CN110270318A - A kind of metal organic frame lactic acid composite material and the preparation method and application thereof - Google Patents
A kind of metal organic frame lactic acid composite material and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110270318A CN110270318A CN201910593152.XA CN201910593152A CN110270318A CN 110270318 A CN110270318 A CN 110270318A CN 201910593152 A CN201910593152 A CN 201910593152A CN 110270318 A CN110270318 A CN 110270318A
- Authority
- CN
- China
- Prior art keywords
- metal
- composite material
- lactic acid
- organic frame
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses metal organic frame lactic acid composite materials of a kind of surface hydrophobicity and its preparation method and application.Appearance by ring-opening polymerisation in metallo organic material grows polylactic acid hydrophobic macromolecule chain；The metallo organic material is the water wetted material being self-assembly of by the organic ligand containing hydroxy functional group and metal ion, cause lactide using metallo organic material surface hydroxyl and carry out active ring-opening polymerisation, obtains the star-type polymer dewatering nano composite material with high specific surface area.Organometallic polymer nanocomposite prepared by the present invention has high specific surface area, hydrophobic oleophilic oil performance, good biocompatibility and biodegradable properties, and preparation process is simple, has potential application in biomedicine field.
Description
Technical field
The present invention relates to the Coordinative Chemistry of chemical field and polymer chemistry direction more particularly to a kind of hydrophobic metal are organic
Frame lactic acid composite material and its preparation and application.
Background technique
Metal-organic framework materials (referred to as " MOFs ") are a kind of novel stephanoporate framework materials, by organic ligand with
Transition metal ions coordination is self-assembly of periodic network topological structure.Therefore, MOFs, which usually has, biggish compares table
Area, is easy to the advantages that functionalization at regular orderly cellular structure, absorption with separate, be catalyzed, carry medicine, imaging and sensing, from
The fields such as sub- exchange, photoelectric conversion have wide practical use.However, major part MOFs is hydrophilic material, and coordinate bond
To water sensitive, most of MOFs has water stability difference, limits its practical ranges.Prepare hydrophobicity MOFs
Material, hydrophobic layer can reduce contact of the duct to a large amount of water, avoid material surface from being flooded and moisten and performance decline, so as to improve
The stability of MOFs expands its application range.
Design that novel water stability is good, usually there are two types of methods for MOFs material of hydrophobic oleophilic oil: one is closed by design
At hydrophobicity organic ligand, hydrophobicity MOFs material is self-assembly of with metal ion；Another kind is according to existing MOFs material
The designability of structure improves the hydrophilic and hydrophobic of MOFs by the method modified after synthesis.Wherein, the method preparation modified afterwards is dredged
Aqueous MOFs material is simple and easy to do, is a kind of common method.The method that the method for common rear modification improves MOFs hydrophobic performance
Organic ligand is modified including fluorine functional, introduces chain alkyl etc..However, the composite material biocompatibility being prepared compared with
Difference has certain toxicity.Polylactic acid (Poly (lactic acid), PLA) is a kind of biological medical polymer material being concerned
Material has good biological degradability and biocompatibility, is widely used in biomedical engineering field.However, polymer material
Specific surface area is low, limits its practical application value.
CN108948367A discloses the metal-organic framework material and its preparation and application of a kind of surface hydrophobicity.Passing through
The appearance that modification is learned in metal-organic framework material connects hydrophobic grouping；The metal-organic framework material is by containing NH2Official
Can group organic ligand and the water wetted material that is self-assembly of of metal ion, it is modified so that material it is with good stability with
And outer surface hydrophobic oleophilic oil performance.In the prior art still without open metal-organic framework material and the compound hydrophobicity of polylactic acid
The excellent material of energy.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a kind of metals of surface hydrophobicity machine frame
Frame lactic acid composite material and its preparation method and application.
The appearance of a kind of metal organic frame lactic acid composite material, the metal framework material (MOFs) contains hydrophobic polylactic acid
(PLA) macromolecular chain.
The metal-organic framework material contains-OH functional group；The polylactic acid is by D, L- lactide ring-opening polymerisation
It obtains.Metal center metal in the MOFs material is Cu, Zr, Zn, Ti, Co, Mn, Ni, Mg, Fe etc., preferably UiO-66-
OH、UiO-66-(OH)2。
The invention also includes a kind of preparation methods of metal organic frame lactic acid composite material, mainly include following step
It is rapid:
(1) organic ligand containing-OH functional group and metal inorganic salt are dissolved in solvent, 80- with molar ratio 2:1-1:2
220 DEG C of reaction 12-48h, are cooled to room temperature, and are centrifugally separating to obtain MOF- (OH) n；
(2) MOF- (OH) n and D for obtaining step (1), the reaction of L- lactide, nitrogen protection are stirred using toluene as solvent
After mixing melting, it is that catalyst is cooled to room temperature, product first uses dichloro after reacting a period of time that a certain amount of stannous octoate, which is added,
Methane dissolution, after precipitated with n-hexane, repeatedly three times, remove unreacted D, L- lactide monomer and small molecule and catalysis
Agent is dried in vacuo more than for 24 hours.
Organic ligand described in step (1) containing-OH functional group is 2- hydroxyterephthalic acid, 2,3- dihydroxy pair
Phthalic acid, 2,5- dihydric para-phthalic acid, 5- Hydroxy M Phthalic Acid, 4 hydroxyisophthalic acid, 3,6- dihydroxy are adjacent
One or more of phthalic acid, 2,5- dihydroxybiphenyl dioctyl phthalate etc.；
The metal inorganic salt be the halide of Cu, Zr, Zn, Ti, Co, Mn, Ni, Cd, Fe, oxyhalide, nitrate,
One of sulfate, acetate etc.；
MOF- (OH) n and D in step (2), the mass ratio of L- lactide are 1:10-1:50；The stannous octoate catalysis
The dosage of agent is D, the 0.1%-1% of L- lactide quality；The reaction temperature is 130-180 DEG C；The reaction time
For 12-48h.
The invention also includes a kind of applications of metal organic frame lactic acid composite material, are applied to hydrophobic biological
In medical material.
The present invention carries out D by initiator of MOFs crystal, and the active ring-opening polymerisation of L- lactide obtains hydrophobic MOFs@PLA
Composite material, while specific surface area with higher.Compared with prior art, the present invention has the advantage that
(1) hydrophobic MOFs@PLA composite material preparation process of the invention is simple, and hydrophobic performance can be in a big way
It is adjusted, while being able to maintain biggish specific surface area, and hydrophobic performance is good.
(2) hydrophobic MOFs@PLA composite material of the invention has good biocompatibility and degradability, in biology
Field of medicaments has potential using value.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram (XRD) of UiO-66-OH and UiO-66-OH@PLA prepared by embodiment 1；
Fig. 2 is the water contact angle test result of UiO-66-OH in embodiment 1；
Fig. 3 is the water contact angle test result of UiO-66-OH@PLA prepared by embodiment 1；
Fig. 4 is the water contact angle test result of UiO-66-OH@PLA prepared by embodiment 2；
Fig. 5 is UiO-66- (OH) prepared by embodiment 32The water contact angle test result of@PLA；
Fig. 6 is the water contact angle test result of Ni-MOF-74@PLA prepared by embodiment 4；
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
Embodiment 1
5mmol 2- hydroxyterephthalic acid and 5mmol chlorine hydrate oxygen zirconium are dissolved in 30ml water, 30ml is added
Acetic acid is cooled to room temperature after 24 hours as regulator, reflux (100 DEG C), collects solid product, 8000r/min centrifuge separation.
After ethanol washing solid product 3 times, entitled UiO-66-OH, N are obtained2It is 887m that absorption test, which obtains BET specific surface area,2/ g,
XRD, contact angle result are as shown in Figure 1, 2.0.4g UiO-66-OH and 2g D are taken, L- lactide is scattered in toluene, is warming up to
135 DEG C of stirrings melt 5 minutes, 0.010g stannous octoate are added, the reaction was continued 24 hours.It is cooled to room temperature after reaction.It produces
Object is first dissolved with methylene chloride, then is precipitated with n-hexane, is repeated three times to remove unreacted monomer and remaining catalysis
Agent.Obtained solid product is finally dried in vacuo to the UiO-66-OH PLA to get hydrophobically modified, reaction side under the conditions of 80 DEG C
Formula is as shown in Figure 1, N2It is 649m that absorption test, which obtains BET specific surface area,2/ g, XRD, contact angle result are as shown in Figure 1,3.
Embodiment 2
Change the D being added, L- lactide amount is 5g, remaining keeps reaction condition same as Example 1, and UiO- is made
66-OH@PLA, N2It is 614m that absorption test, which obtains BET specific surface area,2/ g, contact angle result are as shown in Figure 4.
Embodiment 3
The 2- hydroxyterephthalic acid in embodiment 1 is replaced with 2,5-Dihydroxyterephthalic acid, remaining keeps and implements
The identical reaction condition of example 1 is made UiO-66- (OH)2@PLA, N2It is 603m that absorption test, which obtains BET specific surface area,2/ g, contact
Angle result is as shown in Figure 5.
Embodiment 4
Replace the chlorine hydrate oxygen zirconium in embodiment 3 as metal precursor using nickel acetate, remaining keeps and embodiment 3
Ni-MOF-74@PLA, N is made in identical reaction condition2It is 355m that absorption test, which obtains BET specific surface area,2/ g, contact angle result
As shown in Figure 6.
Claims (9)
1. the appearance of a kind of metal organic frame lactic acid composite material, the metal framework material contains hydrophobic polylactic acid macromolecular
Chain.
2. metal organic frame lactic acid composite material according to claim 1, it is characterised in that: the metal is organic
Frame material contains-OH functional group；The polylactic acid is obtained by D, L- lactide ring-opening polymerisation.
3. metal organic frame lactic acid composite material according to claim 1, it is characterised in that: the metal is organic
Frame material contains metal center and organic ligand, the metal center metal in the metal-organic framework material be Cu, Zr,
Zn,Ti,Co,Mn,Ni,Mg,Fe；Organic ligand is 2- hydroxyterephthalic acid, 2,3- dihydric para-phthalic acid, 2,5- dihydroxy
Base terephthalic acid (TPA), 5- Hydroxy M Phthalic Acid, 4 hydroxyisophthalic acid, 3,6- dihydroxy phthalic acid, 2,5- dihydroxy
One or more of base biphenyl dicarboxylic acid.
4. metal organic frame lactic acid composite material according to claim 3, it is characterised in that: the metal is organic
Metal center in frame material is UiO-66-OH and UiO-66- (OH)2。
5. metal organic frame lactic acid composite material according to claim 1, it is characterised in that: initiator used is
Metal-organic framework material containing multiple-OH, catalyst used are stannous octoates.
6. a kind of preparation method of metal organic frame lactic acid composite material as described in claim 1, it is characterised in that: main
Want the following steps are included:
(1) organic ligand containing-OH functional group and metal inorganic salt are dissolved in solvent with molar ratio 2:1-1:2,80-220 DEG C
12-48h is reacted, is cooled to room temperature, is centrifugally separating to obtain MOF- (OH) n；
(2) MOF- (OH) n and D for obtaining step (1), the reaction of L- lactide, nitrogen protection, using toluene as solvent, stirring is molten
After melting, addition stannous octoate is that catalyst is cooled to room temperature after reacting a period of time, and product is first dissolved with methylene chloride, rear to use
N-hexane precipitating, repeatedly three times, removes unreacted D, L- lactide monomer and small molecule and catalyst, is dried in vacuo
More than for 24 hours.
7. preparation method according to claim 6, it is characterised in that: metal inorganic salt described in step (1) be Cu,
One of halide, oxyhalide, nitrate, sulfate, acetate of Zr, Zn, Ti, Co, Mn, Ni, Cd, Fe etc..
8. preparation method according to claim 6, it is characterised in that: MOF- (OH) n and D in step (2), L- lactide
Mass ratio is 1:10-1:50；The dosage of the stannous octoate catalyst is D, the 0.1%-1% of L- lactide quality；It is described
Reaction temperature be 130-180 DEG C；The reaction time is 12-48h.
9. a kind of application of metal organic frame lactic acid composite material as described in claim 1, is applied to biological doctor
In medicine field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910593152.XA CN110270318A (en) | 2019-07-03 | 2019-07-03 | A kind of metal organic frame lactic acid composite material and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910593152.XA CN110270318A (en) | 2019-07-03 | 2019-07-03 | A kind of metal organic frame lactic acid composite material and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110270318A true CN110270318A (en) | 2019-09-24 |
Family
ID=67964006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910593152.XA Pending CN110270318A (en) | 2019-07-03 | 2019-07-03 | A kind of metal organic frame lactic acid composite material and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110270318A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110951088A (en) * | 2019-12-13 | 2020-04-03 | 安徽大学 | Zirconium-based metal organic framework material, preparation and application as chromium removal agent |
| CN114534700A (en) * | 2022-02-15 | 2022-05-27 | 辽宁大学 | Durable super-hydrophobic metal organic framework sponge material and preparation method and application thereof |
| CN114984933A (en) * | 2022-06-23 | 2022-09-02 | 宁夏大学 | Dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether and preparation method thereof |
| CN116515125A (en) * | 2023-04-28 | 2023-08-01 | 华中科技大学 | Method for preparing metal-organic framework material from waste polylactic acid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387756A (en) * | 2013-07-30 | 2013-11-13 | 浙江微度医疗器械有限公司 | Modification method and application of hydroxyapatite |
| CN105854853A (en) * | 2016-06-13 | 2016-08-17 | 大连理工大学 | Preparation method of antibacterial metal organic framework composite nanofiber |
| CN106084237A (en) * | 2016-07-19 | 2016-11-09 | 华中科技大学 | A kind of poly phosphate polylactic acid di-block copolymer and preparation method thereof and carrier micelle |
| CN107245179A (en) * | 2017-06-26 | 2017-10-13 | 台山长江塑料制品有限公司 | A kind of magnetic plastics and preparation method thereof |
| CN108368241A (en) * | 2016-01-26 | 2018-08-03 | 夏玲 | MOFs as the catalyst for ring-opening polymerisation |
| CN108948367A (en) * | 2018-07-13 | 2018-12-07 | 江南大学 | A kind of surface hydrophobicity metal-organic framework material and the preparation method and application thereof |
-
2019
- 2019-07-03 CN CN201910593152.XA patent/CN110270318A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387756A (en) * | 2013-07-30 | 2013-11-13 | 浙江微度医疗器械有限公司 | Modification method and application of hydroxyapatite |
| CN108368241A (en) * | 2016-01-26 | 2018-08-03 | 夏玲 | MOFs as the catalyst for ring-opening polymerisation |
| CN105854853A (en) * | 2016-06-13 | 2016-08-17 | 大连理工大学 | Preparation method of antibacterial metal organic framework composite nanofiber |
| CN106084237A (en) * | 2016-07-19 | 2016-11-09 | 华中科技大学 | A kind of poly phosphate polylactic acid di-block copolymer and preparation method thereof and carrier micelle |
| CN107245179A (en) * | 2017-06-26 | 2017-10-13 | 台山长江塑料制品有限公司 | A kind of magnetic plastics and preparation method thereof |
| CN108948367A (en) * | 2018-07-13 | 2018-12-07 | 江南大学 | A kind of surface hydrophobicity metal-organic framework material and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 孙圆: "银金属有机骨架复合抗菌材料的制备及性能", 《大连理工大学专业学位硕士学位论文》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110951088A (en) * | 2019-12-13 | 2020-04-03 | 安徽大学 | Zirconium-based metal organic framework material, preparation and application as chromium removal agent |
| CN114534700A (en) * | 2022-02-15 | 2022-05-27 | 辽宁大学 | Durable super-hydrophobic metal organic framework sponge material and preparation method and application thereof |
| CN114534700B (en) * | 2022-02-15 | 2024-01-09 | 辽宁大学 | Durable super-hydrophobic metal-organic framework sponge material and preparation method and application thereof |
| CN114984933A (en) * | 2022-06-23 | 2022-09-02 | 宁夏大学 | Dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether and preparation method thereof |
| CN114984933B (en) * | 2022-06-23 | 2023-11-21 | 宁夏大学 | Benzyl ether-based dendritic organic micromolecular gel silica-based stationary phase material and preparation method thereof |
| CN116515125A (en) * | 2023-04-28 | 2023-08-01 | 华中科技大学 | Method for preparing metal-organic framework material from waste polylactic acid |
| CN116515125B (en) * | 2023-04-28 | 2024-05-24 | 华中科技大学 | Method for preparing metal-organic framework material from waste polylactic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110270318A (en) | A kind of metal organic frame lactic acid composite material and the preparation method and application thereof | |
| US9469722B2 (en) | Metal cyanide complex catalyst and its preparation and application | |
| CN108368241B (en) | MOFs as catalysts for ring-opening polymerizations | |
| CN107936505B (en) | Polylactic acid antibacterial film and preparation method thereof | |
| KR101729300B1 (en) | Organic zinc catalyst, preparation method of the catalyst and production method of poly(alkylene carbonate) resin over the catalyst | |
| CN113929924B (en) | Isopolymolybdic acid metal organic framework material for preparing polylactic acid and preparation method | |
| CA2861224A1 (en) | Process for preparing high molecular weight polymers by polymerizing epoxide monomers | |
| CN113956499B (en) | Zinc-containing isopolymolybdic acid metal organic framework material and preparation method and application thereof | |
| CN105622445A (en) | Method for synthesizing nanoscale metal-organic framework materials at room temperature | |
| CN114015070A (en) | Isopolymolybdic acid coordination polymer for catalyzing ring-opening polymerization of lactide and preparation method thereof | |
| CN113999401B (en) | Cobalt-containing isopolymolybdic acid metal organic framework material and preparation method and application thereof | |
| KR101606556B1 (en) | Organic-inorganic nanopore materials having surface-modified with polysilsesquioxane and preparation thereof | |
| KR101848797B1 (en) | Linear inorganic coordinated polymer, metal complex, metal nano structure, and catalyst composition comprising the same | |
| CN107383377B (en) | Cyclic polycaprolactone-polyethylene glycol amphiphilic block copolymer, and preparation and application thereof | |
| Yang et al. | Surface activated zinc-glutarate for the copolymerization of CO 2 and epoxides | |
| Pang et al. | Synthesis and catalytic performance of wood cellulose nanofibers grafted with polylactic acid in rare-earth complexes based on tetrazole carboxylic acids | |
| CN114395132A (en) | Isopolymolybdic acid coordination polymer catalyst and preparation method and application thereof | |
| Ferreira et al. | Manganese-sulfonato porphyrin adsorbed on amino kaolinite as heterogeneous catalyst for oxidation and polymerization reactions | |
| KR101138220B1 (en) | Method for preparing nanoparticles | |
| CN1616355A (en) | Uniformly coordinating precipitation method for preparing nano nickel hydroxide | |
| KR102082274B1 (en) | Organic zinc supported catalyst, preparation method of the catalyst, and preparation method of poly(alkylene carbonate) resin using the catalyst | |
| KR20160126117A (en) | Biodegradable triblock copolymers, synthesis methods therefore and microparticles-based drug delivery made there from | |
| KR101791673B1 (en) | Metal complex, metal nano structure and catalyst composition comprising the same | |
| CN117417549B (en) | Layer-functionalized two-dimensional metal organic framework coordination polymer and preparation method thereof | |
| JP2021519855A (en) | A method for producing an organozinc catalyst, and a method for producing a polyalkylene carbonate resin using an organozinc catalyst produced from this method. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190924 |