CN109705290A - A kind of photosensitive block copolymer of the side chain of temperature-responsive and preparation method thereof - Google Patents
A kind of photosensitive block copolymer of the side chain of temperature-responsive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses photosensitive block copolymers of the side chain of a kind of temperature-responsive and preparation method thereof, and the structural formula of the block copolymer is as follows:The present invention is first by n-isopropyl acrylamide and N, N- dimethylacrylamide carries out random copolymerization by atom transfer radical polymerization and obtains poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent, its acryloyloxyalkyl -4- benzene diazenyl benzoic ether obtained again with esterification carries out atom transfer radical polymerization and obtains poly- [(n-isopropyl acrylamide-N,N-DMAA)-acryloyloxyalkyl -4- benzene diazenyl benzoic ether] block copolymer with light and temperature double-response.Block copolymer of the present invention can be used as the carrier material of drug controlled release for fields such as drug targeting treatment, nano-sensor, chemical reservoir, surface modification, shape-memory material, coating, films.
Description
Technical field
The invention belongs to Functional polymer materials technology fields, and in particular to a kind of poly- [(N- of light and temperature double-response
N-isopropylacrylamide-N, N- dimethylacrylamide)-acryloyloxyalkyl -4- benzene diazenyl benzoic ether] block copolymerization
Object and preparation method thereof.
Background technique
Stimuli responsive material as important a member in functional polymer material, these stimulations have temperature, pH, electrolyte,
Redox, magnetic, light etc., response type polymer can directly experience the subtle stimulation variation of external environmental condition, thus
Different degrees of molecule structure change occurs.These variations have reversible, and have irreversible, the degree of molecule structure change is also
The physicochemical property of polymer can further be influenced.
Illumination is a kind of better controlled condition, can be strong to its in the outside of measurement system since it is with penetrability
Degree, prolonged exposure time and special fixed position carry out different irradiations, and compared to the condition of other stimuli responsives, light is rung
It should be with its flexible controllable advantage, persistently by the concern of scientists.On the other hand, ambient temperature stimulation has unique
Advantage, because temperature-responsive polymer has lower critical solution temperature (LCST) property, when temperature is greater than LCST, polymer water
Solution becomes cloudy or insoluble, i.e. temperature stimuli-responsive.
Univ. of Pittsburgh Zhang Xiaolan etc. (X.Zhang, Y.Huang, M.Ghazwani, P.Zhang, J.Li,
S.H.Thorne, S.Li.ACS MacroLett.2015,4,620-623) a kind of nano-micelle of pH response is reported as anti-
The carrier of cancer drug taxol.Hu army, Sichuan University etc. (J.Hu, W.Zhuang, B.Ma, X.Su, T.Yu, G.Li, Y.Hu,
Y.Wang.Bioconjugate Chem.2018,29 (6), 1897-1910) one kind is prepared for aggregation inducing fluorescence imaging
Redox response polymer micelle be used for doxorubicin hydrochloride drug controlled release.However since cancer or diseased region are multiple
Miscellaneous cellular environment, temperature, pH and activity keto concentration etc. are all higher than normal cell, therefore substance stimulus responsive polymer material is
It is not able to satisfy demand of the people to multifunctional macromolecule material, it is necessary to which exploitation has multiple or dual responsiveness drug release
Carrier material.
Summary of the invention
Technical problem to be solved by the present invention lies in the deficiencies for eliminating single stimulating responsive, provide a kind of with uniqueness
Photosensitive poly- [(n-isopropyl acrylamide-N, the N- dimethylacrylamide)-acryloyloxyalkyl -4- benzene of the side chain of temperature-responsive
Diazenyl benzoic ether] block copolymer, and a kind of preparation method is provided for the block copolymer.
Solve the photosensitive poly- [(n-isopropyl acrylamide-N, N- bis- of side chain of temperature-responsive used by the above technical problem
Methacrylamide)-acryloyloxyalkyl -4- benzene diazenyl benzoic ether] block copolymer structural formula it is as follows:
X represents 40~65 integer in formula, and y represents 2~7 integer, and z represents 2~15 integer, the value of m is 1,
1.5,2,2.5 or 3.
The preparation method of above-mentioned block copolymer is made of following step:
1, the macromole evocating agent of poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) is prepared
Using n,N-Dimethylformamide and water volume ratio for 3:2 mixed liquor as solvent, cuprous bromide is catalyst, 2- bromine
Ethyl propionate is initiator, and three (2- dimethylaminoethyl) amine are ligand, by Transfer Radical Polymerization to N- isopropyl
Base acrylamide and N,N-DMAA carry out random copolymerization, obtain poly- (n-isopropyl acrylamide-shown in Formulas I
N, N dimethyl acrylamide) macromole evocating agent.
2, acryloyloxyalkyl -4- benzene diazenyl benzoic ether is prepared
Using methylene chloride as solvent, 4-dimethylaminopyridine is catalyst, and dicyclohexylcarbodiimide is dehydrating agent, by 4-
Esterification occurs for phenyl-diazenyl benzoic acid and hydroxyalkyl acrylates, obtains acryloyloxyalkyl -4- shown in Formula II
Benzene diazenyl benzoic ether;Wherein the hydroxyalkyl acrylates are hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxyl
Butyl propyleneglycol acid esters, hydroxyl acrylate, any one in hydroxyl ethylhexyl acrylate.
3, poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyloxyalkyl -4- benzene phenodiazine is prepared
Enyl benzoate] block copolymer
It is 4:3 as mixed solvent using tetrahydrofuran and methanol volume ratio, cuprous bromide is catalyst, 1, Isosorbide-5-Nitrae, 7,10,
10- hexamethyl trien is ligand, and the macromolecular of poly- (n-isopropyl acrylamide-N,N-DMAA) is drawn
It sends out agent and acryloyloxyalkyl -4- benzene diazenyl benzoic ether carries out atom transition free radical polymerization reaction, obtain poly- [(N-
N-isopropylacrylamide-N, N- dimethylacrylamide)-acryloyloxyalkyl -4- benzene diazenyl benzoic ether] block copolymerization
Object.
In above-mentioned steps 1, preferably 2 bromopropionic acid ethyl ester, n-isopropyl acrylamide, N,N-DMAA, bromination
Cuprous, three (2- dimethylaminoethyl) amine molar ratios are 1:90~95:5~10:1:1.
In above-mentioned steps 2, preferably 4- benzene diazenyl benzoic acid, hydroxyalkyl acrylates, dicyclohexylcarbodiimide, 4-
The molar ratio of dimethylamino naphthyridine is 1.1~1.5:1:1.1~1.5:1.
In above-mentioned steps 3, preferably poly- (n-isopropyl acrylamide-N,N-DMAA) macromole evocating agent,
Acryloyloxyalkyl -4- benzene diazenyl benzoic ether, 1,1,4,7,10,10- hexamethyl trien, cuprous bromide
Molar ratio is 1:25~200:3~1:2~1.
Block copolymer of the present invention has good temperature and ultraviolet-visible light dual responsiveness, low Critical Solution temperature
Spending range is 37~43 DEG C.Under the ultraviolet light irradiation of 365nm, block copolymer of the present invention is become completely from stable transconfiguration
Cis-structure;And under visible light illumination, block copolymer of the present invention can be restored to transconfiguration again, to realize photosensitive turn
Become.Therefore, block copolymer of the present invention is expected the control release applied to anticancer drug, nano-sensor, chemical reservoir, table
The fields such as face modification, shape-memory material, coating, film.
Detailed description of the invention
Fig. 1 is poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy fourth prepared by embodiment 1
Base -4- benzene diazenyl benzoic ether] block copolymer nucleus magnetic hydrogen spectrum figure.
Fig. 2 is poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy fourth prepared by embodiment 1
Base -4- benzene diazenyl benzoic ether] block copolymer light transmittance-hygrogram.
Fig. 3 is poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy fourth prepared by embodiment 1
Base -4- benzene diazenyl benzoic ether] block copolymer ultravioletvisible absorption figure.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
1, poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is prepared
It weighs 4.3g (38mmol) n-isopropyl acrylamide to be added in the dry Shrek bottle of 25mL, then to Shrek
206 μ L (2mmol) N, N- dimethylacrylamide, 3.6mL N,N-dimethylformamide and 2.4mL water, 52 μ L is added in bottle
(0.4mmol) 2 bromopropionic acid ethyl ester, 106.9 μ L (0.4mmol) three (2- dimethylaminoethyl) amine, 0.0574g (0.4mmol) bromine
Change cuprous, be uniformly mixed, gained mixed liquor carries out duplicate three times " freezing-vacuumizing-to thaw " operation and in nitrogen
Under it is closed, 25 DEG C react 24 hours.After reaction, reaction solution is diluted with tetrahydrofuran, using tetrahydrofuran as eluant, eluent
The catalyst that neutral alumina column removes system is crossed to fill concentrate after efflux removes most of solvent by concentrated by rotary evaporation
Enter in the bag filter that molecular weight is 2000, dialyses 4 days in deionized water, the solution after dialysis is freeze-dried, is obtained
GPC number average molecular weight is that poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) that 8800g/mol, PDI are 1.14 is big
Initiator molecule (Formulas I -1);Wherein poly(N-isopropylacrylamide) section nuclear-magnetism molecular weight be 5660g/mol, the degree of polymerization 50,
Poly- (N,N-DMAA) section nuclear-magnetism molecular weight is 590g/mol, the degree of polymerization 6.
2, acryloyl-oxy butyl -4- benzene diazenyl benzoic ether is prepared
4.0g (17.68mmol) 4- benzene diazenyl benzoic acid and 1.795g (14.7mmol) 4-dimethylaminopyridine is molten
In 105mL methylene chloride, 2.04mL (14.7mmol) hydroxyl butyl propyleneglycol acid esters, stir-activating 30 minutes in ice bath are added
Afterwards, the dichloromethane solution that 92mL contains 3.94g (19.11mmol) dicyclohexylcarbodiimide is added dropwise, it will be warm after dripping
Degree rises to 25 DEG C and reacts 24 hours.Crude product is filtered to remove insoluble matter dicyclohexylurea (DCU) after reaction, filtrate is first with saturation
Sodium bicarbonate aqueous solution extracts three times, then three times with deionized water extraction, is dried overnight, is filtered with anhydrous magnesium sulfate, filtrate rotation
After inspissation contracting, then passing through silica gel column chromatography and use methylene chloride as eluent, last vacuum rotary steam falls eluant, eluent,
35 DEG C of vacuum drying, obtain crocus solid product acryloyl-oxy butyl -4- benzene diazenyl benzoic ether shown in Formula II -1.
3, poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy butyl -4- benzene phenodiazine is prepared
Enyl benzoate] block copolymer
Weigh 1.5g (4.26mmol) acryloyl-oxy butyl -4- benzene diazenyl benzoic ether and 0.555g
(0.0888mmol) poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is dissolved in 4.8mL tetra-
In the mixed liquor of hydrogen furans and 3.6mL methanol, 72 μ L (0.2556mmol) 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl Sanya second are added
Urotropine, 0.0021g (0.1704mmol) cuprous bromide, carry out that duplicate three times " freezing-pumping is true after being uniformly mixed
Sky-defrosting " operation is simultaneously closed under a nitrogen, reacts 24 hours at 35 DEG C.After reaction, reaction solution is to wash with tetrahydrofuran
The catalyst that neutral alumina column removes system is crossed in de- agent, is collected product and is precipitated in ice n-hexane twice, sediment vacuum is dry
It is dry, obtain [(n-isopropyl acrylamide-N,N-DMAA)-acryloyl-oxy butyl -4- poly- shown in formula III -1
Benzene diazenyl benzoic ether] block copolymer, the LCST of the block copolymer is 39.5 DEG C, number-average molecular weight 16800g/
Mol, PDI 1.07;The nuclear-magnetism molecular weight of wherein poly- (acryloyl-oxy butyl -4- benzene diazenyl benzoic ether) block is
2470g/mol, the degree of polymerization 7.
Inventor is using nuclear magnetic resonance spectrometry to poly- [(n-isopropyl acrylamide-N, the N- dimethyl propylene of above-mentioned preparation
Acrylamide)-acryloyl-oxy butyl -4- benzene diazenyl benzoic ether] block copolymer chemical structure carried out confirmation as scheme
1;Its Thermo-sensitive is characterized such as Fig. 2 using U-3900H type ultraviolet-uisible spectrophotometer.Using UV-6100S type is ultraviolet can
See that spectrophotometer has carried out characterization such as Fig. 3 to its optical Response.
From Figure 2 it can be seen that absorption peak of the chemical shift between 7.5-8.1 is phenyl ring on 4- benzene diazenyl benzoic ether
Characteristic peak, chemical shift is in the absorption peak that 4.0 be methine in isopropyl in n-isopropyl acrylamide, and chemical shift is 2.9
Left and right is N, the absorption peak of methyl in N- dimethylacrylamide.It follows that poly- [(n-isopropyl acrylamide-N, N- diformazan
Base acrylamide)-acryloyl-oxy butyl -4- benzene diazenyl benzoic ether] block copolymer successfully prepared.From Figure 2 it can be seen that should
The LCST of block copolymer is 39.5 DEG C.As seen from Figure 3, under the ultraviolet light irradiation of 365nm, azobenzene exists in the block copolymer
The remitted its fury of the π-π * absorption peak of 320nm, and the enhanced strength of the n- π * absorption peak at 425nm, by stable anti-after 240 seconds
Formula structure becomes cis-structure completely.And under visible light illumination, it can be restored to transconfiguration again.Illustrate the copolymer material
There is good response to ultraviolet/visible light.
Embodiment 2
1, poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is prepared
The step is identical as the step 1 of embodiment 1.
2, acryloyl-oxy butyl -4- benzene diazenyl benzoic ether is prepared
The step is identical as the step 2 of embodiment 1.
3, poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy butyl -4- benzene phenodiazine is prepared
Enyl benzoate] block copolymer
Weigh 1.5g (4.26mmol) acryloyl-oxy butyl -4- benzene diazenyl benzoic ether and 0.653g
(0.104mmol) poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is dissolved in 4.8mL tetrahydro
In the mixed liquor of furans and 3.6mL methanol, 72 μ L (0.2556mmol) 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triethylenes are added
Tetramine, 0.0021g (0.1704mmol) cuprous bromide, carried out after being uniformly mixed it is duplicate three times " freeze-vacuumize-
Defrosting " operation is simultaneously closed under a nitrogen, reacts 24 hours at 35 DEG C.After reaction, reaction solution is using tetrahydrofuran as eluant, eluent,
The catalyst that neutral alumina column removes system is crossed, product is collected and is precipitated in ice n-hexane twice, sediment vacuum drying obtains
To [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy butyl -4- benzene phenodiazine poly- shown in formula III -2
Enyl benzoate] block copolymer, the number-average molecular weight of the block copolymer is 14800g/mol, PDI 1.07;Wherein gather
The nuclear-magnetism molecular weight of (acryloyl-oxy butyl -4- benzene diazenyl benzoic ether) block is 1410g/mol, the degree of polymerization 4.
Embodiment 3
1, poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is prepared
It weighs 4.12g (36mmol) n-isopropyl acrylamide to be added in the dry Shrek bottle of 25mL, then to Shi Lai
412 μ L (4mmol) N, N- dimethylacrylamide, 3.6mL N,N-dimethylformamide and 2.4mL water, 52 μ L is added in gram bottle
(0.4mmol) 2 bromopropionic acid ethyl ester, 106.9 μ L (0.4mmol) three (2- dimethylaminoethyl) amine, 0.0574g (0.4mmol) bromine
Change cuprous, be uniformly mixed, gained mixed liquor carries out duplicate three times " freezing-vacuumizing-to thaw " operation and in nitrogen
Under it is closed, 25 DEG C react 24 hours.After reaction, reaction solution is diluted with tetrahydrofuran, using tetrahydrofuran as eluant, eluent
The catalyst that neutral alumina column removes system is crossed to fill concentrate after efflux removes most of solvent by concentrated by rotary evaporation
Enter in the bag filter that molecular weight is 2000, dialyses 4 days in deionized water, the solution after dialysis is freeze-dried, is obtained
Number-average molecular weight is that poly- (n-isopropyl acrylamide-N, the N- dimethylacrylamide) that 8400g/mol, PDI are 1.12 is divided greatly
Sub- initiator (Formulas I -2);Wherein poly(N-isopropylacrylamide) section nuclear-magnetism molecular weight is 4980g/mol, and the degree of polymerization 44 is gathered
(N,N-DMAA) section nuclear-magnetism molecular weight is 300g/mol, the degree of polymerization 3.
2, acryloyl-oxy butyl -4- benzene diazenyl benzoic ether is prepared
The step is identical as the step 2 of embodiment 1.
3, poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy butyl -4- benzene phenodiazine is prepared
Enyl benzoate] block copolymer
Weigh 0.25g (0.71mmol) acryloyl-oxy butyl -4- benzene diazenyl benzoic ether and 0.150g
(0.0284mmol) poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is dissolved in 0.8mL tetra-
In the mixed liquor of hydrogen furans and 0.6mL methanol, 23 μ L (0.0852mmol) 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl Sanya second are added
Urotropine, 8mg (0.0568mmol) cuprous bromide, carry out duplicate three times " freeze-vacuumize-solve after being uniformly mixed
Jelly " operation is simultaneously closed under a nitrogen, reacts 24 hours at 35 DEG C.After reaction, reaction solution is using tetrahydrofuran as eluant, eluent, mistake
Neutral alumina column removes the catalyst of system, collects product and precipitates in ice n-hexane twice, and sediment vacuum drying obtains
[(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy butyl -4- benzene diazene poly- shown in formula III -3
Yl benzoic acid ester] block copolymer, the number-average molecular weight of the block copolymer is 13800g/mol, PDI 1.08;Wherein gather
The nuclear-magnetism molecular weight of (acryloyl-oxy butyl -4- benzene diazenyl benzoic ether) block is 3170g/mol, the degree of polymerization 9.
Embodiment 4
1, poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is prepared
The step is identical as the step 1 of embodiment 3.
2, acryloyl-oxy butyl -4- benzene diazenyl benzoic ether is prepared
The step is identical as the step 2 of embodiment 1.
3, poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy butyl -4- benzene phenodiazine is prepared
Enyl benzoate] block copolymer
Weigh 0.5g (1.42mmol) acryloyl-oxy butyl -4- benzene diazenyl benzoic ether and 0.067g
(0.01268mmol) poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is dissolved in 1.6mL tetra-
In the mixed liquor of hydrogen furans and 1.2mL methanol, 6 μ L (0.0213mmol) 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triethylenes are added
Tetramine, 2mg (0.0142mmol) cuprous bromide carry out duplicate three times " freezing-vacuumizing-to thaw " after being uniformly mixed
It operates and closed under a nitrogen, is reacted 24 hours at 35 DEG C.After reaction, reaction solution is using tetrahydrofuran as eluant, eluent, excessively in
Property alumina column remove system catalyst, collect product precipitated in ice n-hexane twice, sediment vacuum drying, obtain formula
[(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy butyl -4- benzene diazenyl poly- shown in III-4
Benzoic ether] block copolymer, the number-average molecular weight of the block copolymer is 20200g/mol, PDI 1.15;Wherein poly- (third
Alkene acyl-oxygen butyl -4- benzene diazenyl benzoic ether) block nuclear-magnetism molecular weight be 4580g/mol, the degree of polymerization 13.
Claims (5)
1. a kind of photosensitive poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy of the side chain of temperature-responsive
Alkyl -4- benzene diazenyl benzoic ether] block copolymer, it is characterised in that: the structural formula of the block copolymer is as follows:
X represents 40~65 integer in formula, and y represents 2~7 integer, and z represents 2~15 integer, the value of m is 1,1.5,2,
2.5 or 3.
2. a kind of poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy alkane described in claim 1
Base -4- benzene diazenyl benzoic ether] block copolymer preparation method, it is characterised in that this method is made of following step:
(1) poly- (n-isopropyl acrylamide-N, N- dimethylacrylamide) macromole evocating agent is prepared
Using n,N-Dimethylformamide and water volume ratio for 3:2 mixed liquor as solvent, cuprous bromide is catalyst, 2 bromopropionic acid
Ethyl ester is initiator, and three (2- dimethylaminoethyl) amine are ligand, by Transfer Radical Polymerization to N- isopropyl third
Acrylamide and N,N-DMAA carry out random copolymerization, obtain (n-isopropyl acrylamide-N, N bis- poly- shown in Formulas I
Methacrylamide) macromole evocating agent;
(2) acryloyloxyalkyl -4- benzene diazenyl benzoic ether is prepared
Using methylene chloride as solvent, 4-dimethylaminopyridine is catalyst, and dicyclohexylcarbodiimide is dehydrating agent, by 4- phenyl
Esterification occurs for diazenyl benzoic acid and hydroxyalkyl acrylates, obtains acryloyloxyalkyl -4- benzene two shown in Formula II
Nitrogen enyl benzoate;
Above-mentioned hydroxyalkyl acrylates are hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxyl butyl propyleneglycol acid esters, hydroxyl amyl
Any one in acrylate, hydroxyl ethylhexyl acrylate;
(3) poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyloxyalkyl -4- benzene diazenyl is prepared
Benzoic ether] block copolymer
Using tetrahydrofuran and methanol volume ratio for 4:3 mixed liquor as solvent, cuprous bromide is catalyst, 1, Isosorbide-5-Nitrae, 7,10,10-
Hexamethyl trien is ligand, and [(n-isopropyl acrylamide-N,N-DMAA) macromolecular is drawn using poly-
It sends out agent and acryloyloxyalkyl -4- benzene diazenyl benzoic ether carries out atom transition free radical polymerization reaction, obtain poly- [(N-
N-isopropylacrylamide-N, N- dimethylacrylamide)-acryloyloxyalkyl -4- benzene diazenyl benzoic ether] block copolymerization
Object.
3. poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy alkane according to claim 2
Base -4- benzene diazenyl benzoic ether] block copolymer preparation method, it is characterised in that: in step (1), the 2- bromine third
Acetoacetic ester, n-isopropyl acrylamide, N, N- dimethylacrylamide, cuprous bromide, three (2- dimethylaminoethyl) amine rub
You are than being 1:90~95:5~10:1:1.
4. poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy alkane according to claim 2
Base -4- benzene diazenyl benzoic ether] block copolymer preparation method, it is characterised in that: in step (2), the 4- benzene two
Nitrence yl benzoic acid, hydroxyalkyl acrylates, dicyclohexylcarbodiimide, 4-dimethylaminopyridine molar ratio be 1.1~
1.5:1:1.1~1.5:1.
5. poly- [(n-isopropyl acrylamide-N, N- dimethylacrylamide)-acryloyl-oxy alkane according to claim 2
Base -4- benzene diazenyl benzoic ether] block copolymer preparation method, it is characterised in that: in step (3), described poly- (N- is different
Propylacrylamide-N, N- dimethylacrylamide) macromole evocating agent, acryloyloxyalkyl -4- benzene diazenyl benzoic acid
Ester, 1,1,4,7,10,10- hexamethyl trien, cuprous bromide molar ratio be 1:25~200:1~3:1~2.
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