CN109456488A - A kind of cinnamic acid derivative base amphiphilic block copolymer and preparation method thereof - Google Patents
A kind of cinnamic acid derivative base amphiphilic block copolymer and preparation method thereof Download PDFInfo
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- CN109456488A CN109456488A CN201811218363.7A CN201811218363A CN109456488A CN 109456488 A CN109456488 A CN 109456488A CN 201811218363 A CN201811218363 A CN 201811218363A CN 109456488 A CN109456488 A CN 109456488A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
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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
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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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
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
Abstract
The present invention relates to a kind of cinnamic acid derivative base amphiphilic block copolymers and preparation method thereof, belong to Functional polymer materials technology field.3- hydroxycinnamic acid (3HCA) is prepared poly- 3- hydroxycinnamic acid (P3HCA) homopolymer of different molecular weight using melt polycondensation and ester exchange reaction by the present invention, and its molecule chain end is carried out chloride.Pass through Transfer Radical Polymerization again, the poly-N-vinylcaprolactam (PNVCL) and polymethylacrylic acid dimethylaminoethyl (PDMAEMA) with terminal hydroxy group are prepared, finally the P3HCA of chloride and PNVCL with terminal hydroxy group or PDMAEMA is reacted and prepares poly- 3- hydroxycinnamic acid-b- poly-N-vinylcaprolactam (P3HCA-b-PNVCL) and poly- 3- hydroxycinnamic acid-b- polymethylacrylic acid dimethylaminoethyl (P3HCA-b-PDMAEMA) block copolymer.Copolymer produced by the present invention has amphipathic, optical Response and temperature-responsive simultaneously, has good structural stability and biocompatibility, can be widely applied to the fields such as drug conveying, organizational project, biology and agricultural.
Description
Technical field
A kind of cinnamic acid derivative base amphiphilic block copolymer and preparation method thereof, belongs to functional polymer material field.
Technical background
Environmental sensitivity polymer is a kind of novel functional polymer that developed recently gets up, the small thorn in the external world
Swashing that it can be generated rapidly influences, and then sudden change occurs from structure, physical property and chemical property.Sensibility
Polymer is realized under faint environmental stimulus, is generated physico by introducing different functional groups on polymer segment
Learn the polymer of change of properties.This kind of functional polymer has wide in fields such as nanotechnology, gene transfection, drug controlled releases
General application becomes the research hotspot of " intelligence " high molecular material.
A kind of important temperature sensitive polymer of poly-N-vinylcaprolactam (PNVCL), minimum Critical Solution temperature
(LCST) is spent in Physiological temperatures range, and PNVCL hydrolysis will not generate toxic small molecule amine, monomer is cheap,
Therefore PNVCL and its copolymer have potential application and preferable industrial prospect in biomedicine field.Poly- methyl
Dimethylaminoethyl acrylate (PDMAEMA) is a kind of pH and temperature sensitive polymer by common concern, in low pH
In medium, tertiary amine groups contained in structure will be protonated, and make PDMAEMA macromolecular chain that extended conformation be presented, and in high pH
Result is exactly the opposite in medium.Its LCST changes with the variation of medium pH simultaneously, in the buffer solution that pH is 7, LCST
About 46 DEG C.Meanwhile PDMAEMA have preferable mechanical strength and good viscoplasticity, intelligent aqueous gel, biomedicine,
The fields such as catalysis and separating-purifying have a good application prospect.
3- hydroxycinnamic acid (3HCA) is a kind of from the plants such as acaroid gum and rice husk " vegetalitas monomer ", is had
The medical efficacies such as antibacterial, antiviral can also be prepared into good thermal stability, fluorescence, mechanical performance, biofacies by polymerization reaction
Capacitive and poly- 3- hydroxycinnamic acid (P3HCA) polymer of degradability.In addition, P3HCA also has light reaction, using purple
Outer illumination regulates and controls its performance, it is expected to be applied to the biomedicine fields such as drug loading, organizational project.
The present invention has synthesized P3HCA by melt polycondensation and ester exchange reaction using 3HCA as raw material, and utilizes thionyl chloride
Realize the chloride of the end P3HCA；Again with dimethylaminoethyl methacrylate (DMAEMA) and N- caprolactam
(NVCL) etc. hydrophilic monomers are raw material, with brominated butyl acid -2- hydroxy methacrylate (HEBI) for initiator, by atom transfer from
Hydroxy-end capped hydrophilic polymer PDMAEMA and PNVCL have been synthesized by base polymerization reaction (ATRP)；Further by acyl chloride terminated
P3HCA and hydroxy-end capped hydrophilic polymer carry out nucleophilic substitution and prepare the poly- methyl-prop of poly- 3- hydroxycinnamic acid-b-
Olefin(e) acid dimethylaminoethyl (P3HCA-b-PDMAEMA) and poly- 3- hydroxycinnamic acid-b- poly-N-vinylcaprolactam (P3HCA-
B-PNVCL) block copolymer.
Summary of the invention
The purpose of the present invention is disclose a kind of multiple sensibility parents based on cinnamic acid derivative and hydrophilic macromolecule
The preparation method of copolymer.
The present general inventive concept is: being prepared into the 3HCA of exhibiting optical function using melt polycondensation and ester-interchange method has end
The degradability uv photosensitivity P3HCA homopolymer of carboxyl；The chloride of P3HCA end group is realized using thionyl chloride；Using
Hydrophilic DMAEMA and NVCL are prepared into PDMAEMA and PNVCL with terminal hydroxy group by ATRP method；By acyl chloride terminated
P3HCA and hydroxy-end capped PDMAEMA and PNVCL carries out nucleophilic substitution and prepares P3HCA-b-PDMAEMA and P3HCA-b-
PNVCL block copolymer.
In order to achieve the above objectives, technical solution provided by the invention are as follows:
1. the P3HCA polymer that synthesis has carboxyl end group
Mass ratio is added separately in acetic anhydride for 100: 1~6 3HCA monomer and anhydrous phosphoric acid sodium catalyst, acetic acid
The mass ratio of acid anhydride and 3HCA are 5~20: 1, nitrogen are continually fed into after mixed at room temperature is uniform, with the mixing speed of 80~600r/min
Under be warming up to 150~160 DEG C, react 2~4h；Continue stirring and temperature is risen to 200~230 DEG C, stops adding after reacting 6~8h
Heat is cooled to room temperature, and entire reaction process is carried out in nitrogen under the conditions of being protected from light；After completion of the reaction, by 4~6 times of matter of product
The n,N-Dimethylformamide (DMF) of amount dissolves, and carries out Precipitation using dehydrated alcohol or methanol as precipitating reagent, in triplicate,
Final product is dry at 30~40 DEG C, obtains the P3HCA polymer that carboxyl end group is had shown in brown formula 1.
2. synthesizing the P3HCA polymer of acyl chloride terminated
By the P3HCA polymer prepared in step 1 and methylene chloride, DMF and thionyl chloride in mass ratio 1: 10~15:
0.05~0.1: 3~5 are uniformly mixed, stirring, are heated to 50~70 DEG C of 10~15h of reaction, and rotary evaporation removes liquid portion, system
The P3HCA polymer of brown solid acyl chloride terminated shown in a standby accepted way of doing sth 2.
3. the hydrophilic polymer of synthesis of hydroxy sealing end
Mass ratio is drawn for 100: 0.5~3 NVCL or DMAEMA monomer and brominated butyl acid -2- hydroxy methacrylate (HEBI)
Hair agent is added separately to dissolve in DMF solvent, and the mass ratio of monomer and solvent is 1: 5~20；Lead to nitrogen after mixing
30min, and cuprous bromide catalyst and N, N, N are quickly added into solution ', N ", N "-pentamethyldivinyltriamine
(PMDETA) ligand, the molar ratio of initiator, catalyst and ligand are 1: 1: 2, are uniformly mixed and continue logical nitrogen 30min, and will
Reactor sealing, is heated to 60~80 DEG C and is stirred to react 5~10h.System temperature is down to room temperature after reaction, and by solution
Cross neutral alumina pillar, repeat precipitating three times as precipitating reagent with ether, prepare hydroxy-end capped PNVCL shown in an accepted way of doing sth 3 or
PDMAEMA polymer.
4. synthesizing responsiveness amphiphilic block copolymer
The PNVCL with terminal hydroxy group that will be synthesized in the P3HCA polymer and step 3 of the acyl chloride terminated prepared in step 2
Or PDMAEMA 1: 1.2-2.4 adding into dichloromethane in mass ratio, the mass ratio of P3HCA and methylene chloride are 1: 10~25；
The pyridine or triethylamine that P3HCA5~15 times quality is added after mixing as acid binding agent, be stirred to react 20 at 20~35 DEG C~
40h is after reaction drained reactant with vacuum pump, and a large amount of dehydrated alcohol supersound washings are added three times, filter and 30~
It dries at 40 DEG C to constant weight, obtains P3HCA-b-PNVCL or P3HCA-b-PDMAEMA responsiveness parents' block copolymerization as shown in Equation 4
Object.
Detailed description of the invention
The nuclear magnetic spectrogram of Fig. 1 responsiveness amphiphilic block copolymer P3HCA-b-PNVCL.
The transmission electron microscope figure of Fig. 2 P3HCA-b-PDMAEMA copolymer micelle.
The absorbance of Fig. 3 P3HCA-b-PDMAEMA copolymer micelle is with ultraviolet lighting time changing curve.
The change of size figure of P3HCA-b-PDMAEMA copolymer micelle before and after Fig. 4 ultraviolet lighting.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but the present invention is not limited to these Examples.
The synthesis of 1 P3HCA-b-PNVCL responsiveness amphiphilic block copolymer of embodiment
(1) synthesis of P3HCA: weighing 3HCA10g, anhydrous sodium phosphate 0.1g, acetic anhydride 80mL, and 250mL reactor is added
In, 155 DEG C are warming up in the case where speed of agitator is 400r/min, after reacting 2h, 200 DEG C is warming up to, continues stirring, isothermal reaction
6h, entire reaction are carried out in nitrogen protection under the conditions of being protected from light.The DMF of 25mL is taken sufficiently to dissolve product, it is heavy with dehydrated alcohol
It forms sediment and purifies, it is in triplicate, finally dry at 30 DEG C, obtain the product of brown.
(2) synthesis of the P3HCA of acyl chloride terminated: taking the P3HCA5g synthesized in step (1), be added 50mL methylene chloride,
0.15gDMF and 20mL thionyl chloride stirs after mixed dissolution, and heating reaction 12h, rotary evaporation remove liquid reactions at 60 DEG C
Object, and reactant is sufficiently drained, obtain the P3HCA of dark-brown acyl chloride terminated.
(3) it the synthesis of hydroxy-end capped PNVCL: takes 2gNVCL monomer and 0.01g HEBI initiator to be dissolved in 20mLDMF, fills
Divide dissolution, lead to nitrogen 30min, continue to rapidly join 0.01g cuprous bromide catalyst and 0.02gPMDETA ligand, continues logical nitrogen
Gas 30min is heated with stirring to 70 DEG C of reaction 8h, after reaction pours into product in the bag filter of weight average molecular weight 1000 and dialyse
Purification 3 days, freeze-drying, obtains white product.
(4) P3HCA1g, the step of the acyl chloride terminated synthesized in step (2) the synthesis of responsiveness amphiphilic block copolymer: are taken
(3) the hydroxy-end capped PNVCL1.4g synthesized in is added in 25mL methylene chloride, is uniformly mixed, and tri- second of 3mL is added
Amine is stirred to react for 24 hours at 30 DEG C, and rotary evaporation removes methylene chloride after reaction, and 100mL dehydrated alcohol ultrasound point is added
It dissipates, agitator treating three times, filters and dry at 30 DEG C, obtains light brown P3HCA-b-PNVCL amphiphilic block copolymer.
The synthesis of 2 P3HCA-b-PDMAEMA responsiveness amphiphilic block copolymer of embodiment
The synthesis step of P3HCA and the P3HCA of acyl chloride terminated are in the same manner as in Example 1 in the present embodiment.
P3HCA-b-PDMAEMA copolymer the preparation method is as follows: taking 2gDMAEMA monomer and 0.01gHEBI initiator molten
It in 20mLDMF, sufficiently dissolves, leads to nitrogen 30min, continue to rapidly join 0.01g cuprous bromide catalyst and 0.02gPMDETA
Ligand is heated with stirring to 70 DEG C of reaction 8h, and product is poured into dialysis in the bag filter of weight average molecular weight 1000 after reaction and is mentioned
Pure 3 days, freeze-drying obtained white hydroxy-end capped PDMAEMA polymer.Take the P3HCA1g, hydroxy-end capped of acyl chloride terminated
PDMAEMA1.3g is added in 25mL methylene chloride, is uniformly mixed, and 3mL triethylamine is added, is stirred to react for 24 hours at 30 DEG C,
Rotary evaporation removes methylene chloride after reaction, and 100mL dehydrated alcohol ultrasonic disperse is added, and agitator treating three times, filters
And it is dry at 30 DEG C, obtain light brown P3HCA-b-PDMAEMA amphiphilic block copolymer.
3 self-assembly method of embodiment prepares P3HCA-b-PNVCL and P3HCA-b-PDMAEMA micella
Using DMF as solvent, P3HCA-b-PNVCL the and P3HCA-b-PDMAEMA copolymer of different compositions is configured to
The solution of 5mg/mL.Under the mixing speed of 800r/min, with microsyringe with the speed of 10 μ L/min to copolymer solution
It is middle that appropriate ultrapure water is added dropwise, copolymer micelle dispersion liquid is made, continues to stir 12h, then the micella dispersion liquid is added dropwise to
In a large amount of ultrapure water in the form of fixing micella, it is subsequently placed in deionized water and dialyses, change a deionized water every 5h, fill
Divide and obtain copolymer micelle dispersion liquid after removing organic solvent, and final concentration is adjusted to 0.2mg/mL.
The optical Response behavior of 4 amphiphilic block copolymer of embodiment
Appropriate P3HCA-b-PNVCL or P3HCA-b-PDMAEMA copolymer micelle dispersion liquid is taken, ultraviolet-visible light is utilized
Spectrophotometer tests its ultraviolet light 0 in 302nm, 5,10,20,30,40,50, the ultra-violet absorption spectrum after 60min
Figure, wave-length coverage carry out light and ring from 200nm to 500nm, and through the variation of particles distribution instrument test light photograph front and back micellar particle size
Answering property is analyzed.
Claims (5)
1. a kind of cinnamic acid derivative base amphiphilic block copolymer and preparation method, it is characterised in that with 3- hydroxycinnamic acid for singly
Body prepares the poly- 3- hydroxycinnamic acid (P3HCA) of acyl chloride terminated；By Transfer Radical Polymerization (ATRP), with N- second
Alkenyl caprolactam and dimethylaminoethyl methacrylate are monomer, prepare the poly-N-vinylcaprolactam with terminal hydroxy group
(PNVCL) and polymethylacrylic acid dimethylaminoethyl (PDMAEMA)；By the P3HCA of acyl chloride terminated and with section hydroxyl
PNVCL and PDMAEMA carries out nucleophilic substitution and prepares poly- 3- hydroxycinnamic acid-b- poly-N-vinylcaprolactam (P3HCA-
) and poly- 3- hydroxycinnamic acid-b- polymethylacrylic acid dimethylaminoethyl (P3HCA-b-PDMAEMA) block copolymerization b-PNVCL
Object.
2. block copolymer according to claim 1, it is characterized in that being constituted main polymer chain with P3HCA and PNVCL segment；
Wherein the molecular weight of P3HCA is 1.0 × 103-5.0×104The molecular weight of g/mol, PNVCL are 1.0 × 103-1.0×105g/
mol；The structure of gained copolymer are as follows:
It indicates to become P3HCA-b-PNVCL.
3. block copolymer according to claim 1, it is characterized in that connecting P3HCA using ethyl isobutyrate as connection unit
The main polymer chain constituted with PDMAEMA segment；Wherein the molecular weight of P3HCA is 1.0 × 103-5.0×104G/mol,
The molecular weight of PDMAEMA is 1.0 × 103-1.0×105g/mol；The structure of gained copolymer are as follows:
It indicates to become P3HCA-b-PDMAEMA.
4. according to the copolymer of the preparation any in claim 2-3, it is characterised in that can be in n,N-Dimethylformamide/water
In carry out being self-assembled into globular micelle, which has certain degradability, under acid, alkalinity and neutrallty condition
Degradation can be achieved, and degradation speed is controllable.
5. according to the copolymer micelle of the preparation any in claim 2-4, it is characterised in that in the ultraviolet light of 300-356nm
Can photo-crosslinking occur according to lower and micellar particle size is caused to reduce, there is optical Response, can be used as environment and biological medicine neck
The carrier in domain.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110302174A (en) * | 2019-06-14 | 2019-10-08 | 中山大学 | A kind of nanometer based on p-Coumaric Acid polymer passs medicine body system and its preparation method and application |
| US11639432B2 (en) | 2021-01-13 | 2023-05-02 | International Business Machines Corporation | Hydroxycinnamic acid-derived crosslinking dimers |
| US11732136B2 (en) | 2021-01-13 | 2023-08-22 | International Business Machines Corporation | Hydroxycinnamic acid-derived crosslinkers |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110302174A (en) * | 2019-06-14 | 2019-10-08 | 中山大学 | A kind of nanometer based on p-Coumaric Acid polymer passs medicine body system and its preparation method and application |
| US11639432B2 (en) | 2021-01-13 | 2023-05-02 | International Business Machines Corporation | Hydroxycinnamic acid-derived crosslinking dimers |
| US11732136B2 (en) | 2021-01-13 | 2023-08-22 | International Business Machines Corporation | Hydroxycinnamic acid-derived crosslinkers |
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