CN106008795B - A kind of cyclic polymer can self-healing gel synthetic method - Google Patents
A kind of cyclic polymer can self-healing gel synthetic method Download PDFInfo
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- 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
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- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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Abstract
The present invention relates to a kind of cyclic polymer can self-healing gel synthetic method, comprise the following steps：The linear furans random copolymer containing furans is synthesized using atom transfer radical polymerization method；Linear furans random copolymer progress azido reaction is obtained into the linear furans random copolymer containing azido group；Cyclization is occurred into for the linear furans random copolymer containing azido group and obtains ring-type furans random copolymer；Ring-type furans random copolymer and BMI are subjected to diene synthesis reaction, obtaining ring-type can self-healing gel.A kind of ring-type of the present invention can self-healing gel synthetic method, reaction condition is gentle, reaction rate is fast, selectivity is high, yield is high and post processing is simple, suitable for industrialized production；And based on the reaction between cyclic polymer and furans and maleimide base group synthesized ring-type can self-healing gel, self-healing performance is good, has a good application prospect.
Description
Technical field
The present invention relates to macromolecule synthesising technology field, more particularly to a kind of ring-type can self-healing gel synthetic method.
Background technology
It is well known that the change of topological structure has a great influence to polymer performance.And cyclic polymer does not have end group, by
In its special topological structure with higher glass transition temperature, bigger diffusion coefficient, less hydrodynamics half
Footpath and stronger fluorescence property etc..
In addition, can self-healing gel be always scientist research focus.Due to can self-healing gel rubber material certain
Under the conditions of can realize selfreparing, to improve the service life of material, economizing on resources and environmental protection provides new method.
At present can the synthesis of self-healing gel rubber material be mostly based on linear polymer, and be almost not based on cyclic polymer
Self-healing gel report.It is primarily due to that the building-up process of cyclic polymer is more complicated, and difficulty is larger, is especially closing
During functional cyclic polymer, often with more side reactions.
So far, cycloaddition (CuAAc) cyclization of ATRP (ATRP) and nitrine-alkynes of copper catalysis
Method combination is the important means of synthesis of cyclic polymer.It is easy to operate and be used widely due to this method efficiency high.And furan
Mutter with the Diels-Alder of maleimide reactions due to invertibity, thus synthesis can in self-healing gel it is extensive
Use.
In view of drawbacks described above, the design people is actively subject to research and innovation, can self-healing to found a kind of cyclic polymer
The synthetic method of gel, make it with more the value in industry.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of cyclic polymer can self-healing gel synthesis
Method, this method technique is simple, combined coefficient is high.
The present invention cyclic polymer can self-healing gel synthetic method, comprise the following steps：
(1) furans vinyl derivative, acrylic ester copolymerization monomer, initiator, catalyst, the first part are dissolved in first
Organic solvent, ATRP (ATRP) reaction is carried out at 40 DEG C~80 DEG C and obtains linear furans random copolymerization
Thing；
(2) linear furans random copolymer, sodium azide, the phase transfer catalyst for obtaining step (1) are added to container
In, and the second organic solvent of addition and water are dissolved, and azido reaction is carried out at 20~50 DEG C and is obtained containing azido group
Linear furans random copolymer；
(3) the linear furans random copolymer containing azido group for obtaining step (2) is dissolved in the 3rd organic solvent and obtained
To the first solution, catalyst, Ligands and the 3rd organic solvent are made into the second solution, it is molten that the first solution is added drop-wise into second
In liquid, generation cyclization obtains ring-type furans random copolymer at 60 DEG C~100 DEG C；
(4) ring-type furans random copolymer that step (3) obtains, BMI are dissolved in the 4th organic solvent, had
Diene synthesis reaction (Diels-Alder reactions) is carried out at 30~80 DEG C after solvent volatilization, obtaining cyclic polymer can self-healing
Close gel.
Further, in step (1), furans vinyl derivative is acrylic acid chaff ester (FA) or methacrylic acid chaff ester
(FMA), the concrete structure formula of acrylic acid chaff ester (FA) and methacrylic acid chaff ester (FMA) is as follows：
Further, in step (1), acrylic ester copolymerization monomer is methyl methacrylate, methacrylic acid fourth
One or more in ester, methyl acrylate and butyl acrylate.
Further, in step (1), the first part is pentamethyl-diethylenetriamine, hexamethyl trien, two
Ethene triamine, N, N, N', N'- tetra- (2- picolyls) ethylenediamine, three (2- pyridylmethyls) amine, three (2- amino-ethyls) amine,
1,10- phenanthroline, Isosorbide-5-Nitrae, 8,11- tetramethyls-Isosorbide-5-Nitrae, the decane of 8,11- tetraazacyclododecane four and one kind or several in 2,2'- bipyridyl
Kind.
Further, in step (1), initiator is 2- isobutyl bromide alkynes propyl ester (PBMP) or 2- isobutyl bromide alkynes butyl esters
(BBMP), PBMP and BBMP concrete structure formula is as follows：
Further, catalyst is the one or more in stannous chloride, cuprous bromide and cuprous iodide.
Further, in step (1), the first organic solvent be toluene, methyl phenyl ethers anisole, benzene, paraxylene, ortho-xylene,
One kind in dimethyl sulfoxide or N,N-dimethylformamide.
Further, in step (1), in molar ratio, furans vinyl derivative:Acrylic ester copolymerization monomer:Trigger
Agent:Catalyst:First part=100:50~400:0.5~2:0.25~2:0.25~2, furans vinyl derivative has with first
The volume ratio of solvent is 50~300:100.
Further, in step (2), in molar ratio, linear random copolymer:Sodium azide:Phase transfer catalyst=
10:10~100:1~10, the volume ratio of the second organic solvent and water is 5~20:10.
Further, in step (2), phase transfer catalyst is 4-butyl ammonium hydrogen sulfate, four butyl bromation amine, trimethyl
One kind in benzyl ammonium chloride, tri-n-octyl methyl ammonium chloride, cetyl trimethylammonium bromide and triethyl benzyl ammonia chloride or
It is several.
Further, in step (2), the second organic solvent is dichloromethane, chloroform, carbon tetrachloride, acetic acid second
One kind in ester, toluene or methyl phenyl ethers anisole.
Further, in step (3), catalyst is one kind or several in stannous chloride, cuprous bromide and cuprous iodide
Kind.
Further, in step (3), Ligands are pentamethyl-diethylenetriamine, hexamethyl trien, two
Ethene triamine, N, N, N', N'- tetra- (2- picolyls) ethylenediamine, three (2- pyridylmethyls) amine, three (2- amino-ethyls) amine,
1,10- phenanthroline, Isosorbide-5-Nitrae, 8,11- tetramethyls-Isosorbide-5-Nitrae, the decane of 8,11- tetraazacyclododecane four and one kind or several in 2,2'- bipyridyl
Kind.
Further, in step (3), the 3rd organic solvent is toluene, dimethyl sulfoxide, DMF, two
One kind in chloromethanes, chloroform or benzene.
Further, in step (3), in molar ratio, the linear furans random copolymer containing azido group:Catalyst:
Ligands=1:25~100:25~200.
Further, in step (3), the concentration of the linear furans random copolymer containing azido group is 10-3~10- 2G/mL, rate of addition are 0.1~1mL/min.
Further, in step (4), BMI is diphenyl methane dimaleimide (BMI) or 1,12- bis-
In (dimaleoyl imino) dodecane (12CBMI), concrete structure formula is as follows：
Further, in step (4), the 4th molten organic agent is in toluene, dichloro-benzenes, tetrahydrofuran, methyl phenyl ethers anisole or benzene
One kind.
Further, in step (4), the volatile organic solvent at 80 DEG C~100 DEG C.
Further, in step (4), can in mould of different shapes volatile organic solvent, make cyclic polymer
Can self-healing gel polymerisation into different shapes.
Further, in step (4), furan group and BMI in ring-type furans random copolymer rub
You are than being 10:1~10:5.
The synthetic route of cyclic polymer is as follows in a wherein specific embodiment of the invention：
By such scheme, the present invention has advantages below：
Ring-type provided by the invention can self-healing gel synthetic method, successfully synthesize containing feature furan group
Cyclic polymer, have the advantages that reaction condition is gentle, reaction rate is fast, selectivity is high, yield is high and post processing is simple, be applicable
In industrialized production；Diels-Alder of the synthetic method based on cyclic polymer and furans and maleimide of the present invention
Reaction synthesized ring-type can self-healing gel, self-healing performance is good, has a good application prospect.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the SEC elution curve figures for the linear furans random copolymer that the present invention is obtained using ATRP polymerization method；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure for the linear furans random copolymer that the present invention is obtained using the method for ATRP polymerization；
Fig. 3 is the SEC elution curves of linear furans random copolymer and the linear furans random copolymer containing azido group
Figure；
Fig. 4 is the infrared spectrogram of linear furans random copolymer and the linear furans random copolymer containing azido group；
Fig. 5 is the SEC elution curves of linear furans random copolymer and ring-type furans random copolymer containing azido group
Figure；
Fig. 6 is the infrared spectrogram of linear furans random copolymer and ring-type furans random copolymer containing azido group；
Fig. 7 is the nucleus magnetic hydrogen spectrum figure of linear furans random copolymer and ring-type furans random copolymer containing azido group.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Embodiment 1
Cuprous bromide 0.0980g (0.69mmol), 0.1420g initiators PBMP are sequentially added into Su Lunke bottles
(0.69mmol), comonomer butyl acrylate 5mL (34.7mmol), 5.2770g acrylic acid chaff esters (34.7mmol) and
0.1600g the first part hexamethyl triens (0.69mmol), add toluene 10mL, by standard three times freezing-
After pumping-thaw cycles operation, bottle stopper is screwed.Then Su Lunke bottles are placed in 70 DEG C of oil bath pan, stir 24h, occurred
ATRP is reacted, and takes pipe, is precipitated by precipitating reagent of petroleum ether, and upper strata solvent is toppled over after standing, and it is surplus to add dichloromethane dissolving
Remaining solid, with the aqueous solution washing of disodium EDTA three times, mantoquita is removed, is dried, concentration, then sunk with petroleum ether
Form sediment, topple over upper solution, dry to obtain flaxen linear furans random copolymer.Fig. 1, Fig. 2 are the method using ATRP polymerization
The SEC elution curves figure and nucleus magnetic hydrogen spectrum figure of obtained linear furans random copolymer, from figure 1 it appears that successfully obtaining
The linear furans random copolymer of peak shape normal state, is further calculated by the integrated value of characteristic peak in Fig. 2 nucleus magnetic hydrogen spectrum figures
Into linear furans random copolymer, the number of furan units is 12.
The linear furans random copolymers (0.038mmol) of 0.2g, NaN are sequentially added into round-bottomed flask3 0.025g
(0.38mmol) and 0.0129g 4-butyl ammonium hydrogen sulfates (0.038mmol), and add isometric dichloromethane and water and make reaction
Thing is completely dissolved, 20 DEG C of stirring reaction 24h.By reaction solution liquid separation, dichloromethane layer is collected, and is washed three times, uses anhydrous slufuric acid
Sodium is dried, and is filtered, is rotated, precipitating, drying the linear furans random copolymer that must contain azido group.Fig. 3, Fig. 4 are linear furans
SEC elution curves figure and infrared spectrogram before and after random copolymer Azide, as can be seen from Figure 3 after azido reaction
The SEC elution curves of the obtained linear furans random copolymer containing azido group have almost no change, and illustrate azido reaction
During without occur side reaction；And in 2109cm in Fig. 4 infrared spectrograms-1There is characteristic peak in place, illustrates successfully to be contained
The linear furans random copolymer of azido group.
800mL toluene is added in 1000mL three-necked flask, reaction bulb is placed in 70 DEG C of oil bath pan, logical argon gas stirs
After mixing 2h, 0.143g catalyst CuBr (1mmol) and Ligands pentamethyl-diethylenetriamine 0.306mL is added into reaction bulb
(1.5mmol), the lower stirring 5h of argon gas protection.The linear furans random copolymer 0.1g (0.02mmol) containing azido group is taken to be dissolved in
20mL toluene, suck in 20mL syringe, with micro-injection pump into three-necked flask with 0.6mL/h speed injection, injection
24h is reacted after complete again.Reaction solution is rotated after removing toluene, a small amount of dichloromethane dissolving is added, with disodium ethylene diamine tetraacetate
Salt washing remove mantoquita three times, anhydrous sodium sulfate drying, filters, rotates, precipitating, being dried under vacuum to constant weight and obtain ring-type furans and be randomly total to
Polymers.Fig. 5-Fig. 7 is the SEC elution curves figure, infrared before and after the linear furans random copolymer cyclization containing azido group
Spectrogram and nucleus magnetic hydrogen spectrum figure.It can be seen that after annulation occurs：Fig. 5 SEC elution curves are integrally moved rearwards, Fig. 6
2109cm in infrared spectrogram-1The signal of alkynyl hydrogen in the absworption peak disappearance of the azido group at place and Fig. 7 nucleus magnetic hydrogen spectrum
It is wholly absent, illustrates successfully to have obtained ring-type furans random copolymer, and purity is very high.
By ring-type furans random copolymer 0.1g (0.019mmol) and 12CBMI 0.037g (0.1mmol) at 80 DEG C it is molten
In 1mL toluene, inject while hot in mould, toluene is evaporated at 100 DEG C, then recover to 30 DEG C of reaction 24h, obtain yellow ring-type and gather
Compound can self-healing gel.
Whole piece gel is taken, cuts a cross mouth on gel with pocket knife, gel is clamped with two pieces of quartz glass, is put into
24h is reacted in 130 DEG C of high temperature ovens, then 12h is reacted in 50 DEG C of baking ovens, it can be found that the cross recess of gel disappears after reaction
Lose, return to and just start the apperance without wound.The cyclic polymer gel for illustrating to obtain has can self-healing performance.
Embodiment 2
Stannous chloride (0.1725mmol), 0.0379g initiator Bs BMP are sequentially added into Su Lunke bottles
(0.1725mmol), comonomer methacrylic acid butyl ester 5mL (34.7mmol), 5.7975g methacrylic acid chaff esters
(34.7mmol) and first part three (2- pyridylmethyls) amine (0.1725mmol), adds methyl phenyl ethers anisole 30mL, by three times
After the operation of standard freezing-pumping-thaw cycles, bottle stopper is screwed.Then Su Lunke bottles are placed in 40 DEG C of oil bath pan, stirred
24h, ATRP reactions occur, takes pipe, is precipitated by precipitating reagent of petroleum ether, upper strata solvent is toppled over after standing, add dichloromethane
Alkane dissolves remaining solid, with the aqueous solution washing of disodium EDTA three times, removes mantoquita, dries, concentration, then uses stone
Oily ether precipitation, topples over upper solution, dries to obtain flaxen linear furans random copolymer.
The linear furans random copolymers (0.038mmol) of 0.2g, NaN are sequentially added into round-bottomed flask3 2.5g
(38mmol) and 0.0129g 4-butyl ammonium hydrogen sulfates (0.038mmol), and the water for the chloroform and 40mL for adding 10mL makes instead
Thing is answered to be completely dissolved, 50 DEG C of stirring reaction 24h.By reaction solution liquid separation, chloroform layer is collected, and wash three times, with anhydrous sulphur
Sour sodium is dried, and is filtered, is rotated, precipitating, drying the linear furans random copolymer that must contain azido group.
800mL dimethyl sulfoxides are added in 1000mL three-necked flask, reaction bulb are placed in 100 DEG C of oil bath pan, are led to
After argon gas stirring 2h, 0.286g catalyst CuBr (2mmol) and Ligands diethylenetriamine 8.16mL is added into reaction bulb
(40mmol), the lower stirring 5h of argon gas protection.The linear furans random copolymer 0.1g (0.02mmol) containing azido group is taken to be dissolved in
10mL dimethyl sulfoxide, suck in 10mL syringe, noted with micro-injection pump into three-necked flask with 0.1mL/h speed
Penetrate, react 24h after having injected again.Reaction solution is rotated after removing dimethyl sulfoxide, a small amount of dichloromethane dissolving is added, with ethylenediamine
Sequestrene AA washing removes mantoquita three times, anhydrous sodium sulfate drying, filters, rotates, precipitating, being dried under vacuum to constant weight and obtain ring-type
Furans random copolymer.
Ring-type furans random copolymer 0.1g (0.019mmol) and BMI 0.037g (0.1mmol) are dissolved at 80 DEG C
1mL tetrahydrofuran, inject while hot in mould, tetrahydrofuran is evaporated at 100 DEG C, then recover to 80 DEG C of reaction 18h, obtain yellow
Cyclic polymer can self-healing gel.
The present invention successfully synthesizes the cyclic polymer of the furan group containing feature, and is based on furan group and maleimide
The Diels-Alder reactions of amine groups are prepared for cyclic polymer can self-healing gel.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of cyclic polymer can self-healing gel synthetic method, it is characterised in that comprise the following steps：
(1) by furans vinyl derivative, acrylic ester copolymerization monomer, initiator, catalyst, that the first part is dissolved in first is organic
Solvent, progress polymerisation obtains linear furans random copolymer at 40 DEG C~80 DEG C；The initiator is 2- isobutyl bromides
Alkynes propyl ester or 2- isobutyl bromide alkynes butyl esters；
(2) the linear furans random copolymer, sodium azide, the phase transfer catalyst for obtaining step (1) are added to container
In, and the second organic solvent of addition and water are dissolved, and azido reaction is carried out at 20~50 DEG C, is obtained containing azido group
Linear furans random copolymer；
(3) the linear furans random copolymer containing azido group for obtaining step (2), which is dissolved in the 3rd organic solvent, obtains
One solution, catalyst, Ligands and the 3rd organic solvent are configured to the second solution, first solution are added drop-wise to described
In second solution, generation cyclization obtains ring-type furans random copolymer at 60 DEG C~100 DEG C；
(4) ring-type furans random copolymer that step (3) obtains, BMI are dissolved in the 4th organic solvent, You Jirong
Diene synthesis reaction is carried out at 30~80 DEG C after agent volatilization, obtaining the cyclic polymer can self-healing gel.
2. cyclic polymer according to claim 1 can self-healing gel synthetic method, it is characterised in that：In step
(1) in, the furans vinyl derivative is acrylic acid chaff ester or methacrylic acid chaff ester, and the acrylic ester copolymerization monomer is
One or more in methyl methacrylate, butyl methacrylate, methyl acrylate and butyl acrylate, described first matches somebody with somebody
Body is selected from pentamethyl-diethylenetriamine, hexamethyl trien, diethylenetriamine, N, N, N', N'- tetra- (2- picolyls)
Ethylenediamine, three (2- pyridylmethyls) amine, three (2- amino-ethyls) amine, 1,10- phenanthrolines, Isosorbide-5-Nitrae, 8,11- tetramethyls-Isosorbide-5-Nitrae, 8,
One or more in the decane of 11- tetraazacyclododecanes four and 2,2'- bipyridyl.
3. cyclic polymer according to claim 1 can self-healing gel synthetic method, it is characterised in that：In step
(1) in, the catalyst is the one or more in stannous chloride, cuprous bromide and cuprous iodide.
4. cyclic polymer according to claim 1 can self-healing gel synthetic method, it is characterised in that：In step
(1) in, in molar ratio, the furans vinyl derivative:Acrylic ester copolymerization monomer:Initiator:Catalyst:First part=
100:50~400:0.5~2:0.25~2:0.25~2.
5. cyclic polymer according to claim 1 can self-healing gel synthetic method, it is characterised in that：In step
(2) in, in molar ratio, the linear random copolymer:Sodium azide:Phase transfer catalyst=10:10~100:1~10.
6. according to claim 1 or 5 cyclic polymer can self-healing gel synthetic method, it is characterised in that：In step
Suddenly in (2), the phase transfer catalyst is 4-butyl ammonium hydrogen sulfate, four butyl bromation amine, trimethyl benzyl ammonia chloride, trioctylphosphine
One or more in ammonio methacrylate, cetyl trimethylammonium bromide and triethyl benzyl ammonia chloride.
7. cyclic polymer according to claim 1 can self-healing gel synthetic method, it is characterised in that：In step
(3) in, the catalyst is the one or more in stannous chloride, cuprous bromide and cuprous iodide, and the Ligands are selected from
Pentamethyl-diethylenetriamine, hexamethyl trien, diethylenetriamine, N, N, N', N'- tetra- (2- picolyls) second two
Amine, three (2- pyridylmethyls) amine, three (2- amino-ethyls) amine, 1,10- phenanthrolines, Isosorbide-5-Nitrae, 8,11- tetramethyls-Isosorbide-5-Nitrae, 8,11-
One or more in the decane of tetraazacyclododecane four and 2,2'- bipyridyl.
8. cyclic polymer according to claim 1 can self-healing gel synthetic method, it is characterised in that：In step
(3) in, in molar ratio, the linear furans random copolymer containing azido group:Catalyst:Ligands=1:25~100:25~
200。
9. cyclic polymer according to claim 1 can self-healing gel synthetic method, it is characterised in that：In step
(4) in, the BMI is diphenyl methane dimaleimide or 1,12- bis- (dimaleoyl imino) dodecane.
10. cyclic polymer according to claim 1 can self-healing gel synthetic method, it is characterised in that：In step
(4) in, the mol ratio of furan group and the BMI in the ring-type furans random copolymer is 10:1~10:
5。
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