CN109705290B - Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof - Google Patents
Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN109705290B CN109705290B CN201811618849.XA CN201811618849A CN109705290B CN 109705290 B CN109705290 B CN 109705290B CN 201811618849 A CN201811618849 A CN 201811618849A CN 109705290 B CN109705290 B CN 109705290B
- Authority
- CN
- China
- Prior art keywords
- isopropylacrylamide
- dimethylacrylamide
- poly
- block copolymer
- acryloyloxyalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a temperature-responsive side-chain photosensitive block copolymer and a preparation method thereof, wherein the structural formula of the block copolymer is as follows:
the method comprises the steps of carrying out random copolymerization on N-isopropylacrylamide and N, N-dimethylacrylamide through atom transfer radical polymerization to obtain poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator, and carrying out atom transfer radical polymerization on the poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate obtained through esterification reaction to obtain poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate) with dual responses of light and temperature]A block copolymer. The block copolymer can be used as a carrier material for controllable release of drugs and used in the fields of drug targeting therapy, nano sensors, chemical reservoirs, surface modification, shape memory materials, coatings, films and the like.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a light and temperature dual-response poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] block copolymer and a preparation method thereof.
Background
The stimulus responsive material is an important member of functional polymer materials, the stimuli include temperature, pH, electrolyte, oxidation reduction, magnetism, light and the like, and the responsive polymer can directly sense the slight stimulus change of external environmental conditions, so that the molecular structure changes to different degrees. Some of these changes are reversible and some are irreversible, and the degree of change in molecular structure can further affect the physicochemical properties of the polymer.
Illumination is a condition that is best controlled because of its penetration, and its intensity, duration and specific fixation site can be differently illuminated outside the measurement system, and the light response continues to be of interest to scientists with the advantage of being flexible and controllable compared to other stimuli-responsive conditions. On the other hand, the external temperature stimulus has a unique advantage that since the temperature-responsive polymer has a Low Critical Solution Temperature (LCST) property, when the temperature is higher than the LCST, the aqueous polymer solution becomes cloudy or insoluble, i.e., the temperature stimulus responsiveness.
The use of pH-responsive nanomicelles as carriers for the anticancer drug paclitaxel was reported by Zhang, Y.Huang, M.Ghazwaii, P.Zhang, J.Li, S.H.Thorne, S.Li.ACS MacroLett.2015,4,620-623, Zhang et al, university of Pittsburgh, USA. The Sichuan university Hoojun et al (J.Hu, W.Zhuang, B.Ma, X.Su, T.Yu, G.Li, Y.Hu, Y.Wang.bioconjugate chem.2018,29(6),1897-1910) prepared a polymeric micelle with an aggregation-induced fluorescence imaging redox response for controlled release of an oxytocin hydrochloride drug. However, since the complex cellular environment of cancer or diseased region, temperature, pH and active oxygen concentration are higher than those of normal cells, the single stimuli-responsive polymer material cannot meet the demand of people for multifunctional polymer materials, and it is necessary to develop a drug release carrier material with multiple or dual responsiveness.
Disclosure of Invention
The invention aims to solve the technical problem of eliminating the deficiency of single stimulus responsiveness, provide a side chain photosensitive poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] block copolymer with unique temperature response, and provide a preparation method for the block copolymer.
The temperature-responsive side-chain photosensitive poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] block copolymer adopted for solving the technical problems has the following structural formula:
wherein x represents an integer of 40-65, y represents an integer of 2-7, z represents an integer of 2-15, and m is 1, 1.5, 2, 2.5 or 3.
The preparation method of the block copolymer comprises the following steps:
1. macroinitiator for preparing poly (N-isopropyl acrylamide-N, N-dimethyl acrylamide)
The method comprises the steps of taking a mixed solution of N, N-dimethylformamide and water in a volume ratio of 3:2 as a solvent, cuprous bromide as a catalyst, ethyl 2-bromopropionate as an initiator and tris (2-dimethylaminoethyl) amine as a ligand, and carrying out random copolymerization on N-isopropylacrylamide and N, N-dimethylacrylamide by an atom transfer radical polymerization method to obtain the poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator shown in the formula I.
2. Preparation of acryloyloxyalkyl-4-benzodiazelnylbenzoic acid esters
Using dichloromethane as a solvent, 4-dimethylamino pyridine as a catalyst and dicyclohexyl carbodiimide as a dehydrating agent, and carrying out esterification reaction on 4-phenyl diazenyl benzoic acid and hydroxyalkyl acrylate to obtain acryloyloxyalkyl-4-phenyl diazenyl benzoic acid ester shown in a formula II; wherein the hydroxyalkyl acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate and hydroxyhexyl acrylate.
3. Preparation of Poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] Block copolymer
Taking tetrahydrofuran and methanol in a volume ratio of 4:3 as a mixed solvent, cuprous bromide as a catalyst, 1,1,4,7,10, 10-hexamethyltriethylenetetramine as a ligand, and carrying out atom transfer radical polymerization on a macroinitiator of poly (N-isopropylacrylamide-N, N-dimethylacrylamide) and acryloyloxyalkyl-4-benzodiazepine benzoic acid ester to obtain the poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazepine benzoic acid ester ] block copolymer.
In the step 1, the molar ratio of ethyl 2-bromopropionate, N-isopropylacrylamide, N-dimethylacrylamide, cuprous bromide and tris (2-dimethylaminoethyl) amine is preferably 1: 90-95: 5-10: 1:1.
In the step 2, the molar ratio of 4-benzodiazelnylbenzoic acid, hydroxyalkyl acrylate, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is preferably 1.1 to 1.5:1:1.1 to 1.5: 1.
In the step 3, the molar ratio of the poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator, the acryloyloxyalkyl-4-benzodiazepine benzoate, the 1,1,4,7,10, 10-hexamethyltriethylenetetramine and the cuprous bromide is preferably 1:25 to 200:3 to 1:2 to 1.
The segmented copolymer has good dual responsivity of temperature and ultraviolet-visible light, and the low critical solution temperature range of the segmented copolymer is 37-43 ℃. Under the irradiation of a 365nm ultraviolet lamp, the block copolymer is completely changed into a cis structure from a stable trans structure; under the irradiation of visible light, the block copolymer of the present invention can restore to the trans structure to realize photosensitive conversion. Therefore, the block copolymer of the invention is expected to be applied to the fields of anticancer drug controlled release, nano sensors, chemical reservoirs, surface modification, shape memory materials, coatings, films and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer prepared in example 1.
FIG. 2 is a graph of light transmittance versus temperature for poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer prepared in example 1.
FIG. 3 is a graph of the UV-vis absorbance of the poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer prepared in example 1.
Detailed Description
The invention will be described in more detail hereinafter with reference to the accompanying drawings and specific examples, to which, however, the invention is not limited.
Example 1
1. Preparation of Poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator
4.3g (38mmol) of N-isopropylacrylamide are weighed out and introduced into a 25mL dry Schlenk flask, 206. mu.L (2mmol) of N, N-dimethylacrylamide, 3.6mL of N, N-dimethylformamide and 2.4mL of water, 52. mu.L (0.4mmol) of ethyl 2-bromopropionate, 106.9. mu.L (0.4mmol) of tris (2-dimethylaminoethyl) amine and 0.0574g (0.4mmol) of cuprous bromide are added to the Schlenk flask and mixed well with stirring, and the mixture is subjected to three repeated "freeze-pump-thaw" operations and sealed under nitrogen and reacted at 25 ℃ for 24 hours. After the reaction is finished, diluting the reaction liquid with tetrahydrofuran, removing a catalyst of a system by using tetrahydrofuran as an eluent through a neutral alumina column, removing most of a solvent from an effluent liquid through rotary evaporation and concentration, filling the concentrated liquid into a dialysis bag with the molecular weight of 2000, dialyzing in deionized water for 4 days, and freeze-drying the dialyzed solution to obtain a poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator (formula I-1) with the GPC number average molecular weight of 8800g/mol and the PDI of 1.14; wherein the nuclear magnetic molecular weight of the poly (N-isopropylacrylamide) segment is 5660g/mol, the polymerization degree is 50, the nuclear magnetic molecular weight of the poly (N, N-dimethylacrylamide) segment is 590g/mol, and the polymerization degree is 6.
2. Preparation of Acryloxybutyl-4-benzodiazelnylbenzoic acid ester
4.0g (17.68mmol) of 4-benzodiazelnylbenzoic acid and 1.795g (14.7mmol) of 4-dimethylaminopyridine are dissolved in 105mL of dichloromethane, 2.04mL (14.7mmol) of hydroxybutyl acrylate are added, and after stirring and activation in an ice bath for 30 minutes, 92mL of a dichloromethane solution containing 3.94g (19.11mmol) of dicyclohexylcarbodiimide are added dropwise, and after completion of the addition, the temperature is raised to 25 ℃ for reaction for 24 hours. And after the reaction is finished, filtering the crude product to remove insoluble dicyclohexylurea, extracting the filtrate for three times by using saturated sodium bicarbonate aqueous solution, extracting for three times by using deionized water, drying over night by using anhydrous magnesium sulfate, carrying out suction filtration, carrying out rotary evaporation and concentration on the filtrate, purifying by using dichloromethane as eluent through silica gel column chromatography, finally carrying out rotary evaporation under reduced pressure to remove the eluent, and carrying out vacuum drying at 35 ℃ to obtain an orange solid product, namely acryloyloxybutyl-4-benzodiazepine benzoic acid ester shown in the formula II-1.
3. Preparation of Poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -Acryloxybutyl-4-Benzodicarbamate ] Block copolymer
1.5g (4.26mmol) of acryloyloxybutyl-4-benzodiazepinylbenzoate and 0.555g (0.0888mmol) of poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator were weighed out and dissolved in a mixture of 4.8mL of tetrahydrofuran and 3.6mL of methanol, 72. mu.L (0.2556mmol) of 1,1,4,7,10, 10-hexamethyltriethylenetetramine and 0.0021g (0.1704mmol) of cuprous bromide were added, and after stirring and mixing uniformly, the procedure of "freeze-vacuum-thaw" was repeated three times, and the mixture was sealed under nitrogen and reacted at 35 ℃ for 24 hours. After the reaction is finished, the reaction solution uses tetrahydrofuran as an eluent, a neutral alumina column is used for removing a catalyst of the system, a product is collected and precipitated twice in ice-N-hexane, and the precipitate is dried in vacuum to obtain a poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer shown in formula III-1, wherein the LCST of the block copolymer is 39.5 ℃, the number average molecular weight is 16800g/mol, and the PDI is 1.07; wherein the nuclear magnetic molecular weight of the poly (acryloyloxybutyl-4-benzodiazelnylbenzoate) block is 2470g/mol, and the polymerization degree is 7.
The present inventors confirmed the chemical structure of the poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer prepared above by nuclear magnetic resonance spectroscopy as shown in fig. 1; the temperature sensitivity of the sample is characterized by adopting a U-3900H type ultraviolet-visible spectrophotometer shown in figure 2. The light responsiveness of the sample was characterized by using a UV-6100S type ultraviolet-visible spectrophotometer, as shown in FIG. 3.
As can be seen from FIG. 2, the absorption peak with chemical shift between 7.5 and 8.1 is the characteristic peak of benzene ring on 4-benzodiazelnylbenzoate, the absorption peak with chemical shift at 4.0 is the absorption peak of methine in isopropyl group on N-isopropylacrylamide, and the absorption peak with chemical shift at about 2.9 is the absorption peak of methyl group on N, N-dimethylacrylamide. From this, it was found that a poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer was successfully produced. As can be seen from FIG. 2, the LCST of the block copolymer was 39.5 ℃. As can be seen from FIG. 3, the azobenzene in the block copolymer has a reduced intensity of the pi-pi absorption peak at 320nm and an increased intensity of the n-pi absorption peak at 425nm under 365nm UV irradiation, and the stabilized trans structure is completely changed into the cis structure after 240 seconds. And under the irradiation of visible light, the structure can be restored to the trans-form structure. The copolymer material is proved to have good response to ultraviolet/visible light.
Example 2
1. Preparation of Poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator
This step is the same as step 1 of example 1.
2. Preparation of Acryloxybutyl-4-benzodiazelnylbenzoic acid ester
This step is the same as step 2 of example 1.
3. Preparation of Poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -Acryloxybutyl-4-Benzodicarbamate ] Block copolymer
1.5g (4.26mmol) of acryloyloxybutyl-4-benzodiazepinylbenzoate and 0.653g (0.104mmol) of poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator were weighed out and dissolved in a mixture of 4.8mL of tetrahydrofuran and 3.6mL of methanol, 72. mu.L (0.2556mmol) of 1,1,4,7,10, 10-hexamethyltriethylenetetramine and 0.0021g (0.1704mmol) of cuprous bromide were added, and after stirring and mixing uniformly, "freeze-pump vacuum-thaw" operation was repeated three times and the mixture was sealed under nitrogen, reacted at 35 ℃ for 24 hours. After the reaction is finished, the reaction liquid uses tetrahydrofuran as an eluent, a neutral alumina column is used for removing a catalyst of the system, a product is collected and precipitated twice in ice-N-hexane, and the precipitate is dried in vacuum to obtain a poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer shown as a formula III-2, wherein the number average molecular weight of the block copolymer is 14800g/mol, and the PDI is 1.07; wherein the nuclear magnetic molecular weight of the poly (acryloyloxybutyl-4-benzodiazelnylbenzoate) block is 1410g/mol, and the polymerization degree is 4.
Example 3
1. Preparation of Poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator
4.12g (36mmol) of N-isopropylacrylamide are weighed out and introduced into a 25mL dry Schlenk flask, 412. mu.L (4mmol) of N, N-dimethylacrylamide, 3.6mL of N, N-dimethylformamide and 2.4mL of water, 52. mu.L (0.4mmol) of ethyl 2-bromopropionate, 106.9. mu.L (0.4mmol) of tris (2-dimethylaminoethyl) amine and 0.0574g (0.4mmol) of cuprous bromide are added to the Schlenk flask and mixed well with stirring, and the mixture is subjected to three repeated "freeze-pump-thaw" operations and sealed under nitrogen and reacted at 25 ℃ for 24 hours. After the reaction is finished, diluting the reaction liquid with tetrahydrofuran, removing a catalyst of a system by using tetrahydrofuran as an eluent through a neutral alumina column, removing most of a solvent from an effluent liquid through rotary evaporation concentration, filling the concentrated liquid into a dialysis bag with the molecular weight of 2000, dialyzing in deionized water for 4 days, and freeze-drying the dialyzed solution to obtain a poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator (formula I-2) with the number average molecular weight of 8400g/mol and the PDI of 1.12; wherein the nuclear magnetic molecular weight of the poly (N-isopropylacrylamide) segment is 4980g/mol, the polymerization degree is 44, the nuclear magnetic molecular weight of the poly (N, N-dimethylacrylamide) segment is 300g/mol, and the polymerization degree is 3.
2. Preparation of Acryloxybutyl-4-benzodiazelnylbenzoic acid ester
This step is the same as step 2 of example 1.
3. Preparation of Poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -Acryloxybutyl-4-Benzodicarbamate ] Block copolymer
0.25g (0.71mmol) of acryloyloxybutyl-4-benzodiazepinylbenzoate and 0.150g (0.0284mmol) of poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator were weighed out and dissolved in a mixture of 0.8mL of tetrahydrofuran and 0.6mL of methanol, and 23. mu.L (0.0852mmol) of 1,1,4,7,10, 10-hexamethyltriethylenetetramine and 8mg (0.0568mmol) of cuprous bromide were added thereto, and after stirring and mixing uniformly, three repeated "freeze-pump-vacuum-thaw" operations were carried out and sealing was carried out under nitrogen, and the reaction was carried out at 35 ℃ for 24 hours. After the reaction is finished, the reaction liquid uses tetrahydrofuran as an eluent, a neutral alumina column is used for removing a catalyst of the system, a product is collected and precipitated twice in ice-N-hexane, and the precipitate is dried in vacuum to obtain a poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer shown in formula III-3, wherein the number average molecular weight of the block copolymer is 13800g/mol, and the PDI is 1.08; wherein the nuclear magnetic molecular weight of the poly (acryloyloxybutyl-4-benzodiazelnylbenzoate) block is 3170g/mol, and the polymerization degree is 9.
Example 4
1. Preparation of Poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator
This step is the same as step 1 of example 3.
2. Preparation of Acryloxybutyl-4-benzodiazelnylbenzoic acid ester
This step is the same as step 2 of example 1.
3. Preparation of Poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -Acryloxybutyl-4-Benzodicarbamate ] Block copolymer
0.5g (1.42mmol) of acryloyloxybutyl-4-benzodiazepinylbenzoate and 0.067g (0.01268mmol) of poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator were weighed out and dissolved in a mixture of 1.6mL of tetrahydrofuran and 1.2mL of methanol, 6. mu.L (0.0213mmol) of 1,1,4,7,10, 10-hexamethyltriethylenetetramine and 2mg (0.0142mmol) of cuprous bromide were added, and after stirring and mixing uniformly, three repeated "freeze-pump-vacuum-thaw" operations were carried out and sealing was carried out under nitrogen, and the reaction was carried out at 35 ℃ for 24 hours. After the reaction is finished, the reaction liquid uses tetrahydrofuran as an eluent, a neutral alumina column is used for removing a catalyst of the system, the product is collected and precipitated twice in ice-N-hexane, and the precipitate is dried in vacuum to obtain a poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxybutyl-4-benzodiazelnylbenzoate ] block copolymer shown as a formula III-4, wherein the number average molecular weight of the block copolymer is 20200g/mol, and the PDI is 1.15; wherein the nuclear magnetic molecular weight of the poly (acryloyloxybutyl-4-benzodiazelnylbenzoate) block is 4580g/mol, and the polymerization degree is 13.
Claims (5)
1. A temperature responsive side chain photosensitive poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] block copolymer characterized by: the structural formula of the block copolymer is as follows:
wherein x represents an integer of 40-65, y represents an integer of 2-7, z represents an integer of 2-15, and m is 1, 1.5, 2, 2.5 or 3.
2. A method of preparing the poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] block copolymer of claim 1, characterized by comprising the steps of:
(1) preparation of Poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator
Taking a mixed solution of N, N-dimethylformamide and water in a volume ratio of 3:2 as a solvent, cuprous bromide as a catalyst, ethyl 2-bromopropionate as an initiator and tris (2-dimethylaminoethyl) amine as a ligand, and carrying out random copolymerization on N-isopropylacrylamide and N, N-dimethylacrylamide by an atom transfer radical polymerization method to obtain a poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator shown in formula I;
(2) preparation of acryloyloxyalkyl-4-benzodiazelnylbenzoic acid esters
Using dichloromethane as a solvent, 4-dimethylamino pyridine as a catalyst and dicyclohexyl carbodiimide as a dehydrating agent, and carrying out esterification reaction on 4-phenyl diazenyl benzoic acid and hydroxyalkyl acrylate to obtain acryloyloxyalkyl-4-phenyl diazenyl benzoic acid ester shown in a formula II;
the hydroxyalkyl acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate and hydroxyhexyl acrylate;
(3) preparation of Poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] Block copolymer
The method comprises the steps of taking a mixed solution with a volume ratio of tetrahydrofuran to methanol of 4:3 as a solvent, cuprous bromide as a catalyst, 1,1,4,7,10, 10-hexamethyltriethylenetetramine as a ligand, and carrying out atom transfer radical polymerization reaction on poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator and acryloyloxyalkyl-4-benzodiazepine benzoic acid ester to obtain a poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazepine benzoic acid ester ] block copolymer.
3. The method of claim 2, wherein the poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] block copolymer is prepared by: in the step (1), the molar ratio of the ethyl 2-bromopropionate to the N-isopropylacrylamide to the N, N-dimethylacrylamide to the cuprous bromide to the tris (2-dimethylaminoethyl) amine is 1: 90-95: 5-10: 1:1.
4. The method of claim 2, wherein the poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] block copolymer is prepared by: in the step (2), the molar ratio of the 4-benzodiazelnylbenzoic acid to the hydroxyalkyl acrylate to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 1.1-1.5: 1: 1.1-1.5: 1.
5. The method of claim 2, wherein the poly [ (N-isopropylacrylamide-N, N-dimethylacrylamide) -acryloyloxyalkyl-4-benzodiazelnylbenzoate ] block copolymer is prepared by: in the step (3), the molar ratio of the poly (N-isopropylacrylamide-N, N-dimethylacrylamide) macroinitiator, the acryloyloxyalkyl-4-benzodiazepine benzoate, the 1,1,4,7,10, 10-hexamethyltriethylenetetramine and the cuprous bromide is 1: 25-200: 1-3: 1-2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811618849.XA CN109705290B (en) | 2018-12-28 | 2018-12-28 | Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811618849.XA CN109705290B (en) | 2018-12-28 | 2018-12-28 | Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109705290A CN109705290A (en) | 2019-05-03 |
| CN109705290B true CN109705290B (en) | 2021-01-01 |
Family
ID=66258842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811618849.XA Expired - Fee Related CN109705290B (en) | 2018-12-28 | 2018-12-28 | Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705290B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045778B (en) * | 2021-03-19 | 2022-05-31 | 常州大学 | Preparation method of dual-response self-repairing hydrogel |
| CN113150228B (en) * | 2021-04-21 | 2022-05-10 | 中国科学院深圳先进技术研究院 | Ultrasonic response type polymer and nano-particles thereof, and preparation method and application thereof |
| CN114507448B (en) * | 2022-02-15 | 2023-09-29 | 武汉利眠生物科技有限公司 | Sustained-release sleep-aiding microcapsule, preparation method thereof, magnetic therapy adhesive body containing same and magnetic therapy adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865014A (en) * | 2014-03-21 | 2014-06-18 | 东华大学 | Preparation method for amphipathic copolymerization network |
| CN107955098A (en) * | 2017-12-01 | 2018-04-24 | 广东电网有限责任公司电力科学研究院 | A kind of elastomer and preparation method thereof |
-
2018
- 2018-12-28 CN CN201811618849.XA patent/CN109705290B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865014A (en) * | 2014-03-21 | 2014-06-18 | 东华大学 | Preparation method for amphipathic copolymerization network |
| CN107955098A (en) * | 2017-12-01 | 2018-04-24 | 广东电网有限责任公司电力科学研究院 | A kind of elastomer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| GANG WANG.Azobenzene-Based Initiator for Atom Transfer Radical Polymerization of Methyl Methacrylate.《Journal of polymer science part a-polymer chemistry》.2005,第43卷(第11期), * |
| S. L. Sin.Photochemical and Thermal Isomerizations of Azobenzene-Containing Amphiphilic Diblock Copolymers in Aqueous Micellar Aggregates and in Film.《Macromolecules》.2005,第38卷(第9期), * |
| Shereen Tan.Azobenzene-Functionalised Core Cross-Linked Star Polymers and their Host-Guest Interactions.《AUSTRALIAN JOURNAL OF CHEMISTRY》.2013,第67卷(第1期), * |
| 李丽霞.新型交联高分子载体材料的设计、制备及在催化反应中的应用.《中国博士学位论文全文数据库 工程科技I辑》.2013,(第8期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109705290A (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109705290B (en) | Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof | |
| Cui et al. | Synthesis and characterization of Eu (III) complexes of modified cellulose and poly (N-isopropylacrylamide) | |
| Dang et al. | Tunable white-light emission hybrids based on lanthanide complex functionalized poly (ionic liquid): Assembly and chemical sensing | |
| CN104861172A (en) | Preparation method of porphyrin core star copolymer with fluorescence effect, PH responsiveness and temperature responsiveness | |
| CN101200526B (en) | Multiple environment-responsive tri-block copolymer and preparation method thereof | |
| Ventura et al. | Synthesis and photochemical properties of spiropyran graft and star polymers obtained by ‘click’chemistry | |
| Abiko et al. | Thermoresponsive core–shell nanoparticles with cross-linked π-conjugate core based on amphiphilic block copolymers by RAFT polymerization and palladium-catalyzed coupling reactions | |
| Zhang et al. | Synthesis and ion responsiveness of optically active polyacetylenes containing salicylidene Schiff-base moieties | |
| Cheng et al. | Pyridine-functionalized luminescent organoboron quinolate block copolymers as versatile building blocks for assembled nanostructures | |
| Bojinov et al. | Synthesis of new polymerizable 1, 8-naphthalimide dyes containing a 2-hydroxyphenylbenzotriazole fragment | |
| CN109320636B (en) | Triple stimulus-responsive core-crosslinked polymer micelle and preparation method and application thereof | |
| Joshi et al. | Light-regulated growth of polymer chains from the surface of RAFT agent primed mesoporous silica nanoparticles | |
| CN110483709B (en) | Responsive crosslinked polymer micelle based on multiple hydrogen bond interaction, and preparation method and application thereof | |
| CN103881073B (en) | Preparation method of fluorescent polymer capable of realizing fluorescence enhancement by using self-assembly | |
| KR101595034B1 (en) | Ultraviolet ray blocking film, acrylamide based compound and polymer included therein | |
| CN108641092A (en) | The preparation method of supermolecule polymer composite micelle based on hydrogen bond | |
| KR20140099388A (en) | Propiolamide based compound, propiolamide based polymer and preparation method thereof | |
| KR101719036B1 (en) | Polymer for pH sensor and manufacturing method thereof, and pH sensor using it | |
| CN103254371B (en) | Synthetic method of amphiphilic block polymer with near-infrared fluorescence characteristic | |
| Li et al. | Preparation of PNIPAM-Azo by RAFT polymerization and their application in thermo-and light-responsive hydrogel | |
| CN102617779B (en) | 2,3,4,5-tetraphenylsilole-based water-soluble polymer and its preparation method and use | |
| CN111234241B (en) | Triple-stimulus-responsive degradable nano polymer micelle and preparation method and application thereof | |
| Dikmen et al. | In-situ formation of fluorophore cross-linked micellar thick films and usage as drug delivery material for Propranolol HCl | |
| CN103980398A (en) | Self-assembly with perylene derivative or analog as fluorescent chromogenic end group and preparation method thereof | |
| JPS6355527B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210101 Termination date: 20211228 |