CN106632925A - Preparation method for amphiphilic segmented copolymer with pH value and temperature sensitivities - Google Patents
Preparation method for amphiphilic segmented copolymer with pH value and temperature sensitivities Download PDFInfo
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- CN106632925A CN106632925A CN201611215247.0A CN201611215247A CN106632925A CN 106632925 A CN106632925 A CN 106632925A CN 201611215247 A CN201611215247 A CN 201611215247A CN 106632925 A CN106632925 A CN 106632925A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Abstract
The invention relates to a preparation method for an amphiphilic segmented copolymer with pH value and temperature sensitivities. The preparation method comprises the following steps: by adopting a reversible addition-fragmentation chain transfer polymerization process, synthesizing a macromolecular chain transfer agent namely tert-butyl polyacrylate, and subjecting the tert-butyl polyacrylate with dimethylaminoethyl methacrylate and ethylene glycol monomethyl ether methacrylate to the reversible addition-fragmentation chain transfer (RAFT) polymerization process again so as to synthesize the amphiphilic segmented copolymer P(tBA)-b-P(DMAEMA-co-PEGMA. The segmented copolymer provided by the invention can self-assemble to form micelles in an aqueous solution, and has pH value and temperature sensitivities, wherein the micelles have a critical pH value of 7 and a critical temperature of 37.5 DEG C. The preparation method provided by the invention has the advantages of high yield, relatively wide applicable monomer range, low requirements on reaction conditions, simple and convenient operation, greenness and environmental friendliness; and the amphiphilic segmented copolymer prepared by using the method provided by the invention has double pH value and temperature sensitivities and broad application prospects, and can be applied to the chemical production fields like dye adsorption, the environment protection fields like heavy metal pollution treatment, and the biomedical fields like controllable release of insoluble drugs.
Description
Technical field
The invention belongs to chemical industry and new material technology field, and in particular to a kind of amphipathic with pH and temperature sensitivity
Segmented copolymer P (tBA)-b-P(DMAEMA-co- PEGMA) preparation method.
Background technology
Environment-responsive polymeric material, refers in the case where less external environment changes, it may occur that some are obvious
The macromolecular material being physically or chemically mutated, this kind of material would generally in specific environment occurred conformation adjust with to ring
Border response for changing response, so as to the transformation that phase structure occurs, using this feature of environment-responsive polymeric material,
The intellectual material of specific response can be according to demand designed with.Amphipathic multi-block copolymer is in some selective solvents
In self assembly phenomenon can occur, form the structures such as the micella and vesica of ad hoc structure.With reference to the two advantage, synthesis
Amphipathic multi-block copolymer with environment-responsive can not only be made to the stimulation that pH and temperature etc. change external environment
Reaction, can also carry the medicine or organic dyestuff that are insoluble in water, therefore this kind of thing by forming the aggregations such as micella and vesica
Matter has using value in the numerous areas such as biomedical, Chemical Manufacture and environmental protection.
At present, the synthetic method of most of environment-responsive polymeric materials and general block or graft copolymer and
Branched polymer is identical.Conventional method includes GTP (GTP) and Controlled Living Radical Polymerization (CLRP), wherein
CLRP is divided into reversible addition-fracture-transferring free-radical polymerization (RAFT), ATRP (ATRP) and nitrogen oxygen again
Regulation and control radical polymerization (NMP).
GTP is now widely used for the synthesis of poly- methacrylate esters responsive polymer, but GTP is not based on certainly
By base mechanism, synthesis is also only limitted to Tri- n -butyltin methacrylate monomer, and NMP polymerizations reaction rate is relatively low in CLRP, is suitable for
The scope of monomer is narrower；The shortcoming of ATRP polymerization method is cannot to be applied to acid, alkalescence, acid amides or halogen-containing vinyl monomer
Direct polymerization, and during the course of the reaction use metallic element.Although with updating for ATRP technologies, the use of metallic element
Amount greatly reduces, but is in order to suitable environment and toxicological point consideration, and the problem using metallic element is inevitable, therefore
The development of ATRP polymerization method is restricted, and particularly in biomedical sector application, this is particularly problematic.And RAFT is poly-
The legal shortcoming for overcoming above two method, the functional polymer needed for can directly preparing in reaction medium, while
We can be further modified the dithioesters of resulting polymers end or three thioesters, for needed for subsequent reactions are provided
Functional group.Therefore the present invention selected the method for RAFT living polymerizations prepare amphipathic multi-block copolymer p (tBA)-b-P
(DMAEMA-co-PEGMA)。
The content of the invention
It is an object of the invention to overcome the shortcomings of that prior art is present, there is provided a kind of with pH and temperature sensitivity two
Parent's property segmented copolymer P (tBA)-b-P(DMAEMA-co- PEGMA) preparation method.
The present invention propose a kind of amphipathic multi-block copolymer p (tBA) with pH and temperature sensitivity-b-P
(DMAEMA-co- PEGMA) preparation method.The method has synthesized Macromolecular chain transfer agent poly- third initially with RAFT polymerizations
Enoic acid ter-butyl ester (P (tBA)), subsequently by Macromolecular chain transfer agent P (tBA), dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA) and
Methoxypolyethylene glycol methacrylate (PEGMA) carry out RAFT polymerizations synthesized amphipathic multi-block copolymer p (tBA)-b-P(DMAEMA-co-PEGMA).In aqueous, the segmented copolymer can be self-assembled into quick with pH and temperature dual
The micella of perception, wherein hydrophilic P (DMAEMA-co- PEGMA) shell of micella is constituted, and PPEGMA comb shapes segmented structure can be with
Strengthen the biocompatibility of micella, and hydrophobic P (tBA) is then gathered into the core of micella.
The present invention proposes a kind of preparation method with pH and the amphipathic multi-block copolymer of temperature sensitivity, described
Amphipathic multi-block copolymer be P (tBA)-b-P(DMAEMA-co- PEGMA), comprise the following steps that：
(1) synthesis of the polyacrylic acid tert-butyl ester (P (tBA))
Weigh 1 ~ 5 g tert-butyl acrylates (tBA) to be placed in 50 mL single necked round bottom flask, take 5 ~ 50 mg 4- cyano group -4- (sulphur
For benzoyl) valeric acid and 1 ~ 10 mg azodiisobutyronitriles in 50 mL beakers, add the dissolving of 5 ~ 15 mL dioxane.Then
Both are mixed, by " T-shaped " threeway, single-necked flask is vacuumized at 0 DEG C, and be passed through nitrogen.It is placed under nitrogen protection
6 ~ 24 h, uniform magnetic agitation are reacted under 60 ~ 90 DEG C of oil baths.Reaction leads to air after after terminating flask is cooled down in ice-water bath,
Solution after cooling is added drop-wise to into 100 ~ 300 mL methanol/water (v: v = 2 :1) in mixed solution, 1 ~ 6 h is stood, is removed
Supernatant liquid, obtains bottom pale pink precipitation.Repeat above settling step once, finally vacuum is done at 30 ~ 50 DEG C by sample
Dry 6 ~ 72 h, obtains the polyacrylic acid tert-butyl ester (P (tBA)).
(2) amphipathic multi-block copolymer p (tBA)-b-P(DMAEMA-co- PEGMA) synthesis
By 0.5 ~ 2.5 g dimethylaminoethyl acrylate methyls ammonia ethyl ester (DMAEMA) and 0.1 ~ 0.5 g EGME methacrylates
(PEGMA) in being placed in 50 mL single necked round bottom flask.Weigh 0.5 ~ 1.5 g steps（1）Product polypropylene tert-butyl acrylate (P
) and 0.5 ~ 2.5 mg azodiisobutyronitriles are in 50 mL beakers, (tBA) dissolving of 5 ~ 15 mL dioxane is added.Then will
Both mixing, by " T-shaped " threeway, vacuumize to single-necked flask at 0 DEG C, and are passed through nitrogen.60 are placed under nitrogen protection
6 ~ 36 h, uniform magnetic agitation are reacted under ~ 90 DEG C of oil baths.Reaction leads to air after after terminating flask is cooled down in ice-water bath, will
Solution after cooling is added drop-wise in 100 ~ 300 mL ice petroleum ethers, stands 4 h, removes supernatant liquid, obtains bottom viscous samples.
Repeat above settling step once, finally sample is vacuum dried into 6 ~ 72 h at 30 ~ 50 DEG C, obtain amphipathic multi-block copolymerization
Thing P (tBA)-b-P(DMAEMA-co-PEGMA)。
(3)P(tBA)-b-P(DMAEMA-co- PEGMA) micella preparation
Weigh 5 ~ 25 mg steps（2）In P (tBA)-b-P(DMAEMA-co- PEGMA) polymer, 1 ~ 10 mL N are dissolved in,
In dinethylformamide, electromagnetic agitation is until dissolving, by 5 ~ 15 mL deionized waters instillation solution, can be observed solution general
Indigo plant, continues to stir half an hour after dripping off, and then solution loaded the bag filter deionization of the Da of molecular cut off 2000 ~ 5000
Water dialyse 12 ~ 72 h remove DMF, obtain P (tBA)-b-P(DMAEMA-co- PEGMA) micella.
Compared with prior art, advantages of the present invention mainly has following three points：
1. the present invention is a kind of based on a kind of amphipathic multi-block copolymerization with pH and temperature sensitivity of RAFT polymerizations synthesis
The method of thing, the method is for other Controlled Living Radical Polymerizations, and yield is higher, and rate of polymerization is higher, is suitable for
Monomer scope is relatively wide, and reaction condition is required relatively low.2. the amphipathic multi-block copolymer that prepared by the present invention has
PH and temperature dual-sensitivity.When temperature is increased to lower critical solution temperature, the hydrophily of polymer segment weakens therewith, micella
Reunite；After temperature is reduced, this micella reunited can be separated again, realize the invertibity response changed to environment temperature；
When pH increases, the shell structurre of copolymer micelle presents shrinks to some extent, and particle diameter reduces therewith.3. system of the invention
Preparation Method is easy to operate, environmental protection, has a extensive future, and can be applicable at the chemical production fields such as Dye Adsorption, pollutant
The biomedicine fields such as the controlled release of the field of environment protection such as reason and insoluble medicine, are a kind of novel intelligent polymeric materials.
Description of the drawings
Fig. 1 be embodiment 1 based on RAFT polymerizations synthesis P (tBA)-b-P(DMAEMA-co- PEGMA) schematic diagram.
Fig. 2 be the fluorescence probe method of embodiment 1 measure P (tBA)-b-P(DMAEMA-co- PEGMA) critical micell is dense
Degree.
Fig. 3 be P (tBA) under the difference pH of embodiment 1-b-P(DMAEMA-co- PEGMA) micella (1 mg/L) hydrodynamics
Diameter.
Fig. 4 be P (tBA) under the different temperatures of embodiment 1-b-P(DMAEMA-co- PEGMA) micella (1 mg/L) fluid force
Learn diameter.
Specific embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
The first step：Weigh 2.75 g tert-butyl acrylates (tBA) to be placed in 50 mL single necked round bottom flask, take 20 mg 4- cyano group-
4- (thio benzoyl) valeric acids and 3.52 mg azodiisobutyronitriles add the dissolving of 10 mL dioxane in 50 mL beakers.So
Both are mixed afterwards, by " T-shaped " threeway, single-necked flask is vacuumized at 0 DEG C, and be passed through nitrogen.Put under nitrogen protection
12 h, uniform magnetic agitation are reacted under 70 DEG C of oil baths.Reaction leads to air after after terminating flask is cooled down in ice-water bath, will be cold
But the solution after is added drop-wise to 200 mL methanol/water (v: v = 2 :1) in mixed solution, 4 h are stood, remove supernatant liquid,
Obtain bottom pale pink precipitation.Repeat above settling step once, finally sample is vacuum dried into 48 h at 40 DEG C, obtain light
Pink colour sample, that is, obtain the polyacrylic acid tert-butyl ester (P (tBA)).
Second step：By 1.22 g dimethylaminoethyl acrylate methyls ammonia ethyl ester (DMAEMA) and 0.24 g EGME metering systems
Acid esters (PEGMA) is placed in 50 mL single necked round bottom flask.Weigh the product polypropylene tert-butyl acrylate (P (tBA)) of the 1 g first steps
With 1.27 mg azodiisobutyronitriles in 50 mL beakers, the dissolving of 10 mL dioxane is added.Then both are mixed, is led to
" T-shaped " threeway is crossed, single-necked flask is vacuumized at 0 DEG C, and be passed through nitrogen.It is placed under nitrogen protection under 70 DEG C of oil baths anti-
Answer 24 h, uniform magnetic agitation.Reaction leads to air after after terminating flask is cooled down in ice-water bath, and the solution after cooling is added dropwise
To in 200 mL ice petroleum ethers, 4 h are stood, remove supernatant liquid, obtain bottom viscous samples.Repeat above settling step one
It is secondary, finally sample is vacuum dried into 48 h at 40 DEG C.Faint yellow sample is obtained, that is, obtains amphipathic multi-block copolymer p
(tBA)-b-P(DMAEMA-co-PEGMA)。
3rd step：Weigh 15 mg P (tBA)-b-P(DMAEMA-co- PEGMA) polymer, it is dissolved in 5 mL N, N- bis-
In NMF, electromagnetic agitation instills 10 mL deionized waters in solution up to dissolving, and solution blueing can be observed, and drips off
Continue afterwards to stir half an hour, then remove bag filter deionized water 48 h of dialysis that solution loads the Da of molecular cut off 3500
Remove DMF, obtain P (tBA)-b-P(DMAEMA-co- PEGMA) micella.
Using dynamic light scattering (DLS) to amphipathic multi-block copolymer p (tBA)-b-P(DMAEMA-co- PEGMA) glue
Beam particle diameter is tested with the change (pH=2 ~ 11) of pH, and as a result as shown in figure 3, as can be seen from Figure 3, the micella has
Obvious pH response performances, when pH is 6.5, particle diameter is undergone mutation.
Reuse DLS to be tested micella particle diameter variation with temperature (T=30 ~ 45 DEG C), as a result such as Fig. 4 institutes
Show, figure 4, it can be seen that the micella has obvious temperature response performance, when temperature is 37.5 DEG C, particle diameter is undergone mutation.
Embodiment 2
Compared with Example 1, tert-butyl acrylate in the first step (P (tBA)) consumption is changed into into 2.29 g, other conditions keep not
Become, then monomer propylene tert-butyl acrylate, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acids and initiator azo two are different in system
The mol ratio of butyronitrile is changed into 250: 1 : 0.3.
Embodiment 3
Compared with Example 1, tert-butyl acrylate in the first step (P (tBA)) consumption is changed into into 1.84 g, other conditions keep not
Become, then monomer propylene tert-butyl acrylate, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acids and initiator azo two are different in system
The mol ratio of butyronitrile is changed into 200: 1 : 0.3.
Embodiment 4
Compared with Example 1, tert-butyl acrylate in the first step (P (tBA)) consumption is changed into into 1.38 g, other conditions keep not
Become, then monomer propylene tert-butyl acrylate, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acids and initiator azo two are different in system
The mol ratio of butyronitrile is changed into 150: 1 : 0.3.
Embodiment 5
Compared with Example 1, dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA) consumption in second step is changed into into 1.01 g, other
Part keeps constant, then monomer methacrylic acid diformazan ammonia ethyl ester, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid in system
It is changed into 250 with the mol ratio of initiator (azodiisobutyronitrile): 1 : 0.3.
Embodiment 6
Compared with Example 1, dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA) consumption in second step is changed into into 0.81 g, other
Part keeps constant, then monomer methacrylic acid diformazan ammonia ethyl ester in system, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid
It is changed into 200 with the mol ratio of initiator azodiisobutyronitrile: 1 : 0.3.
Embodiment 7
Compared with Example 1, dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA) consumption in second step is changed into into 0.61 g, other
Part keeps constant, then monomer methacrylic acid diformazan ammonia ethyl ester in system, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid
It is changed into 150 with the mol ratio of initiator azodiisobutyronitrile: 1 : 0.3.
Embodiment 8
Compared with Example 1, EGME methacrylate (PEGMA) consumption in second step is changed into into 0.36 g, other
Condition keeps constant, then monomer EGME methacrylate, chain-transferring agent 4- cyano group -4- (thio benzoyl) in system
The mol ratio of valeric acid and initiator azodiisobutyronitrile is changed into 15: 1 : 0.3.
Embodiment 9
Compared with Example 1, EGME methacrylate (PEGMA) consumption in second step is changed into into 0.48 g, other
Condition keeps constant, then monomer EGME methacrylate, chain-transferring agent 4- cyano group -4- (thio benzoyl) in system
The mol ratio of valeric acid and initiator azodiisobutyronitrile is changed into 20: 1 : 0.3.
The amphipathic multi-block polymer P (tBA) with pH and temperature dual sensitiveness obtained in embodiment 2-9-b-P
(DMAEMA-co- PEGMA) there is similar performance with the product of embodiment 1.
Claims (3)
1. a kind of preparation method with pH and the amphipathic multi-block copolymer of temperature sensitivity, it is characterised in that the amphiphilic
Property segmented copolymer be P (tBA)-b-P(DMAEMA-co- PEGMA), comprise the following steps that：
(1) synthesis of the polyacrylic acid tert-butyl ester (P (tBA))
Weigh 1 ~ 5 g tert-butyl acrylates (tBA) to be placed in 50 mL single necked round bottom flask, take 5 ~ 50 mg 4- cyano group -4- (sulphur
For benzoyl) valeric acid and 1 ~ 10 mg azodiisobutyronitriles in 50 mL beakers, add the dissolving of 5 ~ 15 mL dioxane；Then
Both are mixed, by " T-shaped " threeway, single-necked flask is vacuumized at 0 DEG C, and be passed through nitrogen；It is placed under nitrogen protection
6 ~ 24 h, uniform magnetic agitation are reacted under 60 ~ 90 DEG C of oil baths；Reaction leads to air after after terminating flask is cooled down in ice-water bath,
Solution after cooling is added drop-wise to into 100 ~ 300 mL methanol/water (v: v = 2 :1) in mixed solution, 1 ~ 6 h is stood, is removed
Supernatant liquid, obtains bottom pale pink precipitation；Repeat above settling step once, finally vacuum is done at 30 ~ 50 DEG C by sample
Dry 6 ~ 72 h, obtains the polyacrylic acid tert-butyl ester (P (tBA))；
(2) amphipathic multi-block copolymer p (tBA)-b-P(DMAEMA-co- PEGMA) synthesis
By 0.5 ~ 2.5 g dimethylaminoethyl acrylate methyls ammonia ethyl ester (DMAEMA) and 0.1 ~ 0.5 g EGME methacrylates
(PEGMA) in being placed in 50 mL single necked round bottom flask；Weigh 0.5 ~ 1.5 g steps（1）Product polypropylene tert-butyl acrylate (P
) and 0.5 ~ 2.5 mg azodiisobutyronitriles are in 50 mL beakers, (tBA) dissolving of 5 ~ 15 mL dioxane is added；Then will
Both mixing, by " T-shaped " threeway, vacuumize to single-necked flask at 0 DEG C, and are passed through nitrogen；60 are placed under nitrogen protection
6 ~ 36 h, uniform magnetic agitation are reacted under ~ 90 DEG C of oil baths；Reaction leads to air after after terminating flask is cooled down in ice-water bath, will
Solution after cooling is added drop-wise in 100 ~ 300 mL ice petroleum ethers, stands 4 h, removes supernatant liquid, obtains bottom viscous samples；
Repeat above settling step once, finally sample is vacuum dried into 6 ~ 72 h at 30 ~ 50 DEG C, obtain amphipathic multi-block copolymerization
Thing P (tBA)-b-P(DMAEMA-co-PEGMA)；
(3) P(tBA)-b-P(DMAEMA-co- PEGMA) micella preparation
Weigh 5 ~ 25 mg steps（2）In P (tBA)-b-P(DMAEMA-co- PEGMA) polymer, 1 ~ 10 mL N are dissolved in,
In dinethylformamide, electromagnetic agitation is until dissolving, by 5 ~ 15 mL deionized waters instillation solution, can be observed solution general
Indigo plant, continues to stir half an hour after dripping off, and then solution loaded the bag filter deionization of the Da of molecular cut off 2000 ~ 5000
Water dialyse 12 ~ 72 h remove DMF, obtain P (tBA)-b-P(DMAEMA-co- PEGMA) micella.
2. a kind of preparation side with pH and the amphipathic multi-block copolymer of temperature sensitivity according to claim 1
Method, it is characterised in that described many blocks are respectively polyacrylic acid tert-butyl ester block (P (tBA)) and the poly- (methyl of random copolymer
Acrylic acid diformazan ammonia ethyl ester-co- methoxypolyethylene glycol methacrylate) block (P (DMAEMA-co-PEGMA))。
3. a kind of preparation side with pH and the amphipathic multi-block copolymer of temperature sensitivity according to claim 1
Method, it is characterised in that the described polyacrylic acid tert-butyl ester (P (tBA)) and the polyacrylic acid tert-butyl ester-b- poly- (dimethylaminoethyl acrylate methyl
Ammonia ethyl ester-co- methoxypolyethylene glycol methacrylate) (P (tBA)-b-P(DMAEMA-co- PEGMA)) chemical structural formula
Difference is as follows：
Here, m=80 ~ 2000
(a) polyacrylic acid tert-butyl ester (P (tBA))
Here, m=80 ~ 2000, n=80 ~ 2000
(b) amphipathic multi-block copolymer p tBA-b-P(DMAEMA-co-PEGMA)。
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