CN107216462A - A kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition - Google Patents
A kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition Download PDFInfo
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- CN107216462A CN107216462A CN201710432395.6A CN201710432395A CN107216462A CN 107216462 A CN107216462 A CN 107216462A CN 201710432395 A CN201710432395 A CN 201710432395A CN 107216462 A CN107216462 A CN 107216462A
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Abstract
The present invention relates to a kind of preparation method of carboxylated graphene oxide surface grafting PLA particulate.This method for raw material, by the Steglish esterification reaction methods of improvement, prepares carboxylated graphene oxide surface grafting polylactic acid composition (GO COOH PLLA PEG PLLA) with carboxylated graphene oxide (GO COOH).By infrared spectrum (FTIR) and NMR spectrum (1HNMR) composite structure is characterized, it is determined that the molecule of synthesis is consistent with target molecular structure.Using the inventive method carboxyl grafting graphene oxide and PLA, so that grafting rate is up to 99.13%, and experiment condition is gentle, it is easy to operate, course of reaction no coupling product, substantially increases the purity of polymer, and organic solvent-free is remained, experimental cost is low, improves its application prospect in bio-medical field.
Description
Technical field
The present invention relates to field of biomedical polymer materials, specifically a kind of carboxylated graphene oxide surface grafting gathers
The preparation method of amine-lactic acid complex.
Technical background
PLA (PLLA) has high crystalline, very strong hydrophobicity, largely limits it and is released in medical
Put the application on carrier material.In order to improve the deficiency of PLLA performances, in recent years, the country is obtained to PLLA functional modification
Outer material scholar's is widely studied.At present, the modification to PLLA mainly has chemical modification and physics filling-modified.Chemical modification master
Will be by the way that lactic acid and other materials be carried out into copolymerization, then chain extension forms block composite；Or added in PLLA multifunctional
The crosslinking agent of group, such as dioctyl phthalate (DOP) is carried out cross-linking modified；Or pass through the carboxyl at graphene oxide edge
With the esterification between PLLA terminal hydroxy groups, PLLA is grafted to preparation PLLA/ graphene composite materials on graphene, connect
Branch is modified.PLLA combination property is can effectively improve by way of chemical modification.Physical modification is mainly by PLLA matrixes
It is middle to add filler to obtain high performance PLLA composites.
Graphene is preferable two-dimension nano materials now, because it has excellent physical and chemical performance and obtains wide
General research and application.The carboxylated graphene oxide (GO-COOH) of low molecule amount has relatively low crystallinity, hydrophily pole
By force, specific surface area is big, can effectively avoid protein absorption and the phagocytosis of mononuclear phagocytic cells (MPS).Carboxylated is aoxidized into stone
Black alkene is grafted to preparation carboxylated graphene oxide grafted polylactic acid compound on PLA, can both improve the hydrophilic of PLA
Property, its crystallinity is reduced, the specific surface area of polymer support is considerably increased again so that PLA and carboxylated graphene oxide
Composite has more preferable pharmaceutical carrier performance, improves the theoretical research value of polymeric medicine controlled release carrier, has it
There is better application prospect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition.
To achieve the above object, technical scheme is as follows：
A kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition, it is characterised in that with carboxyl
It is raw material to change graphene oxide (GO-COOH), by the Steglish esterification reaction methods of improvement, is grafted to PLA (PLLA)
On, prepare carboxylated graphene oxide surface grafting polylactic acid composition (GO-COOH-PLLA-PEG-PLLA), synthetic route
It is as follows：
Above-mentioned preparation method comprises the following steps：
(1) by GO-COOH ultrasonic dissolutions in deionized water, GO-COOH solution is obtained；PLLA is dissolved in dichloromethane
In, obtain PLLA-PEG-PLLA solution；Wherein GO-COOH and PLLA mass ratio is 1:The concentration of 1~4, GO-COOH solution
(mg/ml) it is 1~3 with the ratio of the concentration (mg/ml) of PLLA-PEG-PLLA solution:1~3；
(2) 50ml ethanol is added after GO-COOH solution is mixed with PLLA-PEG-PLLA solution makes its dispersed, then to
EDC and DMAP in mass ratio 1~5 is added in mixed solution:1 mixture, leads to nitrogen protection and carries out graft reaction, 40~90 DEG C
3~20h of lower stirring reaction；Wherein EDC and DMAP quality and the quality of GO-COOH and PLLA-PEG-PLLA in step (1)
Ratio be 1~2:1；
(3) after above-mentioned reaction terminates, reaction solution is fitted into bag filter, dialysed 3~5 days, freeze-drying obtains GO-
COOH-PLLA-PEG-PLLA。
Preferably, GO-COOH and PLLA mass ratio is 1 in step (1):2.
Preferably, the concentration (mg/ml) of GO-COOH solution and the concentration of PLLA-PEG-PLLA solution in step (1)
(mg/ml) ratio is 2:1.
Preferably, EDC and DMAP mass ratio is 2 in step (2):1.
Preferably, EDC and DMAP quality and the matter of GO-COOH and PLLA-PEG-PLLA in step (1) in step (2)
The ratio of amount is 2:1.
Preferably, reaction temperature is 70 DEG C, reaction time 5h in step (3).
Synthesis mechanism：GO-COOH carboxyl and 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides first
(EDC) isourea intermediate of the generation with O- acyl groups, activates to carbonyl, forms it into acid ion；Then 4- diformazans ammonia
The electrophilic carbonyl carbon of nucleopilic reagent nitrogen-atoms attack acid anhydrides on the pyridine of yl pyridines (DMPA), forms pyridiniujm, wherein pyridiniujm
Cation and acid ion one untight ion pair of formation.The carbonyl carbon that the oxygen atom attack of alcoholic extract hydroxyl group is connected with pyridine from
Son, the acid ion that then first step is produced captures the hydrogen of alcoholic extract hydroxyl group immediately, and then oxygen is negative extrudes pyridine, produces ester, together
When regenerate DMAP catalyst.Reaction mechanism such as Fig. 1 institutes of carboxylated graphene oxide surface grafting polylactic acid composition
Show.
Compared with prior art, the advantage of the invention is that：The inventive method carboxyl grafting graphene oxide and poly- breast
Acid, grafting rate is high, and experiment condition is gentle, and easy to operate, course of reaction no coupling product substantially increases the purity of polymer, and nothing
Organic solvent residual, experimental cost is low, and grafting rate is up to 99.13%, improves its application prospect in bio-medical field.
Brief description of the drawings
The reaction mechanism of Fig. 1 carboxylated graphene oxide surface grafting polylactic acid compositions；
The infrared spectrogram of Fig. 2 carboxylated graphene oxide surface grafting polylactic acid compositions；
The proton nmr spectra spectrogram of Fig. 3 carboxylated graphene oxide surface grafting polylactic acid compositions.
Embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
Take 0.01g GO-COOH ultrasonic dissolutions in 10mL deionized waters, obtain GO-COOH solution；By 0.02g's
PLLA is added in 40mL dichloromethane, obtains PLLA-PEG-PLLA solution；By GO-COOH solution and PLLA-PEG-PLLA
Adding 50mL ethanol after solution mixing makes its dispersed, then addition 0.04g EDC and 0.02g into mixed solution
DMAP, leads to stirring reaction 5h at nitrogen protection, 70 DEG C, after reaction terminates, reaction solution is fitted into bag filter, dialyse 5 days, freezing
PLA carboxyl grafting graphite oxide (GO-COOH-PLLA-PEG-PLLA) product is dried to obtain, grafting rate is 99.13%.
Embodiment 2
Take 0.01g GO-COOH ultrasonic dissolutions in 10mL deionized waters, obtain GO-COOH solution；By 0.02g's
PLLA is added in 10mL dichloromethane, obtains PLLA-PEG-PLLA solution；By GO-COOH solution and PLLA-PEG-PLLA
Adding 50mL ethanol after solution mixing makes its dispersed, then addition 0.04g EDC and 0.02g into mixed solution
DMAP, leads to stirring reaction 15h at nitrogen protection, 85 DEG C, after reaction terminates, reaction solution is fitted into bag filter, dialyse 5 days, cold
Jelly is dried to obtain PLA carboxyl grafting graphite oxide (GO-COOH-PLLA-PEG-PLLA) product, and grafting rate is
96.58%.
Embodiment 3
Take 0.01g GO-COOH ultrasonic dissolutions in 10mL deionized waters, obtain GO-COOH solution；By 0.02g's
PLLA is added in 60mL dichloromethane, obtains PLLA-PEG-PLLA solution；By GO-COOH solution and PLLA-PEG-PLLA
Adding 50mL ethanol after solution mixing makes its dispersed, then addition 0.05g EDC and 0.01g into mixed solution
DMAP, leads to stirring reaction 20h at nitrogen protection, 55 DEG C, after reaction terminates, reaction solution is fitted into bag filter, dialyse 5 days, cold
Jelly is dried to obtain PLA carboxyl grafting graphite oxide (GO-COOH-PLLA-PEG-PLLA) product, and grafting rate is
98.82%.
Fig. 2 is the infrared spectrogram of the carboxylated graphene oxide surface grafting polylactic acid composition obtained in embodiment 1.
In figure：(a) GO-COOH characteristic peak respectively appears in 1736cm-1(carbonyl-C=O stretching vibration peaks in carboxylic acid), 1629cm-1
(the C=C vibrations in aromatic hydrocarbon ring), 1411cm-1(the O-H deformation vibrations peak in carboxyl), 1090cm-1(C-O keys stretch in carboxyl
Vibration peak), 3000~3600cm in addition-1The big broad peak occurred is probably remaining water peak；(b) PLLA-PEG-PLLA exists
3505cm-1There are terminal hydroxy group-OH characteristic peaks, in 2998cm-1、2880cm-1、2946cm-1Place is-CH respectively3、-CH2,-CH it is special
Levy peak, 1758cm-1Place is carbonyl-C=O characteristic peaks, 1360~1386cm-1Locate as-C-H stretching vibration peaks, 1457cm-1It is C-
O-H deformation vibrations peak in OH, 1044~1215cm-1Place is the stretching vibration of-C-O keys and-C-O-C- stretching vibrations in alcoholic extract hydroxyl group
Characteristic peak；(c) infrared spectrogram is contrasted, it can be seen that polymer GO-COOH-PLLA-PEG-PLLA is in 1650cm-1Place occurs right
The absorption of vibrations characteristic peak of carbonyl-C=O in new ester bond is moved, carbonyl absorption peak 1736cm-1 is to lower wave number from GO-COOH
1650cm-1It is mobile, meet the rule of carbonyl absorption peak between carboxyl and corresponding ester group, the presence of vibration absorption peak is demonstrated
GO-COOH carboxyl and PLLA-PEG-PLLA hydroxyl are covalently attached by there occurs that esterification forms ester bond,
1736cm-1Place's absworption peak reduces with the increase of polymer molecular weight, because carbonyl in the larger polymer of molecular weight-
C=O proportions reduce.The above results show that the absworption peak in spectrogram meets GO-COOH-PLLA-PEG-PLLA feature
Absworption peak.
Fig. 3 is obtained carboxylated graphene oxide surface grafting polylactic acid composition in embodiment 11H-NMR spectrum.Figure
In：Displacement is in 3.49~3.53ppm (D) appearance, and this is the main structure-CH of PEG in PLLA-PEG-PLLA2CH2Methylene in O-
Base proton peak；5.20 (F) go out signal peak and then belong to proton peak in-CH；1.23ppm (A) place signal peak belongs to-CH3Onychostroma
Sub- peak；And peak area F:A is similar to 1:3；1.47ppm (B) place signal peak is hydroxyl proton peak in PLLA-PEG-PLLA；And by
Contain a large amount of hydrogen bonds in GO-COOH, signal peak is broad peak at 3.90ppm (E) place；The signal peak at 2.51ppm (C) place is solvent
The absworption peak of (deuterated dimethyl sulfoxide).1The structure for occurring GO-COOH and PLLA-PEG-PLLA on HNMR spectrograms simultaneously is special
Levy, illustrate that GO-COOH and PLLA-PEG-PLLA is grafted successfully.
By infrared spectrum Fig. 2 and nuclear magnetic resonance Fig. 3 analysis shows, carboxylated graphene oxide surface grafting PLA
(GO-COOH-PLLA-PEG-PLLA) structure of product is consistent with design.
Claims (7)
1. a kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition, it is characterised in that with carboxylated
Graphene oxide (GO-COOH) is raw material, by the Steglish esterification reaction methods of improvement, is grafted on PLA (PLLA),
Carboxylated graphene oxide surface grafting copolymer of poly lactic acid (GO-COOH-PLLA-PEG-PLLA) is prepared, synthetic route is such as
Under：
2. a kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition according to claim 1,
Characterized in that, the described method comprises the following steps：
(1) by GO-COOH ultrasonic dissolutions in deionized water, GO-COOH solution is obtained；PLLA is dissolved in dichloromethane,
Obtain PLLA-PEG-PLLA solution；Wherein GO-COOH and PLLA mass ratio is 1:Concentration (the mg/ of 1~4, GO-COOH solution
Ml it is) 1~3 with the ratio of the concentration (mg/ml) of PLLA-PEG-PLLA solution:1~3；
(2) 50ml ethanol is added after GO-COOH solution in step (1) is mixed with PLLA-PEG-PLLA solution makes it uniformly divide
Dissipate, then the addition EDC and DMAP in mass ratio 1~5 into mixed solution:1 mixture, leads to nitrogen protection and carries out graft reaction,
3~20h of stirring reaction at 40~90 DEG C；Wherein EDC and DMAP quality and GO-COOH and PLLA-PEG-PLLA in step (1)
Quality ratio be 1~2:1；
(3) after above-mentioned reaction terminates, reaction solution is fitted into bag filter, dialysed 3~5 days, freeze-drying obtains GO-COOH-
PLLA-PEG-PLLA。
3. a kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition according to claim 2,
Characterized in that, GO-COOH and PLLA mass ratio is 1 in step (1):2.
4. a kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition according to claim 2,
Characterized in that, in step (1) concentration (mg/ml) of GO-COOH solution and PLLA-PEG-PLLA solution concentration (mg/ml)
Ratio be 2:1.
5. a kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition according to claim 2,
Characterized in that, EDC and DMAP mass ratio is 2 in step (2):1.
6. a kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition according to claim 2,
Characterized in that, GO-COOH and PLLA-PEG-PLLA quality in EDC and DMAP quality and step (1) in step (2)
Than for 2:1.
7. a kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition according to claim 2,
Characterized in that, reaction temperature is 70 DEG C, reaction time 5h in step (3).
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| CN113416313A (en) * | 2021-05-25 | 2021-09-21 | 暨南大学 | Biodegradable compatilizer and preparation method and application thereof |
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