carrier can be used as the carrier of biological micromolecule or cell, filtering and separating film, matter
Proton exchange, the electrode material of energy storage.
However, poromeric microstructure often determines its performance and application.In other words, have special appearance special
The porous polymer of point often shows better performance.In the structure that these have been designed, micro- Porous hollow organic nano
Ball has been received more and more attention as a kind of novel 3 D stereo material, this also mainly has benefited from it with porous shell
Layer, controllable hollow structure and biggish specific surface area.Its 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, Fe3O4, MOF etc., then by these templates
Ball removal, to obtain hollow nanospheres.Such as silicon of the Wu et al. by the method in situ for causing free radical polymerization after modification
Ball surface coats 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
Layer, finally gets rid of sol-gel using HF and 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 will often face surface modification, complicated template
Synthesis step and subsequent the problems such as removing the toxic reagent used needed for removing template, these problems also lead to hard template method repetitive rate
It is low, at high cost.Opposite, soft template rule eliminates the step of last template removes, and substantially reduces synthesis step, reduces
Last synthesis cost.Most of all, soft template method can relatively simply adjust the knot of the ectonexine shell of hollow nanospheres
Structure and property.For example it is that can sacrifice template one-step synthesis to receive that Wang et al., which is reported with the degradable cross linked polyacrylate of multiform looks,
The new method of meter level conjugation microporous polymer micro-capsule glue.No matter for hard template or soft template, the two requires to spend additional
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.It
Synthesis mechanism mainly include Ostwald curing, Kirkendall effect, electrochemical displacement and surface protection etching etc..
However, self-template methods are generally only used for synthesizing the inorganic hollow structure of some metals or metal oxide-type.Recently,
Banerjee et al., which successfully synthesizes a kind of hollow sphere that shell contains meso-hole structure conjugation using Ostwald maturing process, to be had
Machine 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 simple, economical and effective method be used to synthesize size uniformity micro- Porous hollow organic nano ball be one quite intentionally
Justice and the work full of challenge.
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 nano ball cross-linked networks
Synthetic method, first pass through ring-opening polymerisation and reversible addion-fragmentation chain transfer polymerization synthesize to obtain di-block copolymer, by this
Copolymer is prepared in described by Fu Kechao cross-linking reaction and is had in vain under the action of catalyst aluminum trichloride (anhydrous) or ferric trichloride
Machine porous nano ball cross-linked network.Method of the invention is easy to operate, reaction condition is mild, participates in without noble metal, is at low cost,
Hollow organic porous nano ball cross-linked network size uniformity, controllable, the specific surface area height being prepared.
The invention proposes a kind of di-block copolymer polylactic acid-b- polystyrene (PLA-b-PS), structure such as following formulas
(I) shown in:
Wherein, n=60~150, m=60~250.
Preferably, n=150, m=250.
The invention also provides the synthetic methods of the di-block copolymer (PLA-b-PS), pass through ring-opening polymerisation (ROP)
Synthesizing polylactic acid polymerize then in the end modified chain transfer agents of polylactic acid finally by reversible addion-fragmentation chain transfer
(RAFT) method connects polystyrene, synthesizes the di-block copolymer (PLA-b-PS).
The method specifically includes the following steps:
(a) synthesis of polylactic acid (PLA)
Under melting condition, 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 (II):
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 3 hours.
In step (a), the catalyst is selected from stannous octoate and triethyl aluminum；It preferably, is stannous octoate.The catalysis
The effect of agent 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, the synthesis step of the polylactic acid (PLA) include: 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.It uses after reaction
The dissolution of 20ml methylene chloride, is precipitated in methyl alcohol, is collected sediment and is dissolved in methylene chloride, is deposited in methanol again
In, it is repeated in three times.The white product finally obtained hollow drying 24 hours at room temperature obtain polylactic acid (PLA) polymerization
Object, the PLA degree of polymerization is 150 to nuclear-magnetism as the result is shown, sees Fig. 3.
(b) synthesis of PLA-TC
In a solvent, three monothioester of dodecyl (TC) is reacted with acylating agent, PLA, obtains the end modified chain
The PLA of three monothioester of transfering reagent dodecyl (TC), i.e. PLA-TC.
Wherein, shown in three monothioester of dodecyl (TC) structure such as following formula (i):
Shown in reaction process such as following formula (III):
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 (5-10): (50-
100):(1-2)；It preferably, is 5:10:1.
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
Chlorine sulfoxide, phosgene, two (trichloromethyl) carbonic esters etc.；It preferably, is oxalyl chloride, wherein the structure of the oxalyl chloride is as follows
Shown in formula (ii):
(c) synthesis of di-block copolymer polylactic acid-b- polystyrene (PLA-b-PS)
The PLA-TC and styrene synthesized under the action of initiator, in step (b) passes through reversible addion-fragmentation chain transfer
Polymerization reaction makes PLA-TC connect polystyrene, obtains the di-block copolymer PLA-b-PS.Reaction process such as following formula (IV)
It is shown:
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 PLA-TC, initiator, styrene molar ratio be (1-2): (0.1-0.5): (400-
2000)；It preferably, is 1:0.1:2000.
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, benzoyl peroxide (BPO), azobisisoheptonitrile, cyclohexanone peroxide, tert-butyl hydroperoxide etc.；It is preferred that
Ground is AIBN.
In a specific embodiment, the synthetic method of the di-block copolymer (PLA-b-PS) includes following step
It is rapid:
(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 3 hours.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 150 to nuclear-magnetism as the result is shown.See Fig. 3.
(b) synthesis of PLA-TC
Three monothioester of dodecyl (TC, 384mg) 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. 4.
(c) synthesis of PLA-b-PS
The PLA-TC (500mg) that will be synthesized in step (b), AIBN (0.7mg) and styrene (9.7ml) are added to reaction tube
In, 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 beats
Corkage lid is passed through air and terminates reaction, and precipitates in methyl alcohol.Obtain block polymer PLA-b-PS.PS is embedding as the result is shown for nuclear-magnetism
Section chain polymerization degree is 250.See Fig. 5.
The invention also provides di-block copolymer prepared by the above method (PLA-b-PS), two block is total
Polymers (PLA-b-PS) is linked together to obtain by two sections of homopolymers, wherein one section is made of degradable polymer PLA, it is another
Duan Ze is made of the polystyrene that can carry out Friedel-Crafts reaction.The di-block copolymer is at micro-yellow powder
Shape.The maximum advantage of the method for the present invention is that the molecular weight that every section of homopolymer can be effectively controlled by adjusting reaction condition is (long
Degree), such as at that same temperature, molecular weight can be improved by extending the reaction time；Within the identical reaction time, it can pass through
Temperature is improved to improve molecular weight；Under the equality of temperature same reaction time, molecular weight can be improved by improving monomer concentration.
The invention also provides the di-block copolymers (PLA-b-PS) to prepare hollow organic porous nano ball crosslinking
Application in network.
The invention also provides a kind of synthetic method of hollow organic porous nano ball cross-linked network, hollow organic micropore is received
Rice ball cross-linked network is obtained by PLA-b-PS di-block copolymer through the super crosslinking of a step.The described method includes: in organic solvent,
Di-block copolymer (PLA-b-PS) passes through a step Fu Ke under the action of catalyst aluminum trichloride (anhydrous) or ferric trichloride
(Friedel-Crafts) super cross-linking reaction obtains hollow organic porous nano ball cross-linked network；The reaction process is such as
Shown in Fig. 2, in the process, polylactic acid PLA, which can be hydrolyzed, fragments into oligomer or lactic acid monomer.
Wherein, the organic solvent is carbon tetrachloride.
Wherein, the temperature of the super cross-linking reaction of the Fu Ke (Friedel-Crafts) is 75-90 DEG C；It preferably, is 90 DEG C.
Wherein, the time of the super cross-linking reaction of the Fu Ke (Friedel-Crafts) is 12-24 hours；It preferably, is 24
Hour.
Wherein, the concentration of the di-block copolymer (PLA-b-PS) in a solvent is between 1~10mg/ml；Preferably,
For 10mg/ml.
Wherein, in the di-block copolymer (PLA-b-PS) phenyl ring, aluminum trichloride (anhydrous) or ferric trichloride molar ratio
For 1:2-4；It preferably, is 1:4.
Wherein, the super cross-linking reaction of the Fu Ke (Friedel-Crafts) preferably carries out under capping.
Wherein, the effect of the aluminum trichloride (anhydrous) or ferric trichloride is catalysis Fu Kechao cross-linking reaction.
Wherein, the hollow organic porous nano ball cross-linked network being prepared is mutual as structural unit by hollow nanospheres
Crosslinking accumulation composition；The spherical shell of the hollow nanospheres is made of the polystyrene in bi-block copolymer through super crosslinking；It is hollow
The diameter of nanosphere is 30-40nm, and shell thickness is 6-7nm, it is preferable that diameter 30nm, shell thickness are 7nm；It is described hollow organic micro-
The structure of hole nanosphere cross-linked network is uniform, and has porosity and high-specific surface area, and specific surface area is 582~806m2g-1, micro-
Hole area is 102~217m2g-1, total pore volume is 0.77~1.28m3g-1, it is preferable that specific surface area 806m2g-1, micropore area
For 133m2g-1, total pore volume 1.28m3g-1；Hollow organic porous nano ball cross-linked network is to CO2With preferable absorption
Property, the adsorbance in 273K is 36cm3g-1, the adsorbance in 296K is 22cm3g-1。
In a specific embodiment, the synthetic method of hollow organic porous nano ball cross-linked network, comprising: will
The di-block copolymer is directly dissolved in carbon tetrachloride, and catalyst aluminum trichloride (anhydrous) or ferric trichloride, temperature is then added
Degree control is at 90 DEG C, in closed container for 24 hours by Fu Ke (Friedel-Crafts) super cross-linking reaction, after reaction,
Purify obtained solid with mixed solution, the methanol of 95% second alcohol and water (4:1) respectively, last normal-temperature vacuum is dry for 24 hours
To hollow organic porous nano ball cross-linked network.
The invention also provides hollow organic porous nano ball cross-linked networks prepared by the above method, wherein in
The diameter for having machine porous nano ball in vain is 30-40nm, and shell thickness is 6-7nm, it is preferable that diameter 30nm, shell thickness are 7nm；It is described
The structure of hollow organic porous nano ball cross-linked network is uniform, and have porosity and high-specific surface area, specific surface area be 582~
806m2g-1, micropore area is 102~217m2g-1, total pore volume is 0.77~1.28m3g-1；Preferably, specific surface area 806m2g-1, micropore area 133m2g-1, total pore volume 1.28m3g-1。
The invention also provides hollow organic porous nano ball cross-linked networks in CO2Application in absorption.In described
Machine porous nano ball cross-linked network is had in vain to CO2With preferable adsorptivity, the adsorbance in 273K is 36cm3g-1,
Adsorbance when 296K is 22cm3g-1。
In a specific embodiment, the synthetic method of hollow organic porous nano ball cross-linked network, specific as follows:
(1)PLA150-b-PS250The synthesis of di-block copolymer
First using racemic form lactide as monomer, by ring-opening polymerisation synthesizing polylactic acid, then repaired in polylactic acid end
Chain transfer agents on decorations connect polystyrene finally by reversible addion-fragmentation chain transfer polymerization, obtain two block copolymerizations
Object.Shown in reaction route such as following formula (V):
Wherein, the degree of polymerization of polylactic acid is about 150, and the degree of polymerization of polystyrene is about 250；That is n=150；M=250.
(2) synthesis of hollow organic porous nano ball cross-linked network
Above-mentioned di-block copolymer is directly dissolved in carbon tetrachloride, catalyst aluminum chloride, temperature control is then added
At 90 DEG C, standing reaction is crosslinked for 24 hours by the way that Fu Ke (Friedel-Crafts) is super in closed container, after reaction, point
Obtained solid is not cleaned three times with mixed solution, the methanol of 95% second alcohol and water (4:1), and last normal-temperature vacuum is dry for 24 hours
Obtain hollow organic porous nano ball cross-linked network.Hollow organic porous nano ball cross-linked network is by two block of PLA-b-PS
Copolymer is obtained through the super crosslinking of a step.
In step (1), the temperature of the ring-opening polymerization is 130 DEG C.
In step (1), the time of the ring-opening polymerization is 3 hours.
In step (1), the D, the molar ratio of L- lactide, stannous octoate and benzyl alcohol is 100:0.5:1
In step (1), catalyst used in the ring-opening reaction is stannous octoate.
In step (1), in the PLA-TC synthesis, three monothioester of dodecyl (TC) and oxalyl chloride first carry out being acylated instead
It answers, then carries out esterification with PLA again.
In step (1), in the PLA-TC synthesis, solvent is dry methylene chloride.
In step (1), in the PLA-TC synthesis, the temperature of acylation reaction is 25 DEG C.
In step (1), in the PLA-TC synthesis, the time of acylation reaction is 2 hours.
In step (1), in the PLA-TC synthesis, the temperature of esterification is 25 DEG C.
In step (1), in the PLA-TC synthesis, the time of esterification is 24 hours.
In step (1), in PLA-TC synthesis, three monothioester of dodecyl (TC), oxalyl chloride, PLA molar ratio be
5:10:1。
In step (1), the PLA150-b-PS250In synthesis, the temperature of reversible addion-fragmentation chain transfer polymerization reaction is
70℃。
In step (1), the PLA150-b-PS250In synthesis, the time of reversible addion-fragmentation chain transfer polymerization reaction is
12 hours.
In step (1), the PLA150-b-PS250In synthesis, reversible addion-fragmentation chain transfer polymerization reaction is in nitrogen atmosphere
Enclose lower progress.
In step (1), the PLA150-b-PS250In synthesis, PLA-TC, AIBN, styrene molar ratio be 1:0.1:
2000。
In step (2), the di-block copolymer is in the concentration in carbon tetrachloride between 1~10mg/ml.
In step (2), the molar ratio of phenyl ring and alchlor is 1:4 in di-block copolymer (PLA-b-PS).
In step (2), the super cross-linking reaction temperature of Fu Ke (Friedel-Crafts) is 90 DEG C.
In step (2), the super cross-linking reaction system of Fu Ke (Friedel-Crafts) is in closed environment.
In step (2), in hollow organic porous nano ball cross-linked network, the diameter of hollow organic nano ball 30~
40nm, shell thickness are 7nm.
In step (2), hollow organic porous nano ball cross-linked network, specific surface area 806m2g-1, micropore area
For 133m2g-1, total pore volume 1.28m3g-1。
In step (2), hollow organic porous nano ball cross-linked network is to CO2With preferable adsorptivity, in 273K
When adsorbance be 36cm3g-1, the adsorbance in 296K is 22cm3g-1。
The beneficial technical effect of the present invention lies in the method that the present invention synthesizes di-block copolymer (PLA-b-PS) has can
Control property, simplicity；Present invention firstly provides hollow organic porous nano ball prepared by di-block copolymer (PLA-b-PS) hand over
The method of networking network is easy to operate, reaction condition is mild, is not necessarily to precious metal catalyst, is at low cost, under conditions of no additional template,
Di-block copolymer PLA-b-PS can form hollow microporous organic nano ball cross-linked network through super one step of cross-linking reaction, and can pass through
Control knot of the degree of polymerization realization to hollow microporous organic nano ball cross-linked network of PLA and PS in di-block copolymer PLA-b-PS
The size Control of structure unit.The size of the structural unit is by the mutually coordinated control of PLA and PS；Specifically, with two blocks
Copolymer p LA150-b-PS250For the structural unit cavity for the hollow microporous organic nano ball cross-linked network that precursor preparation obtains
Diameter is 16nm, wall thickness 7nm；With di-block copolymer PLA60-b-PS60The hollow microporous obtained for precursor preparation is organic to be received
The structural unit cavity diameter of rice ball cross-linked network is 26nm, wall thickness 7nm；With di-block copolymer PLA150-b-PS130It is preceding
The structural unit cavity diameter for driving the hollow microporous organic nano ball cross-linked network that body is prepared is 23nm, wall thickness 6nm.This
Inventing the hollow organic porous nano ball cross-linked network being prepared is 3 D stereo organic porous material, and structure is uniform, controllable,
Specific surface area is high.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of hollow organic porous nano ball cross-linked network.
Fig. 2 is the process of hollow organic porous nano ball cross-linked network preparation method.
Fig. 3 is the nuclear magnetic spectrum of PLA polymer prepared by embodiment 1.
Fig. 4 is the nuclear magnetic spectrum of PLA-TC polymer prepared by embodiment 1.
Fig. 5 is the nuclear magnetic spectrum of PLA-b-PS di-block copolymer prepared by embodiment 1.
Fig. 6 is the SEM figure of hollow organic porous nano ball cross-linked network prepared by embodiment 2.
Fig. 7 is the TEM figure of hollow organic porous nano ball cross-linked network prepared by embodiment 2.
Fig. 8 is nitrogen adsorption desorption curve figure and the hole of hollow organic porous nano ball cross-linked network prepared by embodiment 2
Diameter distribution map.
Specific embodiment
In conjunction with following specific embodiments and attached drawing, the present invention is described in further detail, 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 1 di-block copolymer of embodiment (PLA-b-PS)
First by ring-opening polymerization method synthesizing polylactic acid, then in the end modified upper chain transfer agents of polylactic acid, finally
Polystyrene is connected by reversible addion-fragmentation chain transfer polymerization, obtains di-block copolymer PLA-b-PS.
Shown in its synthesis process such as formula (VI):
Wherein, n=150, m=250.
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 3 hours.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 150 to nuclear-magnetism as the result is shown.See Fig. 3.The peak a is polylactic acid end in figure
The characteristic peak for the secondary methylene being connected with hydroxyl, the peak b are then the characteristic peak of time methylene in polylactic acid chain.The peak face at the peak b and the peak a
The ratio between product is then the degree of polymerization of polylactic acid.
(b-1) synthesis of PLA-TC
Three monothioester of dodecyl (TC, 384mg) 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. 4.The peak a is to close on three sulfide linkages on TC in figure
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-PS
The PLA-TC (500mg) that will be synthesized in step (b), AIBN (0.7mg) and styrene (9.7ml) are added to reaction tube
In, 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 beats
Corkage lid is passed through air and terminates reaction, and precipitates in methyl alcohol.Obtain di-block copolymer PLA-b-PS.Nuclear-magnetism PS as the result is shown
Block chain polymerization degree is 250.See Fig. 5.The peak a is the characteristic peak that the methylene of three sulfide linkages is closed on TC in figure, and the peak e is polylactic acid chain
In time methylene characteristic peak.The peak b, the peak c and the peak d are the resultant peak of five protons on phenyl ring in polystyrene.By calculate b,
C, the ratio of the group peak area and e peak area at the peak d, converts the degree of polymerization 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 cross-linked network of embodiment 2
The di-block copolymer PLA-b-PS that embodiment 1 synthesizes is dissolved in carbon tetrachloride, quantitative anhydrous chlorine is then added
Change aluminium, for 24 hours, after reaction, the mixing respectively with 95% second alcohol and water (4:1) is molten for 90 DEG C of standing reactions in closed container
Liquid, methanol clean three times obtained solid, and last normal-temperature vacuum is dry for 24 hours, obtain hollow organic porous nano ball
Cross-linked network.Specifically includes the following steps:
Di-block copolymer PLA-b-PS (700mg) is dissolved in 7ml carbon tetrachloride, after being completely dissolved, 2.5g is added
Anhydrous aluminum chloride.Stirring after five minutes, screws closed with covers reactor, moves it into 90 DEG C of oil bath pans, and it is small to stand reaction 24
When.After reaction solution is cooled to room temperature, lid is opened, the mixed solution that 95% second alcohol and water (4:1) of 100ml is added is stirred
At night, after filtering, gained filter residue obtains the hollow organic porous nano ball cross-linked network of final product after methanol cleans three times.
SEM test result such as Fig. 6, Cong Tuzhong are it can be found that spherical structure unit size is about 30nm, and is mutually piled into
Three-dimensional net structure.
TEM test result such as Fig. 7, Cong Tuzhong are it can be found that each structural unit is that hollow structure, and external shell is presented
Thickness degree is about 7nm, and hollow parts diameter is about 12nm.
Nitrogen adsorption desorption test result such as Fig. 8, 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 1.7nm and 5.5nm that ground, which embodies hollow organic porous nano ball cross-linked network major bore,.
The synthesis of 3 different molecular weight di-block copolymer PLA-b-PS of embodiment
(a)PLA60Synthesis, by D, L- lactide, benzyl alcohol, the ratio of the molar ratio control of stannous octoate in 60:1:0.5
In example, the reaction time is 0.5 hour, and in the same manner as in Example 1, the polylactic acid that the degree of polymerization is 60 can be obtained in other reaction conditions.
(b)PLA60-b-PS60Synthesis, by PLA60- TC, AIBN, the molar ratio of styrene control the ratio in 1:0.1:400
In example, the reaction time is 6 hours, and in the same manner as in Example 1, di-block copolymer PLA can be obtained in other reaction conditions60-b-PS60。
(c)PLA150-b-PS130Synthesis, by PLA150The molar ratio of-TC, AIBN, styrene are controlled in 1:0.1:1000
Ratio in, the reaction time be 7 hours, in the same manner as in Example 1, di-block copolymer PLA can be obtained in other reaction conditions150-b-
PS130。
The preparation of the organic porous nano ball cross-linked network of the different dimension hollows of embodiment 4
(a) with PLA60-b-PS60For presoma, in the same manner as in Example 2, structural unit size is can be obtained in other reaction conditions
For hollow organic porous nano ball cross-linked network of 40nm.Its specific surface area is 582m2g-1, micropore area 102m2g-1, total hole
Holding is 0.93m3g-1。
(b) with PLA150-b-PS130For presoma, in the same manner as in Example 2, structural unit ruler is can be obtained in other reaction conditions
Very little hollow organic porous nano ball cross-linked network for 35nm.Its specific surface area is 674m2g-1, micropore area 217m2g-1, always
Kong Rongwei 0.77m3g-1。
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 (10)
1. di-block copolymer polylactic acid-b- polystyrene PLA-b-PS is in preparing hollow organic porous nano ball cross-linked network
Application；
Wherein, shown in the di-block copolymer polylactic acid-b- polystyrene PLA-b-PS structure such as following formula (I):
Wherein, n=60~150, m=60~250.
2. a kind of synthetic method of hollow organic porous nano ball cross-linked network, which is characterized in that the described method includes: organic
In solvent, di-block copolymer PLA-b-PS passes through Fu Kechao under the action of catalyst aluminum trichloride (anhydrous) or ferric trichloride
Cross-linking reaction obtains hollow organic porous nano ball cross-linked network；
Wherein, shown in the di-block copolymer polylactic acid-b- polystyrene PLA-b-PS structure such as following formula (I):
Wherein, n=60~150, m=60~250.
3. synthetic method as claimed in claim 2, which is characterized in that the concentration of the di-block copolymer in organic solvent
Between 1~10mg/ml.
4. synthetic method as claimed in claim 2, which is characterized in that phenyl ring and anhydrous tri-chlorination in the di-block copolymer
The molar ratio of aluminium or ferric trichloride is 1:(2-4).
5. synthetic method as claimed in claim 2, which is characterized in that the temperature of the Fu Kechao cross-linking reaction is 75-90 DEG C.
6. synthetic method as claimed in claim 2, which is characterized in that the Fu Kechao cross-linking reaction under enclosed environment into
Row.
7. the hollow organic porous nano ball cross-linked network being prepared according to any one the method for claim 2-6.
8. hollow organic porous nano ball cross-linked network according to claim 7, which is characterized in that described hollow organic micro-
Hole nanosphere cross-linked network is made of hollow nanospheres as the structural unit accumulation that is cross-linked with each other；The spherical shell of the hollow nanospheres
It is made of super crosslinked polystyrene；For the diameter of the hollow nanospheres in 30~40nm, shell thickness is 6~7nm；It is described hollow organic
The specific surface area of porous nano ball cross-linked network is 582~806m2g-1, micropore area is 102~217m2g-1, total pore volume is
0.77~1.28m3g-1。
9. hollow organic porous nano ball cross-linked network as claimed in claim 8, which is characterized in that hollow organic micropore
Nanosphere cross-linked network is to CO2With preferable adsorptivity, the adsorbance in 273K is 36cm3g-1, absorption in 296K
Amount is 22cm3g-1。
10. hollow organic porous nano ball cross-linked network as claimed in claim 8 is in CO2Application in absorption.
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