CN108192003A - A kind of free radical thylene maleic acid anhydride copolymer and its synthetic method - Google Patents
A kind of free radical thylene maleic acid anhydride copolymer and its synthetic method Download PDFInfo
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- CN108192003A CN108192003A CN201711478167.9A CN201711478167A CN108192003A CN 108192003 A CN108192003 A CN 108192003A CN 201711478167 A CN201711478167 A CN 201711478167A CN 108192003 A CN108192003 A CN 108192003A
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- acid anhydride
- maleic acid
- anhydride copolymer
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Abstract
The present invention provides a kind of synthetic methods of free radical thylene maleic acid anhydride copolymer, belong to functional polymer chemical field.Thylene maleic acid anhydride copolymer and 4 hydroxyl, 2,2,6,6 tetramethyl piperidine nitrogen oxygen free radical esterification and obtain free radical thylene maleic acid anhydride copolymer by the present invention occurs.The present invention breaches the previous method for relying on complicated cumbersome monomer polymerization and preparing free radical fluidized polymer, only it need to pass through the easy esterification of a step, the free radical thylene maleic acid anhydride copolymer of preparation has molecular weight height, free-radical contents are higher on unit mass repetitive unit, and each monomer molecule free-radical contents may be up to 0.97；Electrolyte resistance is good, and solubility is only 0.59mg/mL in electrolyte solution；Synthetic method reaction simultaneously is simple, and mild condition, the extent of reaction is high, up to 54%.
Description
Technical field
The present invention relates to functional polymer chemical field more particularly to a kind of free radical thylene maleic acid anhydride copolymer and
Its synthetic method.
Background technology
Free radical fluidized polymer is as a kind of novel energy storage material, and fast with charge-discharge velocity, good cycling stability makes
With excellent properties such as long lifespans, it is with a wide range of applications in new energy field.
There are mainly two types of in the synthetic method for having reported free radical fluidized polymer：First, first synthesis is with free radical side group
Monomer, be then polymerized；Second is that monomer of the synthesis with piperidine structure, polymerization is then further oxidized again to obtain phase
The free radical polyalcohol answered.Xiaohuan Zhang et al. prepare 4- allene bases using second method by two-step reaction
Ether -2,2,6,6- tetramethyl piperidine monomers then in 100 DEG C of polymerisations, are further oxidized to corresponding free radical and gather
Close object (Zhang, X.；Li,H.；Li,L.；Lu,G.；Zhang,S.；Gu,L.；Xia,Y.；Huang,X.,Polyallene
with pendant nitroxyl radicals.Polymer 2008,49,(16),3393-3398.).But this was reacted
Journey is cumbersome, needs multistep that can just access.
Invention content
In view of this, present invention aims at provide a kind of free radical thylene maleic acid anhydride copolymer and its synthesis side
Method, method provided by the invention need to only pass through the easy esterification of a step.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of synthetic methods of free radical thylene maleic acid anhydride copolymer, include the following steps：
Under the catalytic action of catalyst system and catalyzing, by ethylene maleic acid anhydride copolymer and 4- hydroxyls -2,2,6,6- tetramethyl piperazines
Esterification occurs in polar organic solvent for pyridine NO free radical, obtains free radical thylene maleic acid anhydride copolymer.
Preferably, the weight average molecular weight of the ethylene maleic acid anhydride copolymer is 100000~450000.
Preferably, the ethylene maleic acid anhydride copolymer and 4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide
The amount ratio of substance is 1：2~2.5.
Preferably, the time of the esterification is 1~4 day.
Preferably, the polar organic solvent is acetone and dichloromethane, and the volume ratio of the acetone and dichloromethane is
10：1~70.
Preferably, the catalyst system and catalyzing of the esterification includes 4-dimethylaminopyridine and the chloro- 1- picolines iodine of 2-
Compound and triethylamine.
Preferably, the amount of the substance of the chloro- 1- methyl pyridinium iodides of the 4-dimethylaminopyridine, 2- and triethylamine it
Than for (1-8)：2：4.
Preferably, the amount of the substance of the catalyst system and catalyzing and 4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide
The ratio between amount of substance is (7-14)：(4-5).
The present invention also provides the free radical thylene maleic acid anhydride copolymer as made from above-mentioned synthetic method, by 4- hydroxyls
Base -2,2,6,6-tetramethylpiperidine nitroxide is grafted in ethylene maleic acid anhydride copolymer by esterification and obtained, institute
It states and includes the unit after following grafting on the main chain of free radical thylene maleic acid anhydride copolymer：
The grafting rate of the free radical thylene maleic acid anhydride copolymer is 20~60%.
Preferably, unit after being grafted shown in a structural formulas on the main chain of the free radical thylene maleic acid anhydride copolymer
Content is 1-20%, and the content of the unit after grafting shown in b structural formulas is the unit after grafting shown in 8~99%, c structural formulas
Content is 1~92%.
Advantageous effects：The present invention breaches the previous cumbersome monomer polymerization of complexity that relies on and prepares free radical fluidized polymer
Method, only need to be by the easy esterification of a step, while synthetic method reaction is simple, mild condition, the extent of reaction is high
Up to 54%.The free radical thylene maleic acid anhydride copolymer of preparation is high with molecular weight, free radical on unit mass repetitive unit
Content is higher, and each monomer molecule free-radical contents may be up to 0.97；Electrolyte resistance is good, is dissolved in electrolyte solution
Degree is only 0.59mg/mL.
Description of the drawings
Fig. 1 is when ethylene maleic acid anhydride polymer repetitive unit is grafted two molecule 4- hydroxyl -2,2,6,6- tetramethyl piperidines
Reaction principle figure during NO free radical；
Fig. 2 is the infrared spectrogram of free radical thylene maleic acid anhydride copolymer synthesized in 1~embodiment of embodiment 4；
Fig. 3 is that the magnetic susceptibility at low temperature of free radical thylene maleic acid anhydride copolymer synthesized in 1~embodiment of embodiment 4 is same
The change curve of temperature；
Fig. 4 is the grafting rate comparison of the free radical thylene maleic acid anhydride copolymer synthesized in 1~embodiment of embodiment 4
Figure；
Fig. 5 is the infrared spectrogram of free radical thylene maleic acid anhydride copolymer in 5~embodiment of embodiment 9；
Fig. 6 is the change that free radical thylene maleic acid anhydride copolymer magnetic susceptibility at low temperature is synthermal in 5~embodiment of embodiment 9
Change curve graph；
Fig. 7 is the comparison diagram of free radical thylene maleic acid anhydride copolymer grafting rate in 5~embodiment of embodiment 9；
Fig. 8 is the dissolving comparison diagram of free radical thylene maleic acid anhydride copolymer obtained in embodiment 7；
Fig. 9 is the ESR spectrograms of gained supernatant；
Standard curve prepared by the nmp solution that Figure 10 is standard TEMPO-OH.
Specific embodiment
The present invention provides a kind of synthetic methods of free radical thylene maleic acid anhydride copolymer, include the following steps：
Under the catalytic action of catalyst system and catalyzing, by ethylene maleic acid anhydride copolymer and 4- hydroxyls -2,2,6,6- tetramethyl piperazines
Esterification occurs in polar organic solvent for pyridine NO free radical, obtains free radical thylene maleic acid anhydride copolymer.
The present invention preferably by ethylene maleic acid anhydride copolymer, 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals,
Esterification is carried out after catalyst system and catalyzing and polar organic solvent mixing, obtains free radical thylene maleic acid anhydride copolymer.This hair
It is bright to have to ethylene maleic acid anhydride copolymer, 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals, catalyst system and catalyzing and polarity
The hybrid mode of solvent is not particularly limited, and selects hybrid mode well known to those skilled in the art.
In the present invention, the weight average molecular weight of the ethylene maleic acid anhydride copolymer is preferably 100000~450000, more
Preferably 200000~300000, most preferably 250000~300000.The present invention to the ethylene maleic acid anhydride copolymer and
The source of 4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide is not particularly limited, and commercial ethylene-maleic acid is selected to be total to
Polymers and 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals.
In the present invention, the ethylene maleic acid anhydride copolymer and 4- hydroxyls -2,2,6,6- tetramethyl piperidine nitrogen oxygen are free
The amount ratio of the substance of base is preferably 1：2~2.5, more preferably 1：2~2.2.
In the present invention, the time of the esterification is preferably 1~4 day, more preferably 1~2 day.The present invention is to esterification
The temperature of reaction is not particularly limited, in the present invention, it is preferred to be reacted at ambient temperature, does not need to heating or the drop of volume
Temperature.
In the present invention, the polar organic solvent is preferably acetone and dichloromethane, the acetone and dichloromethane
Volume ratio is preferably 1：0.1~7, more preferably 1：1~6.In the present invention, the dichloromethane is preferably super dry grade dichloromethane
Alkane, the present invention do not have special restriction to the source of the super dry grade dichloromethane, adopt well known to those skilled in the art commercially available
Commodity.In the present invention, the volume of the polar organic solvent and 4- hydroxyls -2,2,6,6- tetramethyl piperidine nitrogen oxygen are free
The ratio between amount of substance of base is preferably (80-160)：(12-15), more preferably 80：(12-15).
In the present invention, the catalyst system and catalyzing preferably includes 4-dimethylaminopyridine and the chloro- 1- picolines iodate of 2-
The ratio between the amount of substance of object and triethylamine, the chloro- 1- methyl pyridinium iodides of the 4-dimethylaminopyridine, 2- and triethylamine is excellent
It is selected as (1~8)：2：4, more preferably (3~5)：2：4.In the present invention, the amount of the total material of the catalyst system and catalyzing and 4- hydroxyls
The ratio between amount of substance of base -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals is preferably (7~14)：(4~5), more preferably (9
~14):(4~5).
In the present invention, the esterification is preferably reacted in nitrogen atmosphere.
After the esterification obtains esterification reaction solution, the present invention preferably post-processes esterification reaction solution, obtains certainly
By base thylene maleic acid anhydride copolymer, the post processing preferably includes：
By the esterification reaction solution through the mixed solvent in rotary distillation removing reaction system, free radical ethylene horse is obtained
Carry out acid anhydride copolymer crude product I；
It is centrifuged after the free radical thylene maleic acid anhydride copolymer crude product I is mixed with acetone, freedom is obtained by filtration
Base thylene maleic acid anhydride copolymer crude product II；
The free radical thylene maleic acid anhydride copolymer crude product II is washed successively with strong brine, distilled water and
Freeze-drying, obtains free radical thylene maleic acid anhydride copolymer.
In the present invention, the temperature distilled to the esterification reaction solution is preferably 40~80 DEG C, more preferably 60~
70 DEG C, the time of the distillation is preferably 10~40 minutes, more preferably 20~30 minutes.
After obtaining free radical thylene maleic acid anhydride copolymer crude product I, the present invention preferably will be by base ethylene maleic acid
Anhydride copolymer crude product I is centrifuged after being mixed with acetone, is filtered to remove acetone-insoluble impurity and unreacted 4- hydroxyl -2,2,
After 6,6- tetramethyl piperidine nitrogen oxygen free radicals and catalyst, obtain by base thylene maleic acid anhydride copolymer crude product II.This hair
The bright method to the centrifugation and filtering is not particularly limited, and selects method well known to those skilled in the art.The present invention
The dosage of acetone is not particularly limited, free radical thylene maleic acid anhydride copolymer crude product I can be dissolved.
After obtaining free radical thylene maleic acid anhydride copolymer crude product II, the present invention is preferably by free radical ethylene Malaysia
Acid anhydride copolymer crude product II is washed and is freeze-dried successively, obtains free radical thylene maleic acid anhydride copolymer.
The present invention is not particularly limited the method for the washing, selects washing methods well known to those skilled in the art i.e.
Can, the present invention is preferably washed with acetone, strong brine and distilled water successively.The present invention is to the acetone, strong brine and distillation
The dosage and washing times of water do not have special restriction, can remove unreacted TEMPO-OH, DMAP, triethylamine hydrochloride and
The impurity such as the by-product of CMPI.
The present invention is not particularly limited the method for the freeze-drying, selects freezing well known to those skilled in the art dry
Drying method.
The present invention also provides the free radical thylene maleic acid anhydride copolymer as made from above-mentioned synthetic method, by 4- hydroxyls
Base -2,2,6,6-tetramethylpiperidine nitroxide is grafted in thylene maleic acid anhydride copolymer by esterification and obtained, institute
It states and includes the unit after following grafting on the main chain of free radical thylene maleic acid anhydride copolymer：
The grafting rate of the free radical thylene maleic acid anhydride copolymer is 20~60%.
Unit after being grafted shown in a structural formulas on the main chain of the free radical thylene maleic acid anhydride copolymer in the present invention
Content be preferably 1~20%, more preferably 6~20%；The content of unit after grafting shown in b structural formulas is preferably 8~
99%, more preferably 80~99%；The content of unit after grafting shown in c structural formulas is preferably 1~92%, more preferably 1~
5%.
With reference to embodiment to free radical thylene maleic acid anhydride copolymer provided by the invention and preparation method thereof into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Solvent volume matches：
Acetone：70mL；
Super dry dichloromethane：10mL；
The amount proportioning of reaction raw materials substance：
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：3.6mmol；
The chloro- 1- methyl pyridinium iodides (CMPI) of acylating reagent 2-：6mmol；
Organic bases triethylamine：12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls -2,2,6,6- tetra-
Methyl piperidine NO free radical is dissolved completely in 40mL acetone；3.6mmol DMAP are dissolved in 30mL acetone, and drip in aforementioned
In acquired solution；18mmol triethylamines, 6mmol CMPI and 10mL dichloromethane are sequentially added, and room temperature is stirred in nitrogen atmosphere
Mix reaction；After reaction 1 day, the mixed solvent in reaction system is removed by rotary distillation first, is then soaked with 250mL acetone
Remaining solid and through being sufficiently stirred and centrifuging to remove acetone-insoluble impurity such as unreacted TEMPO-OH and catalyst
Deng.Acetone repeated washing three times after, using strong brine and pure water crude product, powder is can obtain through filtering and then being freeze-dried
Shape free radical thylene maleic acid anhydride copolymer, i.e. PETM-S1.
Embodiment 2
Solvent volume matches:
Acetone：60mL；
Super dry dichloromethane：20mL；
The amount proportioning of reaction raw materials substance
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：3.6mmol；
Chloro- 1- methyl pyridinium iodides (CMPI) 6mmol of acylating reagent 2-；
Organic bases triethylamine 12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls
- 2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals are dissolved completely in 40mL acetone；3.6mmol DMAP are dissolved in
20mL acetone, and drip in aforementioned acquired solution；18mmol triethylamines, 6mmol CMPI and 20mL dichloromethane are sequentially added,
And reaction is stirred at room temperature in nitrogen atmosphere；After reaction 1 day, the mixing removed first by rotary distillation in reaction system is molten
Agent then soaks remaining solid and through being sufficiently stirred and centrifuging to remove acetone-insoluble impurity such as with 250mL acetone
Unreacted TEMPO-OH and catalyst etc..Acetone repeated washing three times after, using strong brine and pure water crude product, through filtering
And then it is freeze-dried and is available from by base thylene maleic acid anhydride copolymer PETM-S2.
Embodiment 3
Different solvents composition is probed into
Solvent volume matches
Acetone：40mL；
Super dry dichloromethane：40mL；
The amount proportioning of reaction raw materials substance
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：3.6mmol；
Chloro- 1- methyl pyridinium iodides (CMPI) 6mmol of acylating reagent 2-；
Organic bases triethylamine 12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls -2,2,6,6- tetra-
Methyl piperidine NO free radical is dissolved completely in 40mL acetone；3.6mmol DMAP are dissolved in 20mL and surpass dry dichloromethane, and
It drips in aforementioned acquired solution；18mmol triethylamines, 6mmol CMPI and 20mL dichloromethane are sequentially added, and in nitrogen atmosphere
In reaction is stirred at room temperature；After reaction 1 day, the mixed solvent in reaction system is removed by rotary distillation first, then uses 250mL
Acetone soaks remaining solid and through being sufficiently stirred and centrifuging to remove acetone-insoluble impurity such as unreacted TEMPO-OH
With catalyst etc..Acetone repeated washing three times after, can through filtering and then being freeze-dried using strong brine and pure water crude product
Obtain free radical thylene maleic acid anhydride copolymer PETM-S3.
Embodiment 4
Different solvents composition is probed into
Solvent volume matches：
Acetone：20mL；
Super dry dichloromethane：60mL；
The amount proportioning of reaction raw materials substance
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：3.6mmol；
Chloro- 1- methyl pyridinium iodides (CMPI) 6mmol of acylating reagent 2-；
Organic bases triethylamine 12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls -2,2,6,6- tetra-
Methyl piperidine NO free radical is dissolved completely in 20mL acetone；3.6mmol DMAP are dissolved in 30mL and surpass dry dichloromethane, and
It drips in aforementioned acquired solution；18mmol triethylamines, 6mmol CMPI and 30mL dichloromethane are sequentially added, and in nitrogen atmosphere
In reaction is stirred at room temperature；After reaction 1 day, the mixed solvent in reaction system is removed by rotary distillation first, then uses 250mL
Acetone soaks remaining solid and through being sufficiently stirred and centrifuging to remove acetone-insoluble impurity such as unreacted TEMPO-OH
With catalyst etc..Acetone repeated washing three times after, can through filtering and then being freeze-dried using strong brine and pure water crude product
Obtain free radical thylene maleic acid anhydride copolymer PETM-S4.
Fig. 2 is the infrared spectrogram of free radical thylene maleic acid anhydride copolymer synthesized in 1~embodiment of embodiment 4.
Fig. 2 can illustrate, change the ratio of acetone and super dry dichloromethane in solvent, and TEMPO-OH successfully reacts and freely with PEM
Base activity does not change.
Fig. 3 is that the magnetic susceptibility at low temperature of free radical thylene maleic acid anhydride copolymer synthesized in 1~embodiment of embodiment 4 is same
The change curve of temperature.From the figure 3, it may be seen that the free radical thylene maleic acid anhydride copolymer tool that 1~embodiment of embodiment 4 synthesizes
There is good paramagnetic performance.
Fig. 4 is the grafting rate comparison of the free radical thylene maleic acid anhydride copolymer synthesized in 1~embodiment of embodiment 4
Figure.Calculate that free radical ethylene maleic acid acid anhydride is total to according to two kinds of characterization techniques of elemental analysis and PPMS (comprehensive physical property analysis system)
The comparison diagram of polymers (different solvents composition series) grafting rate is it is found that when the ratio of in the mixed solvent acetone and dichloromethane is 1：
When 1, grafting rate highest.
Embodiment 5
Solvent volume matches
Acetone：40mL；
Super dry dichloromethane：40mL；
The amount proportioning of reaction raw materials substance
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：3mmol；
Chloro- 1- methyl pyridinium iodides (CMPI) 6mmol of acylating reagent 2-；
Organic bases triethylamine 12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls -2,2,6,6- tetra-
Methyl piperidine NO free radical is dissolved completely in 40mL acetone；3mmol DMAP are dissolved in 20mL and surpass dry dichloromethane, and drip
In aforementioned acquired solution；12mmol triethylamines, 6mmol CMPI and 20mL dichloromethane are sequentially added, and in nitrogen atmosphere
Reaction is stirred at room temperature；After reaction 1 day, the mixed solvent in reaction system is removed by rotary distillation first, then with 250mL third
Ketone soak remaining solid and through being sufficiently stirred and centrifuging with remove acetone-insoluble impurity such as unreacted TEMPO-OH and
Catalyst etc..Acetone repeated washing three times after, using strong brine and pure water crude product, obtained through filtering and then being freeze-dried
Free radical thylene maleic acid anhydride copolymer PETM-D1.
Embodiment 6
Solvent volume matches:
Acetone：40mL；
Super dry dichloromethane：40mL；
The amount proportioning of reaction raw materials substance
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：6mmol；
Chloro- 1- methyl pyridinium iodides (CMPI) 6mmol of acylating reagent 2-；
Organic bases triethylamine 12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls -2,2,6,6- tetra-
Methyl piperidine NO free radical is dissolved completely in 40mL acetone；6mmol DMAP are dissolved in 20mL and surpass dry dichloromethane, and drip
In aforementioned acquired solution；12mmol triethylamines, 6mmol CMPI and 20mL dichloromethane are sequentially added, and in nitrogen atmosphere
Reaction is stirred at room temperature；After reaction 1 day, the mixed solvent in reaction system is removed by rotary distillation first, then with 250mL third
Ketone soak remaining solid and through being sufficiently stirred and centrifuging with remove acetone-insoluble impurity such as unreacted TEMPO-OH and
Catalyst etc..Acetone repeated washing three times after, using strong brine and pure water crude product, obtained through filtering and then being freeze-dried
Free radical thylene maleic acid anhydride copolymer PETM-D2.
Embodiment 7
Solvent volume matches：
Acetone：40mL；
Super dry dichloromethane：40mL；
The amount proportioning of reaction raw materials substance：
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：15mmol；
Chloro- 1- methyl pyridinium iodides (CMPI) 6mmol of acylating reagent 2-；
Organic bases triethylamine 12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls -2,2,6,6- tetra-
Methyl piperidine NO free radical is dissolved completely in 40mL acetone；15mmol DMAP are dissolved in 20mL and surpass dry dichloromethane, and drip
In aforementioned acquired solution；12mmol triethylamines, 6mmol CMPI and 20mL dichloromethane are sequentially added, and in nitrogen atmosphere
Reaction is stirred at room temperature；After reaction 1 day, the mixed solvent in reaction system is removed by rotary distillation first, then with 250mL third
Ketone soak remaining solid and through being sufficiently stirred and centrifuging with remove acetone-insoluble impurity such as unreacted TEMPO-OH and
Catalyst etc..Acetone repeated washing three times after, using strong brine and pure water crude product, obtained through filtering and then being freeze-dried
Free radical thylene maleic acid anhydride copolymer PETM-D3.
Embodiment 8
Solvent volume matches
Acetone：40mL；
Super dry dichloromethane：40mL；
The amount proportioning of reaction raw materials substance
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：21mmol；
Chloro- 1- methyl pyridinium iodides (CMPI) 6mmol of acylating reagent 2-；
Organic bases triethylamine 12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls -2,2,6,6- tetra-
Methyl piperidine NO free radical is dissolved completely in 40mL acetone；21mmol DMAP are dissolved in 20mL and surpass dry dichloromethane, and drip
In aforementioned acquired solution；12mmol triethylamines, 6mmol CMPI and 20mL dichloromethane are sequentially added, and in nitrogen atmosphere
Reaction is stirred at room temperature；After reaction 1 day, the mixed solvent in reaction system is removed by rotary distillation first, then with 250mL third
Ketone soak remaining solid and through being sufficiently stirred and centrifuging with remove acetone-insoluble impurity such as unreacted TEMPO-OH and
Catalyst etc..Acetone repeated washing three times after, using strong brine and pure water crude product, obtained through filtering and then being freeze-dried
Free radical thylene maleic acid anhydride copolymer PETM-D4.
Embodiment 9
Solvent volume matches：
Acetone：40mL；
Super dry dichloromethane：40mL；
The amount proportioning of reaction raw materials substance：
Commercial thylene maleic acid anhydride copolymer (Mw=10,0000-45,0000) (PEM) 6mmol；
4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide (TEMPO-OH) 12mmol；
Catalyst 4-dimethylaminopyridine (DMAP)：24mmol；
Chloro- 1- methyl pyridinium iodides (CMPI) 6mmol of acylating reagent 2-；
Organic bases triethylamine 12mmol；
It is matched according to the amount of substance, by 6mmol thylene maleic acid anhydride copolymers and 12mmol 4- hydroxyls -2,2,6,6- tetra-
Methyl piperidine NO free radical is dissolved completely in 40mL acetone；24mmol DMAP are dissolved in 20mL and surpass dry dichloromethane, and drip
In aforementioned acquired solution；12mmol triethylamines, 6mmol CMPI and 20mL dichloromethane are sequentially added, and in nitrogen atmosphere
Reaction is stirred at room temperature；After reaction 1 day, the mixed solvent in reaction system is removed by rotary distillation first, then with 250mL third
Ketone soak remaining solid and through being sufficiently stirred and centrifuging with remove acetone-insoluble impurity such as unreacted TEMPO-OH and
Catalyst etc..Acetone repeated washing three times after, using strong brine and pure water crude product, obtained through filtering and then being freeze-dried
Free radical thylene maleic acid anhydride copolymer PETM-D5.
Fig. 5 is the infrared spectrogram of free radical thylene maleic acid anhydride copolymer in 5~embodiment of embodiment 9.It can by Fig. 5
Know, change catalyst DMAP dosages, TEMPO-OH is successfully reacted with PEM and free radical activity does not change, gained free radical
Fluidized polymer structure is similar.
Fig. 6 is the change that free radical thylene maleic acid anhydride copolymer magnetic susceptibility at low temperature is synthermal in 5~embodiment of embodiment 9
Change curve graph.It will be appreciated from fig. 6 that the free radical thylene maleic acid anhydride copolymer that 5~embodiment of embodiment 9 synthesizes is with good
Paramagnetic performance.
Fig. 7 is the comparison diagram of free radical thylene maleic acid anhydride copolymer grafting rate in 5~embodiment of embodiment 9.By Fig. 7
It is found that calculate PETM (different DMAP dosages systems according to two kinds of characterization techniques of elemental analysis and PPMS (comprehensive physical property analysis system)
Row) grafting rate comparison diagram, illustrate work as the chloro- 1- methyl pyridinium iodides (CMPI) of catalyst DMAP, acylating reagent 2- and three
The ratio between amount of substance of ethamine is 4：1：The grafting rate highest of free radical thylene maleic acid anhydride copolymer when 2.
By the free radical thylene maleic acid anhydride copolymer PETM-D320mg obtained in embodiment 7 respectively in 5mLNMP (N-
Methyl pyrrolidone) and electrolyte solution in (1mol/LLiPF6 EC/DC/EMC volume ratios be 1：1：In 1 solvent) room temperature
Stirring is then centrifuged for gained supernatant for two days.Fig. 8 be embodiment 7 in obtain free radical thylene maleic acid anhydride copolymer it is molten
Solve comparison diagram.As shown in Figure 8, supernatant close to colourless, illustrates that PETM-D3 is practically insoluble in electrolyte solution in electrolyte.
Fig. 9 is the ESR spectrograms of gained supernatant；
Standard curve prepared by the nmp solution that Figure 10 is standard TEMPO-OH.
The free radical thylene maleic acid anhydride copolymer PETM-D3 obtained in embodiment 7 can be calculated with reference to Fig. 9 and Figure 10
Solubility in electrolyte solution is 0.59mg/mL, is not almost dissolved.
The above of the invention is only the preferred embodiment of the present invention, it is noted that for the common of the art
For technical staff, various improvements and modifications may be made without departing from the principle of the present invention, these are improved and profit
Decorations also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of free radical thylene maleic acid anhydride copolymer, includes the following steps：
Under the catalytic action of catalyst system and catalyzing, by ethylene maleic acid anhydride copolymer and 4- hydroxyls -2,2,6,6- tetramethyl piperidine nitrogens
Esterification occurs in polar organic solvent for oxygen radical, obtains free radical thylene maleic acid anhydride copolymer.
2. synthetic method according to claim 1, which is characterized in that the ethylene maleic acid anhydride copolymer is divided equally again
Son amount is 100000~450000.
3. synthetic method according to claim 1, which is characterized in that the ethylene maleic acid anhydride copolymer and 4- hydroxyls-
The amount ratio of the substance of 2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals is 1：2~2.5.
4. according to the synthetic method described in claims 1 to 3 any one, which is characterized in that the time of the esterification is 1
~4 days.
5. synthetic method according to claim 1, which is characterized in that the polar organic solvent is acetone and dichloromethane
The volume ratio of alkane, the acetone and dichloromethane is 10：1~70.
6. synthetic method according to claim 1, which is characterized in that the catalyst system and catalyzing include 4-dimethylaminopyridine,
The chloro- 1- methyl pyridinium iodides of 2- and triethylamine.
7. synthetic method according to claim 6, which is characterized in that the chloro- 1- methyl pyrrole of the 4-dimethylaminopyridine, 2-
The ratio between amount of substance of pyridine iodide and triethylamine is (1~8)：2：4.
8. according to the synthetic method described in claim 1,6 or 7, which is characterized in that the amount and 4- of the substance of the catalyst system and catalyzing
The ratio between amount of substance of hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals is
(7~14)：(4~5).
9. free radical thylene maleic acid anhydride copolymer made from synthetic method described in claim 1~8 any one, by 4- hydroxyls
Base -2,2,6,6-tetramethylpiperidine nitroxide is grafted in ethylene maleic acid anhydride copolymer by esterification and obtained, institute
It states and includes the unit after following grafting on the main chain of free radical thylene maleic acid anhydride copolymer：
The grafting rate of the free radical thylene maleic acid anhydride copolymer is 20~60%.
10. free radical thylene maleic acid anhydride copolymer according to claim 9, which is characterized in that the free radical
The content of unit is 1-20% after grafting shown in a structural formulas on the main chain of thylene maleic acid anhydride copolymer, is grafted shown in b structural formulas
The content of unit afterwards is that the content of the unit after grafting shown in 8~99%, c structural formulas is 1~92%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113555549A (en) * | 2021-07-21 | 2021-10-26 | 中山大学 | Composite electrode material and preparation method thereof |
| CN113880976A (en) * | 2021-11-18 | 2022-01-04 | 中山大学 | Application of ethylene-maleic anhydride alternating copolymer and hydrolysate thereof in preparation of silicon negative electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08505648A (en) * | 1992-11-24 | 1996-06-18 | ビーエーエスエフ アクチエンゲゼルシヤフト | Use as light stabilizers and stabilizers for maleimide-α-olefin copolymers and organic materials |
| US6372855B1 (en) * | 1998-08-31 | 2002-04-16 | The Yokohama Rubber Co., Ltd. | Polymer containing isobutylene as repeating unit and rubber composition containing the same |
| CN102471594A (en) * | 2009-07-30 | 2012-05-23 | 大日精化工业株式会社 | Method for improving weathering property of resinous member for solar light power generation, and resin-property improver for use therein |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08505648A (en) * | 1992-11-24 | 1996-06-18 | ビーエーエスエフ アクチエンゲゼルシヤフト | Use as light stabilizers and stabilizers for maleimide-α-olefin copolymers and organic materials |
| US6372855B1 (en) * | 1998-08-31 | 2002-04-16 | The Yokohama Rubber Co., Ltd. | Polymer containing isobutylene as repeating unit and rubber composition containing the same |
| CN102471594A (en) * | 2009-07-30 | 2012-05-23 | 大日精化工业株式会社 | Method for improving weathering property of resinous member for solar light power generation, and resin-property improver for use therein |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113555549A (en) * | 2021-07-21 | 2021-10-26 | 中山大学 | Composite electrode material and preparation method thereof |
| CN113880976A (en) * | 2021-11-18 | 2022-01-04 | 中山大学 | Application of ethylene-maleic anhydride alternating copolymer and hydrolysate thereof in preparation of silicon negative electrode material |
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