CN109134748A - One kind can functionalized macromolecular photoswitch and its synthetic method - Google Patents
One kind can functionalized macromolecular photoswitch and its synthetic method Download PDFInfo
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Abstract
The invention discloses one kind can functionalized macromolecular photoswitch and its synthetic method, belong to new material technology field.It is a kind of can functionalized macromolecular photoswitch synthetic method, pass through the synthesis for the azobenzene derivatives that double bond is modified, the synthesis of the succinimide derivatives of double bond modification, using the azobenzene derivatives of double bond modification and the succinimide derivatives of double bond modification as raw material, hydroxyethyl methacrylate and n-vinyl pyrrolidone is added as chain diluent, obtaining by free radical polymerization can functionalized macromolecular photoswitch.Ability of the DMSO solution of copolymer of the invention with 100 times or more rotaversions, has the characteristic of photoswitch.
Description
Technical field
The invention belongs to new material technology fields, are related to the synthesis of azobenzene copolymer and its research of response characteristics to light,
It can functionalized macromolecular photoswitch and its synthetic method specifically, being related to one kind.
Background technique
The discovery of azobenzene compound can trace back to for 19th century, have become so far chemical, food, medicine and
A kind of very important color developing agent, intermediate, dyestuff or colorant in all conglomeraties such as light industry.Azobenzene is different there are two same point
Structure body: trans-isomerism and cis-isomer.Different space arrangements leads to different physics and chemical property, azobenzene it is photic
Change dramatically (the μ of isomerization reaction induction dipole momentTrans-azobenzene=0.5D, and μCis-azobenzene=3.1D), and then determine trans- different
Structure and cis-isomer is hydrophobic and water-wet behavior.Trans-azobenzene is not planar structure, secondly face angle N-N-C-C is about
17.5 °, and plane occupied by a phenyl ring and the plane of another phenyl ring are in 56 ° of angles in cis-azobenzene.Therefore, azobenzene
Cis and trans isomers in the distance between farthest two carbon atoms be 0.9 and 0.5nm respectively.The ultraviolet-visible of trans-azobenzene
Absorption spectrum feature is made of 3 main bands: (1) π-π * transition of the band at 228nm derived from the localization on phenyl；(2)
Band at 318nm is derived from the symmetrical permission π-π * transition of the delocalization on the entire molecule for including two nitrogen-atoms；(3) exist
Band at 440nm is derived from the n- π * transition that the symmetry forbidden on central nitrogen-atoms occurs.It is suitable but compared with trans-azobenzene
There are significant difference, the bands of 260nm to be originated from symmetry-allowed π-π * transition for the uv-visible absorption spectra of formula azobenzene, and
This band of transisomer is located at 318nm.
As people are to the research of azobenzene photoisomerization reaction mechanism and characteristic and gradually going deep into for understanding, azobenzene
Derivative either receives theoretically or all a large amount of concerns in terms of experiment.Azobenzene is realized under conditions of optical drive
Its reversible rotaversion, this characteristic make it as the function element of photoswitch response, have been applied not only to synthesis intelligence
Polymer, liquid crystal material, molecular switch and molecule machine, and just promptly penetrate into chemical biology architectural study and analysis
Various aspects.
But there is also the defects of photobleaching, that is, the suitable antireciprocal of this ultraviolet optical drive to turn for azobenzene molecule
Become in the reversible characteristic for losing it after rotaversion several times, and the application range of small molecule be always subjected to its dissolubility,
Intermolecular accumulation and its influence of toxicity.
Summary of the invention
To overcome above-mentioned technical problem, the present invention provides a kind of azobenzene macromolecular, and the modified double bond of azobenzene molecule is led to
It crosses and is switched with the free-radical polymerized excellent high-molecular optical of properties that obtains of other function monomer；Wherein specific function list
The introducing of body make it have can functionalization the characteristics of.
To achieve the above object, the present invention adopts the following technical scheme:
It is a kind of can functionalized macromolecular photoswitch synthetic method, comprising the following steps:
(1) azobenzene derivatives (P of double bond modificationAZO) synthesis:
Using the azobenzene of the substituent group containing reactive hydrogen and acryloyl chloride as raw material, reaction obtains the azo benzenesulfonamide derivative of double bond modification
Object；Spread out by the acid chloride groups on acryloyl chloride with the azobenzene for reacting to obtain double bond modification of reactive hydrogen on azobenzene substituent group
Biology obtains pure product by processes such as washing, extraction, vacuum distillation, vacuum drying,
(2) synthesis of the succinimide derivatives (NAS) of double bond modification
Using acryloyl chloride and n-hydroxysuccinimide as raw material, the succinimide that reaction obtains double bond modification is derivative
Object；Succinyl Asia is modified with the double bond of reacting to obtain of hydroxyl on n-hydroxysuccinimide by the acid chloride groups on acryloyl chloride
Amine derivative, this derivative have the characteristics that react with amino can functionalization, it is dry by washing, extraction, vacuum distillation, vacuum
The processes such as dry obtain pure product,
(3) using the azobenzene derivatives of double bond modification and the succinimide derivatives of double bond modification as raw material, two are selected
There is kind hydrophilic monomer hydroxyethyl methacrylate (HEMA) flexible and n-vinyl pyrrolidone (NVP) to dilute as chain
Agent, being obtained by free radical polymerization can functionalized macromolecular photoswitch.
Further technical solution, the step (1), specific synthetic method are as follows:
The azobenzene of the substituent group containing reactive hydrogen is dissolved in non-aqueous, non-polar oil phase solvent in a dry environment, azobenzene
Concentration be 0.1-10M, be added dropwise acryloyl chloride into system under condition of ice bath, rate of addition 1-15mL/h, acryloyl chloride:
The molar ratio of azobenzene is 1.5:1-1:1, and excessive ethylenediamine is added in reaction time 2-12h into system after reaction,
It is cleaned with saturated salt solution and removes unreacted acyl chlorides and ethylenediamine for several times, product is extracted with ethyl acetate, it is true after vacuum distillation
Sky is dried to obtain pure double bond modification azobenzene derivatives.
Further technical solution, the azobenzene of the substituent group containing reactive hydrogen are P-aminoazobenzene, to hydroxyl idol
Pyridine, to a kind of in carboxyl azobenzene；
The non-aqueous, non-polar oil phase solvent is one of methylene chloride, chloroform, tetrahydrofuran；
The concentration of the azobenzene is 0.5-3M；
The acryloyl chloride: the molar ratio of azobenzene is 1.2:1-1:1；
The rate of addition is 2-10mL/h；
The reaction time is 4-8h；
Further technical solution, the azobenzene of the substituent group containing reactive hydrogen are P-aminoazobenzene, to hydroxyl idol
One kind, preferably P-aminoazobenzene in pyridine；
The non-aqueous, non-polar oil phase solvent is methylene chloride, a kind of in chloroform, preferably methylene chloride；
The concentration of the azobenzene is 1-2M；
The acryloyl chloride: the molar ratio of azobenzene is 1.1:1；
The rate of addition is 5mL/h；
The reaction time is 4-6h.
Further technical solution, the step (2), specific synthetic method are as follows:
N-hydroxysuccinimide is dissolved in a dry environment in non-aqueous, non-polar oil phase solvent, under condition of ice bath
It is added dropwise acryloyl chloride into system, rate of addition 1-15mL/h, acryloyl chloride: the molar ratio of n-hydroxysuccinimide is
1.5:1-1:1, reaction time 2-12h, are added excessive ethylenediamine after reaction in system, clean number with saturated salt solution
It is secondary to remove unreacted acyl chlorides and ethylenediamine, product is extracted with ethyl acetate, vacuum drying obtains pure pair after vacuum distillation
Key modifies succinimide derivatives.
Further technical solution, the non-aqueous, non-polar oil phase solvent are methylene chloride, chloroform, tetrahydrofuran
Middle one kind；
The concentration of the n-hydroxysuccinimide is 0.1-10M；
The acryloyl chloride: the molar ratio of n-hydroxysuccinimide is 1.2:1-1:1；
The rate of addition is 2-10mL/h；
The reaction time is 4-8h；
Further technical solution, the non-aqueous, non-polar oil phase solvent is methylene chloride, a kind of in chloroform, excellent
It is selected as methylene chloride；
The concentration of the n-hydroxysuccinimide is 0.5-3M, preferably 1-2M；
The acryloyl chloride: the molar ratio of n-hydroxysuccinimide is 1.1:1；
The rate of addition is 5mL/h；
The reaction time is 4-6h.
Further technical solution, free radical polymerization uses polymerisation in solution in the step (3), method particularly includes:
By the azobenzene derivatives of double bond modification, succinimide derivatives, the hydroxyethyl methacrylate of double bond modification
It is added in solvent-laden reaction system with these four monomers of n-vinyl pyrrolidone, leads to nitrogen and remove oxygen, after mixing
Be added initiator, seal and is reacted at 50-90 DEG C of temperature, the reaction time for 5-48h after reaction, polymer ether
Precipitating is freeze-dried after gained precipitating filtering, obtains azobenzene copolymer (PAZO)；Wherein, total monomer 0.05-2M；With list
The total number of body is 100 meters, the succinimide derivatives 5-25 that 2-25 parts of the azobenzene derivatives of double bond modification, double bond are modified
Part, 20-55 parts of hydroxyethyl methacrylate, 20-50 parts of n-vinyl pyrrolidone；The initiator is benzoyl peroxide first
It is a kind of in acyl, azo-bis-isobutyl cyanide；The molal quantity of initiator is the 1-10% of the total mole number of monomer.
The solvent is dioxane, tetrahydrofuran weight one kind, preferably dioxane；
The total monomer is 0.1-1M, preferably 0.1-0.5M；
It is in terms of 100 by the total number of monomer, 5-20 parts of azobenzene derivatives, the succinyl of double bond modification of double bond modification are sub-
10-20 parts of amine derivative, 30-50 parts of hydroxyethyl methacrylate, 10-40 parts of n-vinyl pyrrolidone；
It preferably, is in terms of 100 by the total number of monomer, 15-17 parts of the azobenzene derivatives of double bond modification, double bond are modified
15-17 parts of succinimide derivatives, 40-45 parts of hydroxyethyl methacrylate, 20-30 parts of n-vinyl pyrrolidone；
The initiator is benzoyl peroxide；
The molal quantity of the initiator be monomer total mole number 2-5%, preferably 5%；
The reaction temperature is 60-80 DEG C, preferably 70 DEG C；
The reaction time is 10-24h, preferably 16-24h；
The freeze-drying condition is -50 DEG C, 7-8Pa.
Beneficial effect
Compared with prior art, the present invention has the following obvious advantages:
A kind of azobenzene copolymer for fields such as molecular switch, biological diagnosis provided by the invention.This copolymer
Ability of the DMSO solution with 100 times or more rotaversions, the characteristic for having photoswitch (can from Fig. 1 of embodiment 1
Out).Although reversible rotaversion may be implemented in unmodified P-aminoazobenzene (comparative example 1) under action of ultraviolet light,
It is that this change 1 time is weaker than 1 time and has substantially failure, loses its reversible rotaversion completely after undergoing 7 rotaversions
Ability.The present invention has biggish Social benefit and economic benefit.
Detailed description of the invention
Fig. 1 is the P in embodiment 1AZOSolution uv-visible absorption spectra: irradiation response time (a) and recovery time
(b)；PAZOAbsorbance (c) is recycled at 350nm/320nm, PAZORecycle UV photoresponse time and under visible light recovery time
(d)。
Fig. 2 is the AZO in comparative example 1 in different cycle-indexes, with the ultra-violet absorption spectrum of UV illumination: irradiation time
(a, c) and recovery time (b, d), wherein (a, b) is recycled for the first time；(c, d) the 7th circulation.
For the AZO in comparative example 1, absorbance loop parameter (a), AZO at 400nm recycle UV light to Fig. 3 in DMF solution
Response time and in the dark recovery time (b).
Specific embodiment
The affected step of the present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1
It is a kind of can functionalized macromolecular photoswitch synthetic method, comprising the following steps:
Step (1): a certain amount of P-aminoazobenzene is dissolved in methylene chloride in a dry environment, and concentration is
Acryloyl chloride is added dropwise, acryloyl chloride in 1.3M under condition of ice bath into system: the molar ratio of azobenzene is 1.1:1, rate of addition
For 5mL/h, excessive ethylenediamine is added after reacting 6h, is cleaned with saturated salt solution and removes unreacted acyl chlorides and second two for several times
Product is extracted with ethyl acetate in amine, and vacuum drying obtains pure double bond modification azobenzene derivatives after vacuum distillation.
Step (2): a certain amount of n-hydroxysuccinimide is dissolved in methylene chloride in a dry environment, and concentration is
Acryloyl chloride is added dropwise, acryloyl chloride in 1.3M under condition of ice bath into system: the molar ratio of n-hydroxysuccinimide is 1.1:
1, rate of addition 5mL/h are added excessive ethylenediamine after reacting 6h, are cleaned with saturated salt solution and remove unreacted acyl for several times
Product is extracted with ethyl acetate in chlorine and ethylenediamine, and vacuum drying obtains pure double bond modification succinimide after vacuum distillation
Derivative.
Step (3): a certain amount of monomer is added in the reaction system containing dioxane to the total concentration for making final monomer
0.25M, wherein PAZOBe 16.7 parts, NAS be 16.6 parts, HEMA be 41.7 parts, NVP be 25.0 parts, lead to nitrogen to remove oxygen,
Initiator B PO is added in monomer after mixing, its dense molal quantity is the 5% of the total mole number of monomer；Reaction seals at 70 DEG C
After carrying out for 24 hours, polymer is precipitated with ether, is freeze-dried (- 50 DEG C, 7-8Pa) after gained precipitating filtering, is obtained azobenzene copolymer
(PAZO)。
Embodiment 2
It is a kind of can functionalized macromolecular photoswitch synthetic method, comprising the following steps:
Step (1): a certain amount of p hydroxyazobenzene is dissolved in chloroform in a dry environment, and concentration is
Acryloyl chloride is added dropwise, acryloyl chloride in 0.1M under condition of ice bath into system: the molar ratio of azobenzene is 1.5:1, rate of addition
For 15mL/h, excessive ethylenediamine is added after reacting 12h, is cleaned with saturated salt solution and removes unreacted acyl chlorides and second two for several times
Product is extracted with ethyl acetate in amine, and vacuum drying obtains pure double bond modification azobenzene derivatives after vacuum distillation.
Step (2): a certain amount of n-hydroxysuccinimide is dissolved in chloroform in a dry environment, and concentration is
Acryloyl chloride is added dropwise, acryloyl chloride in 0.1M under condition of ice bath into system: the molar ratio of n-hydroxysuccinimide is 1.5:
1, rate of addition 15mL/h, react 12h after excessive ethylenediamine is added, cleaned with saturated salt solution remove for several times it is unreacted
Product is extracted with ethyl acetate in acyl chlorides and ethylenediamine, and it is sub- to obtain pure double bond modification succinyl for vacuum drying after vacuum distillation
Amine derivative.
Step (3): a certain amount of monomer is added in the reaction system containing dioxane to the total concentration for making final monomer
0.05M, wherein PAZO is 2 parts, and NAS is 5 parts, and HEMA is 43 parts, and NVP is 50 parts, and for logical nitrogen to remove oxygen, monomer mixing is equal
Initiator A IBN is added after even, molal quantity is the 1% of the total mole number of monomer；Reaction after sealing progress 10h, gathers at 80 DEG C
It closes object to be precipitated with ether, is freeze-dried (- 50 DEG C, 7-8Pa) after gained precipitating filtering, obtains azobenzene copolymer.
Embodiment 3
It is a kind of can functionalized macromolecular photoswitch synthetic method, comprising the following steps:
Step (1): a certain amount of pair of carboxyl azobenzene being dissolved in tetrahydrofuran in a dry environment, concentration 10M,
Acryloyl chloride is added dropwise into system under condition of ice bath, acryloyl chloride: the molar ratio of azobenzene is 1.2:1, and rate of addition is
10mL/h is added excessive ethylenediamine after reacting 2h, is cleaned with saturated salt solution and remove unreacted acyl chlorides and ethylenediamine for several times,
Product is extracted with ethyl acetate, vacuum drying obtains pure double bond modification azobenzene derivatives after vacuum distillation.
Step (2): a certain amount of n-hydroxysuccinimide is dissolved in tetrahydrofuran in a dry environment, and concentration is
Acryloyl chloride is added dropwise, acryloyl chloride in 10M under condition of ice bath into system: the molar ratio of n-hydroxysuccinimide is 1.2:
1, rate of addition 10mL/h, react 2h after excessive ethylenediamine is added, cleaned with saturated salt solution remove for several times it is unreacted
Product is extracted with ethyl acetate in acyl chlorides and ethylenediamine, and it is sub- to obtain pure double bond modification succinyl for vacuum drying after vacuum distillation
Amine derivative.
Step (3): a certain amount of monomer is added in the reaction system containing dioxane to the total concentration for making final monomer
0.25M, wherein PAZOIt is 5 parts, NAS is 5 parts, and HEMA is 50 parts, and NVP is 40 parts, and for logical nitrogen to remove oxygen, monomer mixing is equal
Initiator B PO is added after even, molal quantity is the 10% of the total mole number of monomer；Reaction after sealing progress 16h, gathers at 70 DEG C
It closes object to be precipitated with ether, is freeze-dried (- 50 DEG C, 7-8Pa) after gained precipitating filtering, obtains azobenzene copolymer.
Embodiment 4
It is a kind of can functionalized macromolecular photoswitch synthetic method, comprising the following steps:
Step (1): a certain amount of P-aminoazobenzene is dissolved in methylene chloride in a dry environment, concentration 5M,
Acryloyl chloride is added dropwise into system under condition of ice bath, acryloyl chloride: the molar ratio of azobenzene is 1:1, rate of addition 1mL/
H is added excessive ethylenediamine after reacting 8h, is cleaned with saturated salt solution and remove unreacted acyl chlorides and ethylenediamine for several times, use second
Acetoacetic ester extracts product, and vacuum drying obtains pure double bond modification azobenzene derivatives after vacuum distillation.
Step (2): a certain amount of n-hydroxysuccinimide is dissolved in methylene chloride in a dry environment, and concentration is
Acryloyl chloride is added dropwise, acryloyl chloride in 5M under condition of ice bath into system: the molar ratio of n-hydroxysuccinimide is 1:1, drop
Acceleration is 1mL/h, react 8h after excessive ethylenediamine is added, clean with saturated salt solution remove for several times unreacted acyl chlorides with
Product is extracted with ethyl acetate in ethylenediamine, and it is derivative to obtain pure double bond modification succinimide for vacuum drying after vacuum distillation
Object.
Step (3): a certain amount of monomer is added in the reaction system containing dioxane to the total concentration for making final monomer
0.1M, wherein PAZOIt is 25 parts, NAS is 25 parts, and HEMA is 30 parts, and NVP is 20 parts, and for logical nitrogen to remove oxygen, monomer mixing is equal
Initiator B PO is added after even, molal quantity is that the total mole number of monomer is 2%；After reaction seals progress for 24 hours at 60 DEG C,
Polymer is precipitated with ether, is freeze-dried (- 50 DEG C, 7-8Pa) after gained precipitating filtering, is obtained azobenzene copolymer.
Embodiment 5
It is a kind of can functionalized macromolecular photoswitch synthetic method, comprising the following steps:
Step (1): a certain amount of P-aminoazobenzene is dissolved in methylene chloride in a dry environment, concentration 3M,
Acryloyl chloride is added dropwise into system under condition of ice bath, acryloyl chloride: the molar ratio of azobenzene is 1.1:1, and rate of addition is
6mL/h is added excessive ethylenediamine after reacting 4h, is cleaned with saturated salt solution and remove unreacted acyl chlorides and ethylenediamine for several times,
Product is extracted with ethyl acetate, vacuum drying obtains pure double bond modification azobenzene derivatives after vacuum distillation.
Step (2): a certain amount of n-hydroxysuccinimide is dissolved in methylene chloride in a dry environment, and concentration is
Acryloyl chloride is added dropwise, acryloyl chloride in 3M under condition of ice bath into system: the molar ratio of n-hydroxysuccinimide is 1.1:1,
Rate of addition is 6mL/h, and excessive ethylenediamine is added after reacting 4h, is cleaned with saturated salt solution and removes unreacted acyl chlorides for several times
And ethylenediamine, product is extracted with ethyl acetate, vacuum drying obtains pure double bond modification succinimide and spreads out after vacuum distillation
Biology.
Step (3): a certain amount of monomer is added in the reaction system containing dioxane to the total concentration for making final monomer
0.5M, wherein PAZOIt is 16.7 parts, NAS is 16.6 parts, and HEMA is 41.7 parts, and NVP is 25.0 parts, and logical nitrogen is single to remove oxygen
Initiator B PO is added in body after mixing, and molal quantity is the 10% of the total mole number of monomer；Reaction is sealed at 80 DEG C and is carried out
After for 24 hours, polymer is precipitated with ether, is freeze-dried (- 50 DEG C, 7-8Pa) after gained precipitating filtering, is obtained azobenzene copolymer.
Test, unmodified P-aminoazobenzene are compared with the product of unmodified P-aminoazobenzene and embodiment 1
For comparative example 1.
Experimental method is as follows:
Azobenzene copolymer is made into about 0.1mg/mL solution with DMSO, P-aminoazobenzene is made into 0.03mg/mL with DMF
Solution.Solution is placed in the sample cell of ultraviolet spectra, with the purple for detecting solution after the 30w 365nm ultraviolet irradiation specific time
External spectrum, until detected ultraviolet spectra no longer changes with light application time.Turn off ultraviolet lamp, detects at regular intervals molten
The ultraviolet spectra of liquid, that is, the reply of conformation.The characteristic that this process is repeated to detect these chemicals as photoswitch.
Claims (10)
1. one kind can functionalized macromolecular photoswitch synthetic method, it is characterised in that: the following steps are included:
(1) synthesis of the azobenzene derivatives of double bond modification
Using the azobenzene of the substituent group containing reactive hydrogen and acryloyl chloride as raw material, reaction obtains the azobenzene derivatives of double bond modification；
(2) synthesis of the succinimide derivatives of double bond modification
Using acryloyl chloride and n-hydroxysuccinimide as raw material, reaction obtains the succinimide derivatives of double bond modification；
(3) using the azobenzene derivatives of double bond modification and the succinimide derivatives of double bond modification as raw material, methyl-prop is added
Olefin(e) acid hydroxyl ethyl ester and n-vinyl pyrrolidone as chain diluent, by free radical polymerization obtain can functionalized macromolecular light open
It closes.
2. it is according to claim 1 can functionalized macromolecular photoswitch synthetic method, it is characterised in that: the step
(1), specific synthetic method are as follows:
The azobenzene of the substituent group containing reactive hydrogen is dissolved in non-aqueous, non-polar oil phase solvent in a dry environment, azobenzene it is dense
Degree is 0.1-10M, and acryloyl chloride, rate of addition 1-15mL/h, acryloyl chloride: azo is added dropwise into system under condition of ice bath
The molar ratio of benzene is 1.5:1-1:1, and excessive ethylenediamine is added in reaction time 2-12h into system after reaction, with full
Unreacted acyl chlorides and ethylenediamine are removed for several times with saline solution cleaning, product are extracted with ethyl acetate, vacuum is dry after vacuum distillation
It is dry to obtain pure double bond modification azobenzene derivatives.
3. it is according to claim 2 can functionalized macromolecular photoswitch synthetic method, it is characterised in that:
The azobenzene of the substituent group containing reactive hydrogen is P-aminoazobenzene, p hydroxyazobenzene, in carboxyl azobenzene one
Kind；
The non-aqueous, non-polar oil phase solvent is one of methylene chloride, chloroform, tetrahydrofuran；
The concentration of the azobenzene is 0.5-3M；
The acryloyl chloride: the molar ratio of azobenzene is 1.2:1-1:1；
The rate of addition is 2-10mL/h；
The reaction time is 4-8h.
4. it is according to claim 3 can functionalized macromolecular photoswitch synthetic method, it is characterised in that:
The azobenzene of the substituent group containing reactive hydrogen is P-aminoazobenzene, a kind of in p hydroxyazobenzene, preferably to ammonia
Base azobenzene；
The non-aqueous, non-polar oil phase solvent is methylene chloride, a kind of in chloroform, preferably methylene chloride；
The concentration of the azobenzene is 1-2M；
The acryloyl chloride: the molar ratio of azobenzene is 1.1:1；
The rate of addition is 5mL/h；
The reaction time is 4-6h.
5. it is according to claim 1 can functionalized macromolecular photoswitch synthetic method, it is characterised in that: the step
(2), specific synthetic method are as follows:
N-hydroxysuccinimide is dissolved in a dry environment in non-aqueous, non-polar oil phase solvent, to body under condition of ice bath
Acryloyl chloride is added dropwise in system, rate of addition 1-15mL/h, acryloyl chloride: the molar ratio of n-hydroxysuccinimide is 1.5:1-
Excessive ethylenediamine is added after reaction, is cleaned with saturated salt solution and is removed for several times by 1:1, reaction time 2-12h in system
Product is extracted with ethyl acetate in unreacted acyl chlorides and ethylenediamine, and vacuum drying obtains pure double bond modification after vacuum distillation
Succinimide derivatives.
6. it is according to claim 5 can functionalized macromolecular photoswitch synthetic method, it is characterised in that:
The non-aqueous, non-polar oil phase solvent is methylene chloride, chloroform, a kind of in tetrahydrofuran；
The concentration of the n-hydroxysuccinimide is 0.1-10M；
The acryloyl chloride: the molar ratio of n-hydroxysuccinimide is 1.2:1-1:1；
The rate of addition is 2-10mL/h；
The reaction time is 4-8h.
7. it is according to claim 6 can functionalized macromolecular photoswitch synthetic method, it is characterised in that: described is anhydrous
Non-polar oil phase solvent is methylene chloride, a kind of in chloroform, preferably methylene chloride；
The concentration of the n-hydroxysuccinimide is 0.5-3M, preferably 1-2M；
The acryloyl chloride: the molar ratio of n-hydroxysuccinimide is 1.1:1；
The rate of addition is 5mL/h；
The reaction time is 4-6h.
8. it is according to claim 1 can functionalized macromolecular photoswitch synthetic method, it is characterised in that: the step
(3) free radical polymerization uses polymerisation in solution in, method particularly includes:
By the azobenzene derivatives of double bond modification, succinimide derivatives, hydroxyethyl methacrylate and the N- of double bond modification
These four monomers of vinyl pyrrolidone are added in solvent-laden reaction system, lead to nitrogen and remove oxygen, are added after mixing
Initiator is sealed at 50-90 DEG C of temperature and is reacted, and the reaction time, polymer was heavy with ether after reaction for 5-48h
It forms sediment, is freeze-dried after gained precipitating filtering, obtains azobenzene copolymer；Wherein, total monomer 0.05-2M；With the total of monomer
Number is 100 meters, 2-25 parts of the azobenzene derivatives of double bond modification, 5-25 parts of the succinimide derivatives of double bond modification, first
20-55 parts of base hydroxy-ethyl acrylate, 20-50 parts of n-vinyl pyrrolidone；The initiator is benzoyl peroxide, azo
It is a kind of in two isobutyl cyanogen；The molal quantity of initiator is the 1-10% of the total mole number of monomer.
9. it is according to claim 8 can functionalized macromolecular photoswitch synthetic method, it is characterised in that:
The solvent is dioxane, tetrahydrofuran weight one kind, preferably dioxane；
The total monomer is 0.1-1M, preferably 0.1-0.5M；
It is in terms of 100 by the total number of monomer, 5-20 parts of the azobenzene derivatives of double bond modification, the succinimide of double bond modification spread out
10-20 parts biological, 30-50 parts of hydroxyethyl methacrylate, 10-40 parts of n-vinyl pyrrolidone；
It preferably, is 15-17 parts of the azobenzene derivatives that double bond is modified, the amber of double bond modification in terms of 100 by the total number of monomer
15-17 parts of imide derivative, 40-45 parts of hydroxyethyl methacrylate, 20-30 parts of n-vinyl pyrrolidone；
The initiator is benzoyl peroxide；
The molal quantity of the initiator be monomer total mole number 2-5%, preferably 5%；
The reaction temperature is 60-80 DEG C, preferably 70 DEG C；
The reaction time is 10-24h, preferably 16-24h；
The freeze-drying condition is -50 DEG C, 7-8Pa.
10. what according to claim 1 prepared by any one of -9 synthetic methods can functionalized macromolecular photoswitch.
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