CN109053976A - A kind of multifunction polymer, preparation method and application - Google Patents
A kind of multifunction polymer, preparation method and application Download PDFInfo
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- CN109053976A CN109053976A CN201810648703.3A CN201810648703A CN109053976A CN 109053976 A CN109053976 A CN 109053976A CN 201810648703 A CN201810648703 A CN 201810648703A CN 109053976 A CN109053976 A CN 109053976A
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- polyethylene glycol
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- glycol dimethacrylate
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- 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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to polymer electrolyte fields, more particularly, to a kind of multifunction polymer, preparation method and are preparing the application in electrolyte.The polymer includes the chain arm of the cross-linked polymer core containing annular polyethylene glycol oxide and the polyethylene glycol oxide containing straight chain, and valence link is connected on cross-linked polymer core chain arm in all, and chain arm arranged radially is in star.The polymer of the multifunction is applied to prepare electrolyte, since the ring structure in polymer can accommodate more lithium ions, sodium ion or potassium ion, the staggeredly chain arm of star polymer keeps the conduction of ion highly efficient simultaneously, so obtains a kind of electrolyte for having multipath ion transmission channel.Ring-shaped P EO structure, cross-linked structure and star structure in the electrolyte can all reduce the crystallinity of PEO, so be expected to solve the problems, such as that lithium ion mobility is difficult at room temperature, ionic conductivity is low.
Description
Technical field
The invention belongs to polymer electrolyte field, more particularly, to a kind of multifunction can promote lithium,
The polymer of sodium and potassium ions conduct, preparation method and application in the electrolyte.
Background technique
The energy is always a part indispensable during human society is produced, lived.Limited earth resource forces people
Various methods are constantly looked for improve the utilization rate to the energy, up to ten thousand economy is arrived in fact up to thousands of times using charge and discharge number
It is one of effective approach with type rechargeable battery.Compared with traditional lead-acid battery and nickel-cadmium cell, lithium ion battery is with its height
The advantages that energy density, low self-discharge rate, memory-less effect, is applied in people's lives more and more widely.Electrolyte is lithium
Critical material in ion battery.The lithium battery of large-scale commercial generallys use liquid electrolyte at present, easily reveals, is inflammable
The safety problems such as burning, explosive constrain this and electrolytelike further apply.And solid polymer electrolyte has safety
Can it is good, energy density is high, operating temperature section is wide, the advantages that having extended cycle life, have highly important application prospect.
Polyethylene oxide base solid polymer electrolyte is a kind of polymer electrolyte of research earliest, most, but
The problems such as lithium ion mobility is difficult at room temperature caused by its high crystalline, ionic conductivity is low has to be solved.In previous research
It is middle reduce PEO crystallinity method have physical method as be blended, addition nanoparticle and chemical method such as block polymer synthesis,
Cross-linked polymer etc., but the lithium ion mobility caused by the high crystalline for solving polyethylene glycol oxide based polyalcohol is difficult, ion
The upper effect of the problems such as conductivity is low is not ideal enough.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of multifunction polymer, its system
Preparation Method and its application in the electrolyte, its object is to contain annular polyethylene glycol oxide (PEO) structure by design construction
The star polymer of the chain arm of cross-linked polymer core and the polyethylene glycol oxide containing straight chain composition, is used for preparing electrolyte, thus
Solve lithium ion mobility caused by the high crystalline of the polyethylene glycol oxide based polyalcohol of the prior art is difficult, ionic conductivity is low etc.
The technical issues of.
To achieve the above object, according to one aspect of the present invention, a kind of multifunction polymer, the polymer are provided
Chain arm including the cross-linked polymer core containing annular polyethylene glycol oxide and the polyethylene glycol oxide containing straight chain, the chain arm pass through covalent bond
It is connected on the cross-linked polymer core, the chain arm structure that the cross-linked polymer core containing annular polyethylene glycol oxide is connect with periphery
At star polymer.
Preferably, shown in the polymer molecular structure general formula such as formula (one):
Wherein, the integer that x:y=1:4~1:5, z are 1~11, R1、R2……RmFor the chain arm, m is not less than 30
Integer, shown in the general structure of the chain arm such as formula (two):
Wherein, the integer that n is 22~113.
Preferably, the cross-linked polymer core containing annular polyethylene glycol oxide is the esters of acrylic acid list by both ends with double bond
Body and cross-linking agents obtain, wherein acrylic ester monomer of the both ends with double bond is glycol dimethacrylates
Ester, shown in molecular structure such as formula (three):
Wherein, the integer that z is 1~11, the molecular weight of the polyethylene glycol dimethacrylate are 330~750；
Preferably, the crosslinking agent is ethylene glycol dimethacrylate, shown in molecular structure such as formula (four):
Other side according to the invention provides a kind of preparation method of multifunctional polymer, includes the following steps:
(1) polyethylene glycol monoether and acid binding agent are dispersed in organic solvent, to obtain polyethyleneglycol ethereal solution；In ice bath
Under the conditions of, brominated reagent is added dropwise into resulting polyethyleneglycol ethereal solution, after being dispersed with stirring, removes ice bath, at room temperature instead
It answers 12~24 hours, is separated by solid-liquid separation, is precipitated, macromole evocating agent will be obtained after gained washing of precipitate drying；
(2) polyethylene glycol dimethacrylate and alkali metal salt are dissolved in solvent, obtain polyethylene glycol diformazan
Base acrylate organic solution；
(3) macromole evocating agent for obtaining step (1) and low-valent metal catalyst, ligand divide under the conditions of anhydrous and oxygen-free
It dissipates in organic solvent, polyethylene glycol dimethyl allene described in ethylene glycol dimethacrylate and step (2) is then added
Acid esters organic solution carries out atom transition free radical polymerization reaction at 60 DEG C~80 DEG C, and the reaction time is 12~24 hours,
Reaction obtains the multifunction polymer.
Preferably, the polyethylene glycol monoether is that poly glycol monomethyl ether, polyethylene glycol monobutyl ether and polyethyleneglycol are pungent
One of ether is a variety of；The polyethylene glycol monoether relative molecular mass is 1000~5000；The acid binding agent be triethylamine,
One of pyridine and dimethylformamide are a variety of；The acid binding agent dosage be the polyethylene glycol monoether 200mol~
300mol%；The organic solvent is tetrahydrofuran and/or methylene chloride；The brominated reagent be 2- bromine isobutyl acylbromide and/or
2 bromo propionyl bromide, the brominated reagent dosage is 200mol~300mol% of the polyethylene glycol monoether.
Preferably, in step (2), the alkali metal salt is one of lithium iodide, sodium iodide and potassium iodide or a variety of；Institute
State 100~200mol% that alkali metal salt dosage is polyethylene glycol dimethacrylate；The polyethylene glycol dimethyl allene
The molecular weight of acid esters is 330~750；The organic solvent is toluene and/or acetonitrile.
Preferably, in step (3), the macromole evocating agent dosage is the 25 of the polyethylene glycol dimethacrylate
~45mol%；The low-valent metal catalyst be one of stannous chloride, frerrous chloride, cuprous bromide and ferrous bromide or
A variety of, the low-valent metal catalyst amount is 5~20mol% of the polyethylene glycol dimethacrylate；The ligand
For pentamethyl-diethylenetriamine and/or 2,2- bipyridyl, the ligand dosage is the polyethylene glycol dimethacrylate
10~40mol%；The ethylene glycol dimethacrylate dosage be the polyethylene glycol dimethacrylate 400~
500mol%；The organic solvent is toluene and/or acetonitrile.
Other side according to the invention provides the application of multifunction polymer described in one kind, is applied to system
Standby electrolyte.
Preferably, the multifunction polymer is applied to prepare electrolyte, comprising the following steps:
(1) the multifunction polymer and the polymer containing polyethylene glycol oxide are dissolved by the mass ratio of 1:1 to 1:3
In organic solvent, it is configured to the solution that concentration is 5wt%-15wt%；
(2) alkali metal salt is added into step (1) described solution, obtains mixed system after mixing, in the mixed system
The molar ratio of the cation of ethyoxyl and the alkali metal salt is 8:1 to 20:1, and casting film, dry that thickness is made after mixing evenly
The polymer dielectric film that degree is 100~300 microns.
Preferably, the polymer containing polyethylene glycol oxide be polyethylene glycol oxide, relative molecular mass be 300000~
7000000；The organic solvent is acetonitrile or/and tetrahydrofuran；The alkali metal salt is lithium salts, sodium salt or sylvite, the lithium
Salt is one of lithium perchlorate, LiBF4, lithium hexafluoro phosphate and bis trifluoromethyl imines sulphonyl lithium or a variety of, the sodium
Salt is one of sodium perchlorate, sodium hexafluoro phosphate and bis trifluoromethyl imines sulphonyl sodium or a variety of, and the sylvite is perchloric acid
One of potassium, Potassium Hexafluorophosphate and bis trifluoromethyl imines sulphonyl potassium are a variety of.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) multifunction polymer provided by the invention, the polymer are by containing annular polyethylene glycol oxide (PEO) structure
The star polymer of the chain arm of cross-linked polymer core and the polyethylene glycol oxide containing straight chain composition obtains wherein changing PEO linear chain structure
Annular corsslinking molecular core can reduce the crystallinity of PEO, while can also accommodate more lithium ions, sodium ion or potassium from
Son provides more ion transmission channels and ion delivering path；In addition, star polymer, which has, is not easy to crystallization and strand
Mobile fast advantage, by chain arm configuration interlaced in star polymer, the conduction of lithium ion, sodium ion or potassium ion is more
It is efficient；
(2) when being applied to the electrolyte of the cation containing different alkali metal salts, for different ions radius
Lithium ion, sodium ion and potassium ion, the present invention, can be with by the molecular weight of regulation monomer and the additive amount of monomer and crosslinking agent
The size for regulating and controlling PEO ring inside cross-linked polymer core, enables adaptation to the alkali metal cation with different ions radius
Complexing and dissociation；
(3) multifunction polymer provided by the invention is applied to the preparation of electrolyte, contains annular corsslinking molecular core
Star polymer is blended with polyoxyethylene polymer flexible, and star polymer has certain mechanical properties strength, polyoxy second
Alkene polymer provides more polyoxyethylene segments, comprehensive to obtain ionic conductivity height, the good solid polymer electricity of mechanical property
Xie Zhi；
(4) method for preparing polymer electrolytes of the present invention, reaction condition is mild, and operating method is relatively simple,
High conversion rate, and can be by selecting the PEGDMA of different molecular weight to regulate and control the structure of polymer, to control the electricity of polymer
Conductance and mechanical performance.
Detailed description of the invention
Fig. 1 is the core of the multifunction star polymer obtained using potassium ion as template prepared in the embodiment of the present invention 1
Magnetic resonance spectrogram, abscissa are chemical shift；
Fig. 2 is the purple of the multifunction star polymer obtained using lithium ion as template prepared in the embodiment of the present invention 2
External spectrum figure, abscissa are wavelength (nm)；
Fig. 3 is the multifunction star polymer obtained using sodium ion as template prepared in the embodiment of the present invention 5, by it
It is prepared as the DSC data of multifunction polymer dielectric film, abscissa is temperature (DEG C)；
Fig. 4 is that the conductivity of the polymer dielectric prepared in the embodiment of the present invention 6 varies with temperature figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
A kind of multifunction polymer proposed by the present invention, the polymer include the cross-linked polymeric containing annular polyethylene glycol oxide
The chain arm of object core and the polyethylene glycol oxide containing straight chain, chain arm are connected on cross-linked polymer core by covalent bond, chain arm " radial direction " row
It is listed in the periphery (diametrical direction that " radial direction " is not limited to stricti jurise here) of the cross-linked polymer core, it is described containing annular
The chain arm composition star polymer that the cross-linked polymer core of polyethylene glycol oxide and periphery are arranged in " radial direction ".The polymer is preferred
Shown in general formula of molecular structure such as formula (one):
Cross-linked polymer core in star polymer of the present invention includes the PEO structure of annular, wherein x:y=1:4~1:5,
This ratio can be regulated and controled by the ratio of control monomer and crosslinking agent, and the control of the ratio of x and y is for maintaining cross-linked polymer
PEO ring structure inside core is very crucial, if the control of the two ratio is improper, PEO ring can avalanche inside core；Z be 1~11 it is whole
Number, the value of z determine the size of PEO ring inside core, and then determine the whether easy complexing of alkali metal cation and dissociation, final to determine
The conductivity of the electrolyte using star polymer preparation is determined；R1、R2……RmFor the chain arm of the polyethylene glycol oxide containing straight chain, m
Numerical value for the integer not less than 30, m is determined by the dosage of reaction time and macromole evocating agent, can specifically pass through GPC points
Son measures examination and obtains, by GPC test in different molecular weight moiety content percentage, monomer and macromolecular after reaction can be obtained
Initiator conversion ratio, so that it is determined that the percentage of star polymer center and arm；Pass through number-average molecular weight, absolute weight average molecular
Star polymer chain arm number m can be calculated in numerical value；Shown in the preferred general structure of the chain arm such as formula (two),
Wherein, the integer that n is 22~113, the size of annular cross-linked polymer core and the length dimension of chain arm should not be too
Great disparity, therefore, the size of the ring of z, n and cross-linked polymer core need to control in a certain range, can guarantee that star is tied
The maintenance of structure, and then ensure higher conductivity.
Preferably, above-mentioned cross-linked polymer core can acrylic ester monomer by both ends with double bond and cross-linking agents obtain
It arrives, wherein acrylic ester monomer of the both ends with double bond is polyethylene glycol dimethacrylate, molecular structure such as formula (three) institute
Show:
Preferably, the molecular weight of polyethylene glycol dimethacrylate is 330~750, wherein the z model in z and formula (one)
Enclose it is identical, be 1~11 integer.This molecular weight ranges actually also determines the size of PEO ring inside cross-linked polymer core,
PEO ring is of moderate size in the molecular weight ranges, and ring structure is stablized.The crosslinking agent is preferably ethyleneglycol dimethacrylate
Ester, shown in molecular structure such as formula (four):
In the design of star polymer, cross-linked polymer core polymerize to obtain the present invention by monomer and crosslinking agent, as
Preferred scheme, is specifically designed monomer and crosslinking agent includes identical structural unit ethylene glycol dimethacrylate, so more
Be conducive to the compatibility of the two and the stability of cross-linked polymer.
The present invention provides a kind of preparation methods of above-mentioned multifunctional polymer, include the following steps:
(1) polyethylene glycol monoether and acid binding agent is evenly dispersed in organic solvent, obtain polyethyleneglycol ethereal solution；?
Under condition of ice bath, brominated reagent is added dropwise into resulting polyethyleneglycol ethereal solution, after being dispersed with stirring, ice bath is removed, in room temperature
Lower reaction 12~24 hours, is separated by solid-liquid separation, is precipitated, and will obtain macromole evocating agent after gained washing of precipitate drying, as
The chain arm of the polyethylene glycol oxide containing straight chain.The polyethylene glycol monoether is poly glycol monomethyl ether, polyethylene glycol monobutyl ether
With one of polyethyleneglycol octyl ether or a variety of, preferably poly glycol monomethyl ether, the polyethylene glycol monoether average molecular
Quality is 1000~5000；The acid binding agent is one of triethylamine, pyridine and dimethylformamide or a variety of, preferably three
Ethamine, the acid binding agent dosage are 200mol~300mol% of the polyethylene glycol monoether；The organic solvent is tetrahydro furan
It mutters and/or methylene chloride, preferably tetrahydrofuran；The brominated reagent be 2- bromine isobutyl acylbromide and/or 2 bromo propionyl bromide, preferably
For 2- bromine isobutyl acylbromide, the brominated reagent dosage is 200mol~300mol% of the polyethylene glycol monoether.
(2) polyethylene glycol dimethacrylate and alkali metal salt are dissolved in solvent, obtain polyethylene glycol diformazan
Base acrylate organic solution；Obtain the structure of the cross-linked polymer core of the small ring structures containing PEO.The alkali metal salt is
One of lithium iodide, sodium iodide and potassium iodide are a variety of；The alkali metal salt dosage is polyethylene glycol dimethacrylate
100~200mol%；The molecular weight of the polyethylene glycol dimethacrylate is 330~750；The organic solvent is
Toluene and/or acetonitrile.
(3) macromole evocating agent for obtaining step (1) and low-valent metal catalyst, ligand are equal under the conditions of anhydrous and oxygen-free
In organic solvent, polyethylene glycol dimethacrylate organic solution and second two described in step (2) is then added in even dispersion
Alcohol dimethylacrylate carries out atom transition free radical polymerization reaction at 60 DEG C~80 DEG C, and the reaction time is 12~24
Hour, reaction makes chain arm and cross-linked polymer verify existing covalently key connection, obtains the multifunction polymer.The macromolecular
Initiator amount is 25~45mol% of the polyethylene glycol dimethacrylate；The low-valent metal catalyst is chlorination
One of cuprous, frerrous chloride, cuprous bromide and ferrous bromide are a variety of, and the low-valent metal catalyst amount is described poly-
5~20mol% of ethylene glycol dimethacrylate；The ligand is pentamethyl-diethylenetriamine and/or 2,2- bipyridyl, institute
State 10~40mol% that ligand dosage is the polyethylene glycol dimethacrylate；The ethylene glycol dimethacrylate
Dosage is 400~500mol% of the polyethylene glycol dimethacrylate；The organic solvent is toluene and/or acetonitrile.
Multifunction polymer of the present invention, can be applied to prepare electrolyte.By the multifunction polymer application
In preparing electrolyte, comprising the following steps:
(1) the multifunction polymer and the polymer containing polyethylene glycol oxide are dissolved by the mass ratio of 1:1 to 1:3
In organic solvent, it is configured to the solution that concentration is 5wt%-15wt%；The polymer containing polyethylene glycol oxide is preferably poly-
Ethylene oxide, relative molecular mass are 300000~7000000；The organic solvent is acetonitrile or/and tetrahydrofuran.
(2) electrolyte lithium salt, electrolyte sodium salt or electrolyte sylvite are added into step (1) described solution, after mixing
To mixed system, the molar ratio of ethyoxyl and Li, Na or K are 8:1 to 20:1 in the mixed system, are cast into after mixing evenly
Film, the dry polymer dielectric film being made with a thickness of 100~300 microns.The lithium salts be lithium perchlorate, LiBF4,
One of lithium hexafluoro phosphate and bis trifluoromethyl imines sulphonyl lithium are a variety of, and the sodium salt is sodium perchlorate, sodium hexafluoro phosphate
With one of bis trifluoromethyl imines sulphonyl sodium or a variety of, the sylvite is potassium hyperchlorate, Potassium Hexafluorophosphate and double fluoroforms
One of base imines sulphonyl potassium is a variety of.
The polymer of multifunction proposed by the present invention is applied to prepare electrolyte, since the ring structure in polymer can
To accommodate more lithium ions, sodium ion or potassium ion, while the staggeredly chain arm of star polymer keeps the conduction of ion more high
Effect, so obtains a kind of electrolyte for having multipath ion transmission channel.Cross-linked structure in the electrolyte with
And star structure can all reduce the crystallinity of PEO, and it is low to be so expected to solve lithium ion mobility difficulty, ionic conductivity at room temperature
Problem.The multifunction electrolyte conductivity at room temperature is very high, and can also keep considerable conductivity under cryogenic.
The following are embodiments:
Shown in the multifunction polymer architecture such as formula (one) of embodiment 1 to embodiment 4 preparation:
Embodiment 1
A kind of multifunction polymer, the polymer is by the cross-linked polymer core of the molecule containing ring structure and containing polyoxyethylene
Alkene chain arm composition, the polyethylene glycol oxide chain arm are connected on the cross-linked polymer core by covalent bond, the chain arm diameter
It is in star to arrangement, structure is as shown above, wherein x:y=4:16, z=11, n=113.
The preparation method of multifunction polymer provided by the invention, comprising the following steps:
(1) taking 25 gram-molecular weights is that 5000 polyethyleneglycol octyl ether is dissolved in 45 milliliters of tetrahydrofuran, by 0.92
Gram dimethylformamide, which is added thereto, to be stirred, and polyethyleneglycol octyl ether solution is obtained.
(2) under condition of ice bath, the 2- bromine of 1.6mL is added dropwise into the polyethyleneglycol octyl ether solution obtained in step (1)
Isobutyl acylbromide, continues stirring until and is added dropwise, and after reacting 12 hours at room temperature, after reaction product filtering, filtrate added drop-wise is to excessively
In ice ether, macromole evocating agent is made after washing is dry in precipitation and separation.
(3) gained 14g macromole evocating agent and 40mg stannous chloride in step (2) are weighed in glove box, are separately taken
0.16mL pentamethyl-diethylenetriamine ligand is dissolved in the acetonitrile for distilling obtain in advance in reaction flask under the conditions of anhydrous and oxygen-free
In, polyethylene glycol dimethacrylate monomer (Mn=750) 6g for being dissolved with 1.99g potassium iodide is then added thereto, adds
It after entering 6.4g ethyleneglycol dimethacrylate crosslinking agent, freezes, vacuumize, applying argon gas, it is free that atom transfer is carried out at 80 DEG C
Base polymerization reaction, reaction time are 24 hours, and reaction product separation is dried to obtain the multifunction polymer.
Fig. 1 is that (polymer is this reality to the star polymer manufactured in the present embodiment obtained using potassium ion as template in Fig. 1
Apply the star polymer that example is prepared) nmr spectrum, abscissa is chemical shift；It will be seen from figure 1 that polymerizeing
When potassium iodide being added in object, due to the coordination of potassium iodide and polymer ring structures, in the chemical shift section of 3.5-4
There is a new small peak, this section is to the ethoxy segment in emergencing copolymer, it was demonstrated that deposit really in band star polymer
In the structure of ring.
Embodiment 2
A kind of multifunction polymer, the polymer is by the cross-linked polymer core of the molecule containing ring structure and containing polyoxyethylene
Alkene chain arm composition, the polyethylene glycol oxide chain arm are connected on the cross-linked polymer core by covalent bond, the chain arm diameter
It is in star to arrangement, structure is as shown above, wherein x:y=4:18, z=6, n=45, m are greater than 30.
The preparation method of multifunction polymer provided by the invention, comprising the following steps:
(1) taking 20 gram-molecular weights is that 2000 poly glycol monomethyl ether is dissolved in 45 milliliters of tetrahydrofuran, by 2.02
Gram triethylamine, which is added thereto, to be stirred, and poly glycol monomethyl ether solution is obtained.
(2) under condition of ice bath, the 2- bromine of 2.56mL is added dropwise into the poly glycol monomethyl ether solution obtained in step (1)
Isobutyl acylbromide, continues stirring until and is added dropwise, and after reacting 18 hours at room temperature, after reaction product filtering, filtrate added drop-wise is to excessively
In ice ether, macromole evocating agent is made after washing is dry in precipitation and separation.
(3) gained 4g macromole evocating agent, 114mg cuprous bromide in step (2) are weighed in glove box, separately take 0.32mL
Pentamethyl-diethylenetriamine ligand is dissolved in the acetonitrile for distilling obtain in advance, so in reaction flask under the conditions of anhydrous and oxygen-free
Polyethylene glycol dimethacrylate monomer (Mn=550) 4.4g for being dissolved with 1.07g lithium iodide is added thereto afterwards, is added
It after 7.2g ethyleneglycol dimethacrylate crosslinking agent, freezes, vacuumize, applying argon gas, atom transferred free radical is carried out at 70 DEG C
Polymerization reaction, reaction time are 24 hours, and reaction product separation is dried to obtain the multifunction polymer.
Fig. 2 is manufactured in the present embodiment to obtain the purple of (multifunction polymer) star polymer by template of lithium ion
External spectrum figure, abscissa are wavelength (nm)；It can be seen that only ultraviolet absorption peak is very weak in the presence of lithium iodide, and only polymer
In the presence of almost without ultraviolet absorption peak, and when lithium iodide and polymer exist simultaneously, ultraviolet absorption peak is very strong, can prove
Ring structure and lithium cation coordination are to absorption peak reinforcement.
Embodiment 3
A kind of multifunction polymer, the polymer is by the cross-linked polymer core of the molecule containing ring structure and containing polyoxyethylene
Alkene chain arm composition, the polyethylene glycol oxide chain arm are connected on the cross-linked polymer core by covalent bond, the chain arm diameter
It is in star to arrangement, structure is as shown above, wherein x:y=4:20, z=1, n=45, m are greater than 30.
The preparation method of multifunction polymer provided by the invention, comprising the following steps:
(1) taking 20 gram-molecular weights is that 2000 polyethylene glycol monobutyl ether is dissolved in 45 milliliters of methylene chloride, by 2.37
Gram pyridine, which is added thereto, to be stirred, and polyethylene glycol monobutyl ether solution is obtained.
(2) under condition of ice bath, the 2- bromine of 3.15mL is added dropwise into the polyethylene glycol monobutyl ether solution obtained in step (1)
Propionyl bromide is continued stirring until and is added dropwise, after reacting 24 hours at room temperature, after reaction product filtering, and filtrate added drop-wise to excessive ice
In ether, macromole evocating agent is made after washing is dry in precipitation and separation.
(3) the 2 of gained 8g macromole evocating agent in step (2), 345mg ferrous bromide and 250mg are weighed in glove box,
2- bipyridine ligand is dissolved in the organic solvent toluene being evaporated under reduced pressure in advance, so in reaction flask under the conditions of anhydrous and oxygen-free
Polyethylene glycol dimethacrylate monomer (Mn=330) 2.64g for being dissolved with 2.4g sodium iodide is added thereto afterwards, 8g is added
It after ethyleneglycol dimethacrylate crosslinking agent, freezes, vacuumize, applying argon gas, atom transfer radical polymerization is carried out at 60 DEG C
Reaction, reaction time are 18 hours, and reaction product separation is dried to obtain the multifunction polymer.
Embodiment 4
A kind of multifunction polymer, the polymer is by the cross-linked polymer core of the molecule containing ring structure and containing polyoxyethylene
Alkene chain arm composition, the polyethylene glycol oxide chain arm are connected on the cross-linked polymer core by covalent bond, the chain arm diameter
It is in star to arrangement, structure is as shown above, wherein x:y=4:18, z=6, n=22, m are greater than 30.
(1) taking 10 gram-molecular weights is that 1000 poly glycol monomethyl ether is dissolved in 45 milliliters of tetrahydrofuran, by 2.02
Gram triethylamine, which is added thereto, to be stirred, and poly glycol monomethyl ether solution is obtained.
(2) under condition of ice bath, the 2- bromine of 2.56mL is added dropwise into the poly glycol monomethyl ether solution obtained in step (1)
Isobutyl acylbromide, continues stirring until and is added dropwise, and after reacting 18 hours at room temperature, after reaction product filtering, filtrate added drop-wise is to excessively
In ice ether, macromole evocating agent is made after washing is dry in precipitation and separation.
(3) gained 0.2g macromole evocating agent, 20.3mg frerrous chloride in step (2) are weighed in glove box, separately take 32 μ
L pentamethyl-diethylenetriamine ligand is dissolved in the acetonitrile for distilling obtain in advance, so in reaction flask under the conditions of anhydrous and oxygen-free
Polyethylene glycol dimethacrylate monomer (Mn=550) 0.44g for being dissolved with 0.107g lithium iodide is added thereto afterwards, is added
It after 0.72g ethyleneglycol dimethacrylate crosslinking agent, freezes, vacuumize, applying argon gas, atom transferred free radical is carried out at 70 DEG C
Polymerization reaction, reaction time are 24 hours, and reaction product separation is dried to obtain the multifunction polymer.
Embodiment 5
The multifunction polymer can be applied to prepare electrolyte.Preparation method includes the following steps:
Multifunction polymer prepared by embodiment 3 is molten according to mass ratio 1:1 with 600000 molecular weight polyoxyethylene ethylene
Solution is configured to the solution of 10wt% in organic solvent tetrahydrofuran, adds by ethyoxyl/Na molar ratio in polymer for 16:1
Enter sodium perchlorate, after mixing evenly casting film, the polymer dielectric film with a thickness of 180 microns is sufficiently obtained after drying.
Fig. 3 is the DSC of multifunction polymer dielectric film manufactured in the present embodiment Yu pure polyethylene oxide electrolyte film
Figure, it can be seen that the glass transition temperature of multifunction polymer dielectric film is -45 DEG C, and pure polyethylene oxide electrolyte film
Glass transition temperature is -33 DEG C, and multifunction polymeric dielectric film is compared to pure polyethylene oxide electrolyte film glass temperature
Reduction and multifunction polymer dielectric film in melting peak disappearance illustrate prepare multifunction polymer dielectric film can
To reduce crystallinity, promote Ion transfer.
Embodiment 6
The multifunction polymer can be applied to prepare electrolyte.Preparation method includes the following steps:
Multifunction polymer prepared by embodiment 2 is molten according to mass ratio 1:1 with 600000 molecular weight polyoxyethylene ethylene
Solution is configured to the solution of 10wt% in organic solvent acetonitrile, is that height is added in 16:1 by ethyoxyl/Li molar ratio in polymer
Lithium chlorate, casting film, sufficiently obtains the polymer dielectric film with a thickness of 150 microns after mixing evenly after drying.
Other steps are identical, be not added that metal salt is prepared during polymer polymerizing be exactly not band star it is poly-
Object is closed, macromole evocating agent is changed into common initiator such as 2- isobutyl ethyl bromide and obtains being exactly band cross-linked polymer.System
It is as shown in Figure 4 that the conductivity of standby electrolyte varies with temperature curve, it can be seen that the electricity of band star polymer of the invention
Conductance is higher than not band star polymer and band cross-linked polymer, illustrates star structure and ring junction in the Patent design structure
Structure is conducive to lithium ion conduction really to which conductivity improves.
Embodiment 7
The multifunction polymer can be applied to prepare electrolyte.Preparation method includes the following steps:
Multifunction polymer prepared by embodiment 1 is molten according to mass ratio 1:3 with 7000000 molecular weight polyoxyethylene ethylene
Solution is configured to the solution of 10wt% in organic solvent acetonitrile, is that 12:1 addition is double by ethyoxyl/K molar ratio in polymer
Trifluoromethanesulfonimide potassium, casting film, sufficiently obtains the polymer dielectric with a thickness of 220 microns after mixing evenly after drying
Film.
Embodiment 8
The multifunction polymer can be applied to prepare electrolyte.Preparation method includes the following steps:
Multifunction polymer prepared by embodiment 4 is molten according to mass ratio 1:1 with 300000 molecular weight polyoxyethylene ethylene
Solution is configured to the solution of 10wt% in organic solvent tetrahydrofuran, adds by ethyoxyl/Li molar ratio in polymer for 20:1
Enter LiBF4, after mixing evenly casting film, the polymer dielectric film with a thickness of 200 microns is sufficiently obtained after drying.
The polymer dielectric film prepared by embodiment, compared to dielectric film prepared by pure polyethylene glycol oxide,
Mechanical performance and room-temperature conductivity have a certain upgrade.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of multifunction star polymer, which is characterized in that the polymer includes that the crosslinking containing annular polyethylene glycol oxide is poly-
The chain arm of object core and the polyethylene glycol oxide containing straight chain is closed, the chain arm is connected on the cross-linked polymer core by covalent bond, institute
It states the chain arm that the cross-linked polymer core containing annular polyethylene glycol oxide is connect with periphery and constitutes star polymer.
2. polymer as described in claim 1, which is characterized in that shown in the polymer molecular structure general formula such as formula (one):
Wherein, the integer that x:y=1:4~1:5, z are 1~11, R1、R2……RmFor the chain arm, m is the integer not less than 30,
Shown in the general structure of the chain arm such as formula (two):
Wherein, the integer that n is 22~113.
3. polymer as described in claim 1, which is characterized in that the cross-linked polymer core containing annular polyethylene glycol oxide is
Acrylic ester monomer and cross-linking agents by both ends with double bond obtain, wherein esters of acrylic acid of the both ends with double bond
Monomer is polyethylene glycol dimethacrylate, shown in molecular structure such as formula (three):
Wherein, the integer that z is 1~11；The crosslinking agent is preferably ethylene glycol dimethacrylate, molecular structure such as formula (four)
It is shown:
4. a kind of preparation method of multifunction star-type polymer, which comprises the steps of:
(1) polyethylene glycol monoether and acid binding agent are dispersed in organic solvent, to obtain polyethyleneglycol ethereal solution；In condition of ice bath
Under, brominated reagent is added dropwise into resulting polyethyleneglycol ethereal solution, after being dispersed with stirring, removes ice bath, reacts 12 at room temperature
It~24 hours, is separated by solid-liquid separation, is precipitated, macromole evocating agent will be obtained after gained washing of precipitate drying；
(2) polyethylene glycol dimethacrylate and alkali metal salt are dissolved in solvent, obtain polyethylene glycol dimethyl propylene
Olefin(e) acid ester organic solution；
(3) macromole evocating agent that step (1) obtains is dispersed under the conditions of anhydrous and oxygen-free with low-valent metal catalyst, ligand
In organic solvent, polyethylene glycol dimethacrylate described in ethylene glycol dimethacrylate and step (2) is then added
Organic solution carries out atom transition free radical polymerization reaction at 60 DEG C~80 DEG C, and the reaction time is 12~24 hours, reaction
Obtain the multifunction polymer.
5. preparation method as claimed in claim 4, in step (1), the polyethylene glycol monoether is poly glycol monomethyl ether, poly-
One of ethylene glycol monobutyl ether and polyethyleneglycol octyl ether are a variety of；The acid binding agent is triethylamine, pyridine and dimethyl methyl
One of amide is a variety of；The acid binding agent dosage is 200mol~300mol% of the polyethylene glycol monoether；The bromine
It is 2- bromine isobutyl acylbromide and/or 2 bromo propionyl bromide for reagent, the brominated reagent dosage is the polyethylene glycol monoether
200mol~300mol%.
6. preparation method as claimed in claim 4, which is characterized in that in the step (2), the alkali metal salt is iodate
One of lithium, sodium iodide and potassium iodide are a variety of；The alkali metal salt dosage is the 100 of polyethylene glycol dimethacrylate
~200mol%；The molecular weight of the polyethylene glycol dimethacrylate is 330~750；The organic solvent is toluene
And/or acetonitrile.
7. preparation method as claimed in claim 4, which is characterized in that in the step (3), the macromole evocating agent dosage
For 25~45mol% of the polyethylene glycol dimethacrylate；The low-valent metal catalyst is stannous chloride, protochloride
One of iron, cuprous bromide and ferrous bromide are a variety of, and the low-valent metal catalyst amount is the polyethylene glycol diformazan
5~20mol% of base acrylate；The ligand is pentamethyl-diethylenetriamine and/or 2,2- bipyridyl, the ligand dosage
For 10~40mol% of the polyethylene glycol dimethacrylate；The ethylene glycol dimethacrylate dosage is described
400~500mol% of polyethylene glycol dimethacrylate；The organic solvent is toluene and/or acetonitrile.
8. the application of the multifunction star polymer as described in claims 1 to 3 any one, which is characterized in that be applied to
Prepare electrolyte.
9. application as claimed in claim 8, which is characterized in that the multifunction polymer is applied to prepare electrolyte,
The following steps are included:
(1) the multifunction polymer as described in any one of claims 1 to 3 and the polymer containing polyethylene glycol oxide are pressed 1:
1 to 1:3 mass ratio dissolution in organic solvent, is configured to the solution that concentration is 5wt%-15wt%；
(2) alkali metal salt is added into step (1) described solution, mixed system, ethoxy in the mixed system is obtained after mixing
The molar ratio of the cation of base and the alkali metal salt is 8:1 to 20:1, after mixing evenly casting film, it is dry be made with a thickness of
100~300 microns of polymer dielectric film.
10. application as claimed in claim 9, which is characterized in that the polymer containing polyethylene glycol oxide is polyethylene glycol oxide,
Its relative molecular mass is 300000~7000000；The organic solvent is acetonitrile or/and tetrahydrofuran；The alkali metal salt
For lithium salts, sodium salt or sylvite, the lithium salts is lithium perchlorate, LiBF4, lithium hexafluoro phosphate and bis trifluoromethyl imines sulphur
One of acyl lithium is a variety of, and the sodium salt is one in sodium perchlorate, sodium hexafluoro phosphate and bis trifluoromethyl imines sulphonyl sodium
Kind is a variety of, and the sylvite is one of potassium hyperchlorate, Potassium Hexafluorophosphate and bis trifluoromethyl imines sulphonyl potassium or a variety of.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111624828A (en) * | 2020-05-18 | 2020-09-04 | 电子科技大学 | Novel gel electrolyte and application thereof in all-solid-state electrochromic device |
| CN111628216A (en) * | 2020-05-18 | 2020-09-04 | 华中科技大学 | Gel polymer electrolyte, preparation method and application thereof |
| CN113956478A (en) * | 2021-10-29 | 2022-01-21 | 汕头大学 | Polymer solid electrolyte and preparation method and application thereof |
| CN114230739A (en) * | 2021-12-14 | 2022-03-25 | 西安交通大学 | Linear-nonlinear block polymer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962726A (en) * | 2006-12-08 | 2007-05-16 | 西南大学 | Stellate reticulum solid or gel polymer electrolyte |
| CN101087823A (en) * | 2004-10-25 | 2007-12-12 | 卢布里佐尔公司 | Star polymers and compositions thereof |
| CN103327966A (en) * | 2010-11-15 | 2013-09-25 | 新泽西鲁特格斯州立大学 | Multifunctional biodegradable peg nanocarrier-based hydrogels for preventing hiv transmission |
| CN103682433A (en) * | 2012-09-26 | 2014-03-26 | 中国科学院研究生院 | Multi-arm star-shaped block polymer based electrolyte and preparation method thereof |
| CN104151501A (en) * | 2014-08-04 | 2014-11-19 | 华中科技大学 | Polymer containing polyethylene oxide as well as preparation method and application thereof |
-
2018
- 2018-06-22 CN CN201810648703.3A patent/CN109053976B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087823A (en) * | 2004-10-25 | 2007-12-12 | 卢布里佐尔公司 | Star polymers and compositions thereof |
| CN1962726A (en) * | 2006-12-08 | 2007-05-16 | 西南大学 | Stellate reticulum solid or gel polymer electrolyte |
| CN103327966A (en) * | 2010-11-15 | 2013-09-25 | 新泽西鲁特格斯州立大学 | Multifunctional biodegradable peg nanocarrier-based hydrogels for preventing hiv transmission |
| CN103682433A (en) * | 2012-09-26 | 2014-03-26 | 中国科学院研究生院 | Multi-arm star-shaped block polymer based electrolyte and preparation method thereof |
| CN104151501A (en) * | 2014-08-04 | 2014-11-19 | 华中科技大学 | Polymer containing polyethylene oxide as well as preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111624828A (en) * | 2020-05-18 | 2020-09-04 | 电子科技大学 | Novel gel electrolyte and application thereof in all-solid-state electrochromic device |
| CN111628216A (en) * | 2020-05-18 | 2020-09-04 | 华中科技大学 | Gel polymer electrolyte, preparation method and application thereof |
| CN113956478A (en) * | 2021-10-29 | 2022-01-21 | 汕头大学 | Polymer solid electrolyte and preparation method and application thereof |
| CN113956478B (en) * | 2021-10-29 | 2023-05-16 | 汕头大学 | Polymer solid electrolyte and preparation method and application thereof |
| CN114230739A (en) * | 2021-12-14 | 2022-03-25 | 西安交通大学 | Linear-nonlinear block polymer and preparation method thereof |
| CN114230739B (en) * | 2021-12-14 | 2023-08-11 | 西安交通大学 | Linear-nonlinear block polymer and preparation method thereof |
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