CN110256611A - A kind of application of MXene as radical initiator - Google Patents

A kind of application of MXene as radical initiator Download PDF

Info

Publication number
CN110256611A
CN110256611A CN201910496381.XA CN201910496381A CN110256611A CN 110256611 A CN110256611 A CN 110256611A CN 201910496381 A CN201910496381 A CN 201910496381A CN 110256611 A CN110256611 A CN 110256611A
Authority
CN
China
Prior art keywords
mxene
application
monomer
initiator
under
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.)
Granted
Application number
CN201910496381.XA
Other languages
Chinese (zh)
Other versions
CN110256611B (en
Inventor
李娟�
张德盘
陶娜
李锡龙
孙晓毅
刘又年
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201910496381.XA priority Critical patent/CN110256611B/en
Publication of CN110256611A publication Critical patent/CN110256611A/en
Application granted granted Critical
Publication of CN110256611B publication Critical patent/CN110256611B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A kind of application the invention particularly discloses MXene as initiator, MXene cause olefinic monomer and polymerize under the conditions of deoxygenation as initiator；The MXene is placed in etching liquid by MAX, and synchronous etching is removed, is then washed under ultrasonic wave added, is obtained.The present invention innovatively has found, MXene made from the synchronous etching stripping means of the ultrasonic wave added unexpectedly has good initiation, itself it can cause polymerizing olefin monomers under without existing conventional initiation conditions (such as under causing without conventional light-initiated or general radical initiator).

Description

A kind of application of MXene as radical initiator
Technical field
The present invention relates to MXene and free radical polymerization field, and the preparation method and MXene of in particular to a kind of MXene Application as radical initiator.
Background technique
Free radical polymerization occupies extremely important status in polymer science and industry, and polymerization reaction category chain polymerization is anti- It answers, mainly includes chain initiation, four chain growth, chain termination and chain tra nsfer elementary reactions.
Two-dimentional MXene lamella is a kind of novel stratified nano materials, and there is two-dimensional structure, the metal of similar graphene to lead Electrical and excellent chemical property etc., it is compound in energy storage, catalysis, bio-medical, sensor and new polymers enhancing base The numerous areas such as material show good application prospect { Journal of Inorganic Materials 2017,32 (06), 561-570 }.
The preparation method of MXene material is generally with HF, LiF/HCl, NaHF at present2、KHF2Or NH4HF2It is first for etching agent Etching, rear to remove { AdvancedMaterials 2018,30 (52), 1804779 }, the processing time is longer, and efficiency is lower.Although There is two-dimentional MXene material that there is self-initiating photo-grafting and photopolymerization (self-initiated photografting now And photopolymerization, abbreviation SIPGP) effect Chemical Communications 2015,51 (2), 314-317 }, the mechanism that such MXene causes polymerization is under the irradiation of ultraviolet light, and the surface MXene, which is excited, to be generated free radicals, Further cause monomer polymerization.It has not yet to see without illumination condition directly using two-dimentional MXene material as radical initiator Cause olefin monomer polymerization and the research of synthetic polymer hydrogel report.
Summary of the invention
A kind of application the purpose of the present invention is to provide MXene as radical initiator.
Second purpose of the invention is, provides and a kind of prepares polyalcohol hydrogel as radical initiator using MXene Method.
A kind of application of MXene as radical initiator causes olefinic monomer in deoxygenation using MXene as initiator Under the conditions of polymerize；
The described MXene's the preparation method comprises the following steps: presoma MAX is placed in etching liquid, the synchronous etching under ultrasonic wave added It removes, is then washed, obtaining MXene two-dimensional material；
The M is at least one of transition metal；Preferably Ti or Nb；
The A is at least one of IIIA or IVA element；Preferably Al；
The X is C and/or N.
The present invention innovatively has found that the ultrasonic wave added, which synchronizes, etches MXene made from stripping means, surface nature, Group is different with existing conventional MXene, the MXene two dimension obtained by the synchronous etching of the ultrasonic wave added and stripping technology Material unexpectedly has initiation, can under without existing conventional initiation conditions (such as without conventional light-initiated or Under general radical initiator causes), itself it can cause polymerizing olefin monomers.
The preparation method of synchronous etching and removing under the ultrasonic wave added of MXene of the present invention is to confer to material obtained Cause the key of function, compared to existing method, two-dimensional material made from preparation method of the present invention unexpectedly be can express Excellent free radical initiation out.
Preferably, the etching liquid is the mixed aqueous solution of LiF/HCl；Wherein, the concentration of LiF be 0.01~ 0.1g/mL；Preferably 0.08g/mL；The molar concentration of HCl is 6~12mol/L, preferably 9mol/L.
Preferably, the power of ultrasound is 50~1000W；Further preferably 300W；Ultrasonic time is 30min~12h； Further preferably 6h.
Currently preferred MXene lamellar compound preparation process are as follows: by LiF/HCl as etching agent, using ultrasound Etching/removing Synchronos method, after etching 12h, with deionized water, centrifuge washing is to pH5~6 at 3500rpm, then uses 12000rpm Centrifugation obtains supernatant, and obtained supernatant is MXene nanometer sheet.
Preferably, polymerization process carries out under the conditions of without light-initiated (being protected from light or unglazed) in the present invention, alternatively, It is carried out under the radical initiator of at least one of no additional persulfate compound, peroxide, riboflavin.
Application of the present invention, the ultrasonic wave added innovated using the present invention is synchronous to etch MXene made from stripping method, can Unexpectedly to play the role of causing polymerizing olefin monomers；It can be not necessarily to ultraviolet lighting or conventional radical initiators (example Such as persulfate, hydrogen peroxide, riboflavin) under the action of, the polymerizing olefin monomers can also be caused even if under dark.No Only in this way, the performance that itself is made and causes the polymer obtained can also be improved.
Preferably, the application, as initiator, initiation olefinic monomer polymerize under the conditions of deoxygenation to be obtained MXene Free copolymer and the polymer being grafted on MXene lamella.
Preferably, the olefinic monomer is acrylic monomer.Preferred olefinic monomer is of the present invention Under the deoxygenation of MXene causes, polymerization and further gelation can be successfully realized.
Further preferably, the hydrocarbon monomer is the monomer with formula 1,2 structural formula of formula；
R1~R3It is alone H, C1~C6Alkyl, C1~C6Alkoxy or C1~C6N- replace alkyl amino；
Most preferably, the olefinic monomer is n-isopropyl acrylamide (NIPAM), N,N-DMAA (DMA), acrylamide (AAm), dimethylaminoethyl methacrylate (DMAEMA), acrylic acid (AAc) and hydroxyethyl methacrylate At least one of monomers such as ethyl ester (HEMA).
Preferably, the mass ratio of the initiator and monomer is 0.01~100.
Preferably, monomer concentration is 0.01~30wt% in polymerization starting soln.
Preferably, the temperature of polymerization reaction is 0~60 DEG C.
Preferably, polymerization reaction time is 5min~for 24 hours.
The present invention also provides a kind of preparation method of polyalcohol hydrogel, the water being made of MXene, acrylic monomer Solution polymerize under the conditions of deoxygenation to be obtained.
In the prior art, acrylic monomer usually need to be in ultraviolet initiation or radical initiator such as persulfuric acid Salt, hydrogen peroxide, riboflavin realize polymerization and gelation.And the present invention innovatively uses the ultrasonic wave added preparation method MXene obtained can be such that acrylic monomer polymerize under dark condition and gelation as initiator.Moreover, compared with it Its initiator causes the gel of preparation, has photothermal conversion property using gel made from this method.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention firstly discovers that and confirmed by the means such as EPR, nuclear magnetic resonance, ultrasonic wave added of the present invention is same Step etching removing means obtain MXene have initiation, can without it is ultraviolet, without conventional radical initiators under, Ji Keyin Send out various of monomer polymerization.
(2) MXene that ultrasonic wave added etching stripping method of the present invention is prepared, can not only cause water-setting made from monomer Glue, and hydrogel can be assigned and show excellent photo-thermal effect.
Detailed description of the invention
2 difference MXene material of Fig. 1 embodiment causes acrylamide monomer and polymerize to form polyalcohol hydrogel figure；
Fig. 2 embodiment 2Ti3C2Electron paramagnetic resonance spectrum figure (EPR)；
Fig. 3 embodiment 3Ti3C2Nanometer sheet causes different monomers and polymerize to form polyalcohol hydrogel figure；
Fig. 4 embodiment 4Ti3C2Nanometer sheet causes NIPAM polymerization1HNMR figure；
Fig. 5 comparative example 3Ti3C2Nanometer sheet causes NIPAM polymerization1HNMR figure；
Fig. 6 embodiment 5Ti3C2Nanometer sheet causes NIPAM and polymerize the heating to form polyalcohol hydrogel under 808nm irradiation Figure.
Specific embodiment
Following embodiment is intended to illustrate invention rather than limitation of the invention further.
The synchronous etching stripping technology of 1. ultrasonic wave added of embodiment prepares Ti3C2、Ti2C、Nb2C two-dimension nano materials
Ti3C2Preparation:
By 0.125g Ti3AlC2It is dispersed in 0.2g LiF/2.5mL HCl (9M) solution, 300W ultrasonic reaction 6h Afterwards, being washed repeatedly with deionized water to pH is about 5~6；Then, supernatant is taken to obtain Ti with 12000rpm centrifugation 10min3C2It receives Rice piece.
Ti2The preparation of C:
By 0.09g Ti2AlC is dispersed in 0.13g LiF/2.5mLHCl (3M) solution, 300W ultrasonic reaction 6h Afterwards, being washed repeatedly with deionized water to pH is about 5~6；Then supernatant is taken to obtain Ti with 12000rpm centrifugation 10min2C nano Piece.
Nb2The preparation of C:
By 0.144g Nb2AlC is dispersed in 0.23g LiF/3mL HCl (9M) solution, 300W ultrasonic reaction 6h Afterwards, being washed repeatedly with deionized water to pH is about 5~6；Then, supernatant is taken to obtain Nb with 12000rpm centrifugation 10min2C receives Rice piece.
2. difference MXene material of embodiment (preparation of embodiment 1) causes acrylamide polymerization
It takes the acrylamide monomer of 80mg to be dissolved in 1mL MXene (1.6wt%) nanometer sheet, is passed through N under ice bath2Deoxygenation After 2min, after being protected from light 10min at 4 DEG C, polyalcohol hydrogel can be formed.The gel figure that different MXene polymerize is shown in Shown in Fig. 1, gel sample does not flow after being inverted, and illustrates that different MXene materials can play initiation monomer polymerization and further obtain Gel.
MXene material of the present invention proves that MXene system generates hydroxyl free by electron paramagnetic resonance spectrum figure (EPR) Base can cause monomer polymerization, specific as follows:
5mg 5,5- dimethyl -1- oxidation pyrrolin (DMPO) is dissolved in 200 μ L Ti3C2In, pass through Ti3C2Electron paramagnetic The spectrogram Bruker A300 spectrometer that resonates carries out free radical detection.EPR result is shown in Fig. 2, shows Ti3C2It can produce hydroxyl free Base, and then cause monomer polymerization.
Embodiment 3.Ti3C2Nanometer sheet (preparation of embodiment 1) causes different monomers polymerization
80mg n-isopropyl acrylamide (NIPAM), N,N-DMAA (DMA), acrylamide are taken respectively (AAm), dimethylaminoethyl methacrylate (DMAEMA), acrylic acid (AAc) and hydroxyethyl methacrylate (HEMA) monomer It is dissolved in 1mL Ti3C2In (1.6wt%) nanometer sheet, N is passed through under ice bath2After deoxygenation 2min, it is protected from light at 4 DEG C after polymerization 10min i.e. Can form polyalcohol hydrogel, the polymer figure of different monomers as shown in Figure 3, Ti3C2It is poly- that nanometer sheet can trigger different monomers It closes.
Commonly etching stripping technology (non-ultrasound assist in synchronization etching and stripping technology) prepares Ti to comparative example 1.3C2Two wieners Rice material
Ti3C2Preparation:
By 0.125g Ti3AlC2It is dispersed in 0.2g LiF/2.5mLHCl (9M) solution, after 35 DEG C of reaction 6h, uses It is about 5~6 that deionized water, which is washed repeatedly to pH,；Then, supernatant is taken to obtain Ti with 12000rpm centrifugation 10min3C2Nanometer sheet.
Comparative example 2 is attempted commonly to etch stripping technology preparation Ti3C2It is different that two-dimension nano materials (preparation of comparative example 1) cause N- Propylacrylamide polymerization
The n-isopropyl acrylamide monomer of 80mg is taken to be dissolved in 1mLTi3C2In (1.6wt%) nanometer sheet, it is passed through under ice bath N2After deoxygenation 2min, after being protected from light 12h at 4 DEG C, sample is in solution state, failed gelation.
Embodiment 4.Ti3C2Nanometer sheet (preparation of embodiment 1) causes NIPAM monomer polymerization nuclear-magnetism characterization
The Ti that embodiment 3 is obtained3C2After nanometer sheet causes the gel refrigeration drying that NIPAM is formed, 5mg is taken to be dissolved in In 0.5mLDMSO, characterize whether monomer polymerize by nuclear-magnetism.
As seen from the figure, sample after freeze-drying1There is the nuclear magnetic resonance absorption of polymer, this etching stripping technology system in H NMR Standby Ti3C2Two-dimension nano materials (preparation of embodiment 1) under equal conditions can trigger NIPAM polymerization (test chart is shown in Fig. 4).
Comparative example 3.Ti3C2Nanometer sheet (preparation of comparative example 1) causes NIPAM monomer polymerization nuclear-magnetism characterization
The Ti that comparative example 1 is obtained3C2After nanometer sheet reacts 12h freeze-drying with NIPAM, 5mg is taken to be dissolved in 0.5mLDMSO In, characterize whether monomer polymerize by nuclear-magnetism.
As seen from the figure, sample after freeze-drying1H NMR has no the nuclear magnetic resonance absorption of polymer, shows common etching stripping The Ti of separating process preparation3C2Two-dimension nano materials (preparation of comparative example 1) cannot under equal conditions cause NIPAM polymerization (test chart See Fig. 5).
Embodiment 5.Ti3C2Nanometer sheet (preparation of embodiment 1) causes the nano combined water that NIPAM monomer polymerization is prepared The photothermal conversion of gel is tested
In order to assess the photo-thermal effect of Nanometer composite hydrogel, to embodiment 2 prepare PNIPAM nano-composite gel, Different capacity density (0.6,0.8,1.0,1.2,1.4W/cm2) under, 5min is irradiated using 808nm near-infrared laser, every 30s Its temperature change is recorded with infrared thermoviewer.It is obtained using Ammonium Persulfate 98.5 (APS) initiation without Ti3C2Gel is as control (1.0W/cm2).As a result as shown in fig. 6, Ti3C2The PNIPAM Nanometer composite hydrogel that nanometer sheet causes is in 1.0W/cm2808nm After laser light shines 5min, temperature is increased up to 55 DEG C, and temperature increases only 27 under the PNIPAM hydrogel equal conditions that APS causes ℃。

Claims (10)

1. a kind of application of MXene as radical initiator, which is characterized in that using MXene as initiator, cause alkene list Body polymerize under the conditions of deoxygenation；
The MXene is placed in etching liquid by MAX, and synchronous etching is removed, is then washed under ultrasonic wave added, is obtained；
The M is at least one of transition metal；
The A is at least one of IIIA or IVA element；
The X is C and/or N.
2. application as described in claim 1, which is characterized in that the etching liquid is the mixed aqueous solution of LiF/HCl；Its In, the concentration of LiF is 0.01~0.1g/mL, preferably 0.08g/mL；The molar concentration of HCl is 6~12mol/L, preferably 9mol/L。
3. application as claimed in claim 2, which is characterized in that ultrasonic power is 50~1000W, preferably 300W；Ultrasound Time is 30min~12h, preferably 6h.
4. application as claimed in any one of claims 1 to 3, which is characterized in that polymerization process carries out under unglazed initiation conditions, Alternatively, being carried out under the radical initiator without at least one of outer plus persulfate compound, peroxide, riboflavin.
5. application as claimed in claim 4, which is characterized in that MXene causes olefinic monomer and be protected from light condition as initiator The polymer that lower polymerization obtains free copolymer and is grafted on MXene lamella.
6. application as described in claim 1, which is characterized in that the olefinic monomer is acrylic monomer；
The preferably monomer with formula 1,2 structural formula of formula；
R1~R3It is alone H, C1~C6Alkyl, C1~C6Alkoxy or C1~C6N- replace alkyl amino.
7. application as claimed in claim 6, which is characterized in that the olefinic monomer is n-isopropyl acrylamide (NIPAM), N, N- dimethylacrylamide (DMA), acrylamide (AAm), dimethylaminoethyl methacrylate (DMAEMA), At least one of acrylic acid (AAc) and hydroxyethyl methacrylate (HEMA).
8. the use as claimed in claim 7, which is characterized in that the mass ratio of the initiator and monomer is 0.01~100；It is poly- It closes in starting soln, monomer concentration is 0.01~30wt%.
9. application as claimed in claim 8, which is characterized in that the temperature of polymerization reaction is 0~60 DEG C；Time be 5min~ 24h。
10. a kind of preparation method of polyalcohol hydrogel, which is characterized in that the aqueous solution being made of MXene, acrylic monomer Logical nitrogen deoxygenation polymerize to obtain；Preferably, the MXene is made by any one of claim 1~9 application method.
CN201910496381.XA 2019-06-10 2019-06-10 Application of MXene as free radical initiator Expired - Fee Related CN110256611B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910496381.XA CN110256611B (en) 2019-06-10 2019-06-10 Application of MXene as free radical initiator

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910496381.XA CN110256611B (en) 2019-06-10 2019-06-10 Application of MXene as free radical initiator

Publications (2)

Publication Number Publication Date
CN110256611A true CN110256611A (en) 2019-09-20
CN110256611B CN110256611B (en) 2020-05-26

Family

ID=67917287

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910496381.XA Expired - Fee Related CN110256611B (en) 2019-06-10 2019-06-10 Application of MXene as free radical initiator

Country Status (1)

Country Link
CN (1) CN110256611B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111634913A (en) * 2020-05-29 2020-09-08 太原理工大学 Stripping Ti3AlC2Preparation of high-purity few-layer Ti3C2Method of Tx slice
CN111785534A (en) * 2020-06-08 2020-10-16 华中科技大学 Method for immobilizing MXene by ionic liquid covalent bonding and product thereof
CN112107547A (en) * 2020-10-16 2020-12-22 温州医科大学附属第二医院（温州医科大学附属育英儿童医院） Hydrogel microsphere with photo-thermal responsiveness and preparation method and application thereof
CN112646094A (en) * 2020-12-19 2021-04-13 南京工业职业技术大学 Preparation method of wear-resistant and high-temperature-resistant window glass and window glass prepared by preparation method
CN112876585A (en) * 2021-01-19 2021-06-01 中南大学 Free radical polymerization initiated by Ag/MXene and preparation method of organic hydrogel
CN113845633A (en) * 2021-10-08 2021-12-28 湖北三棵树新材料科技有限公司 Poly (hydroxyethyl methacrylate) grafted MXene, anticorrosive paint and preparation method thereof
WO2022165989A1 (en) * 2021-02-05 2022-08-11 南方科技大学 Mxene material having organic chelating functional groups grafted on surface and preparation method therefor
CN115068673A (en) * 2022-06-30 2022-09-20 吉林大学 Preparation method and application of MXene-based autocatalytic conductive hydrogel dressing
CN116082538A (en) * 2022-12-15 2023-05-09 德州学院 Method for initiating vinyl monomer polymerization by ultrasonic induced free radical

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104528721A (en) * 2014-12-23 2015-04-22 陕西科技大学 Preparation method of flaky two-dimensional nano-titanium carbide nanometre material
CN108440696A (en) * 2018-02-09 2018-08-24 中南大学 A kind of polyalcohol hydrogel and its preparation and application based on two-dimentional titanium carbide layer shape compound crosslink
CN108441287A (en) * 2018-04-25 2018-08-24 青岛大学 A kind of preparation method of the nano combined er materials of Mxene/PS
CN109232916A (en) * 2018-08-17 2019-01-18 东华大学 A kind of compound thermal response-type hydrogel of Mxene/PNIPAM/ alginate and its preparation and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104528721A (en) * 2014-12-23 2015-04-22 陕西科技大学 Preparation method of flaky two-dimensional nano-titanium carbide nanometre material
CN108440696A (en) * 2018-02-09 2018-08-24 中南大学 A kind of polyalcohol hydrogel and its preparation and application based on two-dimentional titanium carbide layer shape compound crosslink
CN108441287A (en) * 2018-04-25 2018-08-24 青岛大学 A kind of preparation method of the nano combined er materials of Mxene/PS
CN109232916A (en) * 2018-08-17 2019-01-18 东华大学 A kind of compound thermal response-type hydrogel of Mxene/PNIPAM/ alginate and its preparation and application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HUAWEI WEI ET AL: "Ti3C2Tx MXene/polyaniline (PANI) sandwich intercalation structure composites constructed for microwave absorption", 《COMPOSITES SCIENCE AND TECHNOLOGY》 *
MASSOUD MALAKI ET AL: "MXenes and ultrasonication", 《J. MATER. CHEM. A》 *
PARAG KANTHALE ET AL: "Sonoluminescence, sonochemistry (H2O2 yield) and bubble dynamics: Frequency and power effects", 《ULTRASONICS SONOCHEMISTRY》 *
郑伟等: "二维纳米材料MXene的研究进展", 《材料导报A：综述篇》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111634913A (en) * 2020-05-29 2020-09-08 太原理工大学 Stripping Ti3AlC2Preparation of high-purity few-layer Ti3C2Method of Tx slice
CN111785534A (en) * 2020-06-08 2020-10-16 华中科技大学 Method for immobilizing MXene by ionic liquid covalent bonding and product thereof
CN111785534B (en) * 2020-06-08 2021-12-31 华中科技大学 Method for immobilizing MXene by ionic liquid covalent bonding and product thereof
CN112107547A (en) * 2020-10-16 2020-12-22 温州医科大学附属第二医院（温州医科大学附属育英儿童医院） Hydrogel microsphere with photo-thermal responsiveness and preparation method and application thereof
CN112646094A (en) * 2020-12-19 2021-04-13 南京工业职业技术大学 Preparation method of wear-resistant and high-temperature-resistant window glass and window glass prepared by preparation method
CN112646094B (en) * 2020-12-19 2022-03-04 南京工业职业技术大学 Preparation method of wear-resistant and high-temperature-resistant window glass and window glass prepared by preparation method
CN112876585A (en) * 2021-01-19 2021-06-01 中南大学 Free radical polymerization initiated by Ag/MXene and preparation method of organic hydrogel
WO2022165989A1 (en) * 2021-02-05 2022-08-11 南方科技大学 Mxene material having organic chelating functional groups grafted on surface and preparation method therefor
CN113845633A (en) * 2021-10-08 2021-12-28 湖北三棵树新材料科技有限公司 Poly (hydroxyethyl methacrylate) grafted MXene, anticorrosive paint and preparation method thereof
CN113845633B (en) * 2021-10-08 2023-10-20 湖北三棵树新材料科技有限公司 Poly (hydroxyethyl methacrylate) -grafted MXene, anticorrosive paint and preparation method thereof
CN115068673A (en) * 2022-06-30 2022-09-20 吉林大学 Preparation method and application of MXene-based autocatalytic conductive hydrogel dressing
CN116082538A (en) * 2022-12-15 2023-05-09 德州学院 Method for initiating vinyl monomer polymerization by ultrasonic induced free radical

Also Published As

Publication number Publication date
CN110256611B (en) 2020-05-26

Similar Documents

Publication Publication Date Title
CN110256611A (en) A kind of application of MXene as radical initiator
CN108440696B (en) A kind of polyalcohol hydrogel and its preparation and application based on two-dimentional titanium carbide layer shape compound crosslink
JP2018111788A (en) Bond structure, and production method thereof
CN112876585B (en) Free radical polymerization initiated by Ag/MXene and preparation method of organic hydrogel
Bondar et al. Synthesis of cation-exchange adsorbent for anchoring metal ions by modification of poly (glycidyl methacrylate) chains grafted onto polypropylene fabric
JPH11322866A (en) Graft polymer
CN106012525A (en) Super-hydrophobic modification method for polytetrafluoroethylene (PTTE) fibers applied to oily sewage treatment
CN104888627A (en) Preparation method of hydrophilic polyester nonwoven composite membrane
Yamada et al. Radical polymerization of styrene mediated by 1, 3, 5-triphenylverdazyl
CN100383168C (en) Preparation method of repeatedly usable high oil-absorbent material
CA2518557A1 (en) Methods for producing macromolecule identifying polymers
WO2003040194A1 (en) (meth)acrylic acid (salt) polymer and process for production thereof
JPH01275639A (en) Surface modification
Fang et al. Emulsifier-free emulsion copolymerization of styrene and acrylamide using an amphoteric initiator
JPH0616738A (en) Method for grafting vinyl monomer onto polyvinyl alcohol
DE60329974D1 (en) FREE RADICAL RETROGRADGE POLYMERIZATION PROCESS
JP4616593B2 (en) Stereoregular polyacrylonitrile-based polymerization composition and method for producing the same
Omidian et al. Aqueous solution polymerization of neutralized acrylic acid using Na 2 S 2 O 5/(NH 4) 2 S 2 O 8 redox pair system under atmospheric conditions
Nayak et al. Grafting vinyl monomers onto silk fibers IV. Graft copolymerization of methyl methacrylate onto silk using bromate‐thiourea redox system
CN111333759A (en) Preparation method of zwitterionic polymer pattern on surface of solid substrate
Bai et al. Synthesis of microporous pH-sensitive polyacrylic acid/poly (ethylene glycol) hydrogels initiated by potassium diperiodatocuprate (III)
Misra et al. Grafting onto Starch: Part III-Graft Copolymerization of Vinyl Monomers onto Starch by Radical Initiator & Comparison of Monomer Reactivities
JP2002293801A (en) Modified cellulose and its production method
Zhiyu et al. The optimization of synthesizing graft copolymer of starch with vinyl monomers
Imoto et al. Vinyl Polymerization. 368. Polymerization of Methyl Methacrylate with the System of RNA, Water and Cu (II) Ion

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
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200526

Termination date: 20210610