CN111675820B - Surface-grafted curcumin modified degradable polyurethane composite material and preparation method and application thereof - Google Patents

Surface-grafted curcumin modified degradable polyurethane composite material and preparation method and application thereof Download PDF

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CN111675820B
CN111675820B CN202010564308.4A CN202010564308A CN111675820B CN 111675820 B CN111675820 B CN 111675820B CN 202010564308 A CN202010564308 A CN 202010564308A CN 111675820 B CN111675820 B CN 111675820B
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curcumin
polyurethane
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CN111675820A (en
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邹超
侯昭升
景臣
祝敬妥
钟文
滕金伟
徐钧
刘辉
王赛
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Nanjing Training Team Of Fire Rescue Bureau Of Emergency Management Department
Shandong Normal University
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Shandong Normal University
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Abstract

The invention relates toAnd a surface-grafted curcumin modified degradable polyurethane composite material, a preparation method and application thereof. The modified curcumin is composed of polyurethane and modified curcumin grafted with the polyurethane, the polyurethane and the modified curcumin are connected through a-CONH-chemical bond, and the polyurethane material is a polyurethane material with a carbamate structure in the molecular formula; the chemical structural formula of the modified curcumin is shown as a formula II:
Figure DDA0002545837310000011
wherein R is a straight chain or branched chain alkyl of C3-C4.

Description

Surface-grafted curcumin modified degradable polyurethane composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyurethane high polymer materials, and particularly relates to a surface-grafted curcumin modified degradable polyurethane composite material as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Polyurethane is a high molecular material containing a repeating unit of carbamate (-NHCOO-) on the main chain, which is called PU for short. Due to the large differences of properties such as thermodynamics, polarity and the like of each chain segment in the PU macromolecule, microphase separation of a PU aggregation state structure can be caused, so that the PU macromolecule has the advantages of excellent mechanical property, low temperature resistance, solvent resistance and the like. Currently, polyurethane is widely used in the production of foams, synthetic leather, adhesives, coatings, and the like, and has been applied in the biomedical field due to its biocompatibility and blood compatibility.
However, in the field of medical materials, the performance of a single material is difficult to meet the existing requirements, so that the wider application of the single material in the medical field is limited, and the medical composite material with multiple functions becomes a hot spot of research of people.
Patent CN107537069A discloses a polyethylene glycol surface modified nano silver polyurethane medical material, which generates reactive sites on the surface of polyurethane through pre-activation treatment, and then graft copolymerization with polyethylene glycol improves the hydrophilicity and biocompatibility of polyurethane as a medical material, and introduces a second modified layer nano silver into the system to improve the antibacterial performance of polyurethane as a medical material. But has a certain limitation, the influence of the nano silver on the health of organisms has no direct evidence at present, and from some in vitro experiments, the potential hazard that the nano silver can have can be seen. Zhangzhuangyong is a paper from the study on oxidative stress induced by nano-silver and its toxicity mechanism, and the action mechanism of nano-silver on A549 and HepG2 cytotoxicity and the difference reason thereof were preliminarily studied at the cellular and molecular level, so that nano-silver is considered to have a certain cytotoxicity on A549 and HepG2 cells.
The patent CN109575233A discloses a hyperbranched polyester modified polyurethane medical interventional catheter and a preparation method thereof, the hyperbranched polyester is characterized by a large number of end groups, and the polyurethane medical interventional catheter with excellent lubricity and wear resistance can be obtained by combining the chemical bond grafting of the catheter and a coating.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a surface-grafted curcumin modified degradable polyurethane composite material and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the first aspect is that the surface-grafted curcumin modified degradable polyurethane composite material consists of a polyurethane material with a surface-grafted-NCO group and curcumin or modified curcumin, wherein the polyurethane material with the surface-grafted-NCO group (isocyanate group) is connected with the modified curcumin through a-CONH-chemical bond, and the polyurethane material is a polyurethane material with a carbamate structure in the molecular formula;
the chemical structural formula of the modified curcumin is shown as the formula II:
Figure BDA0002545837290000021
wherein R is a straight chain or branched chain alkyl of C3-C4.
In some embodiments of the invention, the polyurethane has the chemical structure shown in formula I:
Figure BDA0002545837290000022
wherein n is 3 to 13, p is 12 to 192, and the number average molecular weight is 40000 to 220000 g/mol.
In some embodiments of the present invention, the polyurethane material is a polyurethane film, a polyurethane foam, a polyurethane spun yarn, a polyurethane sponge, or the like, which has a urethane structure in a molecular formula.
According to the surface-grafted curcumin modified degradable polyurethane composite material, curcumin and derivatives are grafted to degradable polyurethane, so that the degradable excellent performance is reserved, the mechanical strength of the polyurethane material can be enhanced, the polyurethane material has partial characteristics of curcumin and derivatives, and the additional functional value of the polyurethane material is increased. Curcumin is a polyphenol substance, and has antibacterial, antioxidant, antitumor, and blood lipid regulating effects. Hydroxyl hydrogen on a benzene ring can play a role in antioxidation, so that curcumin can obviously resist oxidation and remove free radicals, can enhance the activity of antioxidant enzymes such as superoxide dismutase, catalase and glutathione peroxidase, and has good biological activity. The beta-diketone part of the curcumin exists in an enol structure, can be used as a metal ion chelating agent and acts on the active site of a target protein, so that the curcumin has the capability of interacting with a plurality of target proteins, and can be widely used as a potential target for developing antitumor drugs. Curcumin (CUR) and derivatives are introduced into Polyurethane (PU) in a chemical bonding mode, and after the curcumin and derivatives are used for modifying polyurethane, the defect of single function of the polyurethane can be overcome, so that the polyurethane has partial functions of the curcumin, and the aims of modifying the polyurethane and preparing functional materials can be fulfilled.
In a second aspect, the preparation method of the surface-grafted curcumin modified degradable polyurethane composite material comprises the following steps:
reacting the polyurethane film material with Hexamethylene Diisocyanate (HDI) to obtain polyurethane (PU-NCO) with the surface grafted with isocyanate groups;
reacting curcumin (compound 1) with compound 2 to obtain modified curcumin (structure shown in formula II);
reacting polyurethane with surface grafted isocyanic acid radical group with modified curcumin or curcumin to obtain a surface grafted curcumin modified degradable polyurethane film;
the structural formula of the compound 2 is shown as the formula III:
Figure BDA0002545837290000031
wherein R is a straight chain or branched chain alkyl of C3-C4.
Preferably, the compound 2 is a compound 3, a compound 4, a compound 5, a compound 6, and the structural formulas are respectively:
Figure BDA0002545837290000041
the modified Curcuma rhizomeThe method for preparing the extract comprises adding curcumin, compound 2, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC. HCL) and 4-Dimethylaminopyridine (DMAP) into solvent A, mixing, reacting, and reacting with NaHCO3Extracting, drying and purifying to obtain the modified curcumin.
The modified curcumin is prepared by modifying one hydroxyl group of the curcumin, grafting the modified curcumin with a compound A, not grafting the other hydroxyl group, and carrying out a condensation reaction on the other hydroxyl group and polyurethane with isocyanated surface.
In some embodiments of the invention, the molar ratio of curcumin, compound 2, edc.hcl, DMAP is 1: 0.8-1.2: 0.8-1.2: 1 to 1.2.
In some embodiments of the invention, the solvent A is dichloromethane, and the mixed mass of 1mL of dichloromethane-dissolved curcumin, the compound 2, EDC.HCL and DMAP is 0.01-1 g.
In some embodiments of the invention, the conditions of the reaction are: the temperature is 20-25 ℃, and the reaction time is 0.8-2 h.
The reaction scheme for modified curcumin is as follows:
Figure BDA0002545837290000042
provides a modified curcumin with a structural formula shown as a formula II:
Figure BDA0002545837290000043
wherein R is a straight chain or branched chain alkyl of C3-C4.
The preparation method of the polyurethane with the surface grafted with the isocyanato group comprises the steps of adding Hexamethylene Diisocyanate (HDI) into a solvent B, adding a polyurethane material (structural formula I) and a catalyst, and reacting to obtain the polyurethane with the surface grafted with the isocyanato group.
In some embodiments of the invention, each 1X 1cm2The volume of Hexamethylene Diisocyanate (HDI) added into the polyurethane to be modified is 0.2-1And adding 10-20 mL of anhydrous toluene.
In some embodiments of the invention, the instillation catalyst is dibutyl tin dilaurate (DBTDL) or stannous octoate.
In some embodiments of the invention, the reaction conditions are: the temperature is 40-45 ℃, and the reaction time is 2-6 h.
The method for reacting the polyurethane grafted with the isocyanate group with the modified curcumin comprises the steps of adding the polyurethane grafted with the isocyanate group and the modified curcumin into toluene for reaction, washing and drying to obtain the surface-grafted curcumin modified degradable polyurethane composite material.
grafting-NCO groups on the surface of the polyurethane material, carrying out a condensation reaction between the-NCO groups and-OH of curcumin to graft the curcumin on the surface of the polyurethane material, and obtaining the surface-grafted curcumin modified degradable polyurethane composite material.
In some embodiments of the invention, each 1X 1cm2The modified polyurethane is 0.1-2 mmol of modified curcumin or 0.1-2 mmol of modified curcumin.
In some embodiments of the invention, the conditions of the reaction are: the temperature is 40-45 ℃, and the reaction time is 10-20 h.
In a third aspect, the surface-grafted curcumin modified degradable polyurethane composite material is applied to the fields of textile printing and dyeing, medical equipment, chemical engineering building materials, medical intermediates, radiation-proof materials and the like.
The invention has the beneficial effects that:
1. the modified polyurethane material provided by the invention is obviously improved in mechanical property and thermal stability, and has stable fluorescence, good antibacterial property and biocompatibility.
2. The modified polyurethane material provided by the invention can be widely used for medical consumables, such as dressings, sutures, antibacterial and anti-inflammatory films, catheters made of all contact materials of artificial hearts and blood, and the like.
3. The modified polyurethane material provided by the invention has the wide application in the step 1, which is determined by the structure of the modified polymer, and the modified curcumin is grafted into the structure of Polyurethane (PU) to modify a matrix, so that the molecular structure of the polymer and the functional groups of the polymer are improved on the molecular level, and the additional value of the polyurethane material is obviously improved.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a physical diagram of the degradable polyurethane film and the surface-grafted curcumin modified degradable polyurethane film in example 1, wherein FIG. 1a is before modification, and FIG. 1b is after modification;
fig. 2 is a thermal exploded view of the modified degradable polyurethane film grafted with curcumin in example 1.
Fig. 3 is a drawing graph of the modified degradable polyurethane film grafted with curcumin in example 1.
Fig. 4 is an infrared spectrum of the degradable polyurethane film and the surface-grafted curcumin modified degradable polyurethane film in example 1.
Fig. 5 is an infrared spectrum of curcumin and modified curcumin in example 2.
Fig. 6 is a graph of the relationship between ibuprofen in PBS solution and the cumulative release rate over time on the degradable polyurethane film and the surface-grafted curcumin modified degradable polyurethane film in example 6.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The polyurethane material in the following examples is a polyurethane film material prepared by the method of the patent application No. 201510250602.7.
The invention will be further illustrated by the following examples
Example 1
(1) 0.5mL of Hexamethylene Diisocyanate (HDI) was added to 10mL of anhydrous toluene, and 1X 1cm was added2After the modified polyurethane material is washed by anhydrous toluene until the surface is clean, putting the modified polyurethane material into a mixed solution of the anhydrous toluene and Hexamethylene Diisocyanate (HDI), dropwise adding 1-2 drops of dibutyltin dilaurate serving as a catalyst, carrying out oscillation reaction at 40 ℃ for 2 hours, taking out a membrane and repeatedly washing the membrane after the reaction is finished so as to remove unreacted HDI, and thus obtaining a polyurethane surface isocyanate grafted membrane (PU-NCO);
(2) dissolving 0.368g of curcumin in 10mL of anhydrous toluene solution, then mixing the PEU-NCO film prepared in the step (1) with the solution, stirring and reacting at 45 ℃ for 16h, then washing with anhydrous toluene (measuring washing liquid), washing with ethanol, and drying in a vacuum drying oven for 24h to prepare the degradable polyurethane film with the curcumin-modified surface grafted.
As shown in fig. 1, fig. 1a shows the polyurethane film material before modification, which is a slightly transparent white color, and fig. 1b shows the degradable polyurethane film material with curcumin grafted on the surface, which is a dark yellow color.
As shown in fig. 2, the surface-grafted curcumin modified degradable polyurethane film material has thermal degradability, is a degradable material, and has improved overall thermal stability compared with the polyurethane material before modification.
As shown in fig. 3, the surface-grafted curcumin modified degradable polyurethane film material and the change of the mechanical properties of the degradable polyurethane film material are shown. It can be seen that, due to the addition of curcumin, the tensile strength and the elastic modulus of the material are greatly improved.
As shown in FIG. 4, the degradable polyurethane film with curcumin grafted on the surface is improved compared with the degradable polyurethane filmThe infrared spectrum of the degradable polyurethane film shows that the absorption peak area of the-CONH-group is obviously increased and ranges from 800 cm to 900cm-1And 950-1015 cm-1C-H bending vibration and C-C skeleton vibration absorption peaks of benzene rings respectively appear, and therefore the fact that curcumin is grafted to the surface of the degradable polyurethane film is shown.
Example 2
(1) 0.368g of curcumin, 0.2g of 2- (-4-isobutylphenyl) propionic acid (ibuprofen), 0.2g of 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC.HCL) and 0.12g of 4-Dimethylaminopyridine (DMAP) were added to 15mL of dichloromethane respectively and mixed, and the mixture was stirred at 25 ℃ for 1.5 hours and cooled NaHCO was used3Extracted from dichloromethane and then passed through Na2SO4Drying, concentrating under reduced pressure, purifying by silica gel chromatography, and drying to obtain pure modified curcumin;
(2) 0.5mL of Hexamethylene Diisocyanate (HDI) was added to 10mL of anhydrous toluene, and 1X 1cm was added2After the modified polyurethane material is washed by anhydrous toluene until the surface is clean, putting the modified polyurethane material into a mixed solution of the anhydrous toluene and Hexamethylene Diisocyanate (HDI), dropwise adding 1-2 drops of catalyst dibutyl tin dilaurate, carrying out oscillation reaction at 40 ℃ for 2h, taking out a membrane and repeatedly washing to remove unreacted HDI, and obtaining a polyurethane surface isocyanate grafted membrane (PU-NCO);
(3) and (2) dissolving the pure product modified curcumin prepared in the step (1) in 10mL of anhydrous toluene solution, mixing the PEU-NCO film prepared in the step (2) with the solution, stirring and reacting at 45 ℃ for 16h, washing with anhydrous toluene (measuring washing liquid), washing with ethanol, and drying in a vacuum drying oven for 24h to prepare the degradable polyurethane film with the surface grafted with curcumin modified.
As shown in fig. 5, compared with curcumin modified by ibuprofen, the infrared spectrum of the modified curcumin shows that the modified curcumin has an absorption peak with a-COOR group, which indicates that ibuprofen is bonded and modified into curcumin molecules.
Example 3
(1) 0.552g of curcumin and 0.4g of 2- (-4-iso-propyl) are mixedButylphenyl) propionic acid (ibuprofen), 0.4g of 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC. HCL) and 0.24g of 4-Dimethylaminopyridine (DMAP) were mixed with 20mL of dichloromethane, stirred at 25 ℃ for 2 hours, and cooled NaHCO was used3Extracted from dichloromethane and then passed through Na2SO4Drying, concentrating under reduced pressure, purifying by silica gel chromatography, and drying to obtain pure modified curcumin;
(2) 0.8mL of Hexamethylene Diisocyanate (HDI) was added to 15mL of anhydrous toluene, and 1X 1cm was added2After the modified polyurethane material is washed by anhydrous toluene until the surface is clean, putting the modified polyurethane material into a mixed solution of the anhydrous toluene and Hexamethylene Diisocyanate (HDI), dropwise adding 1-2 drops of a catalyst DBTDL, carrying out oscillation reaction at 45 ℃ for 4 hours, taking out a membrane after the reaction is finished, and repeatedly washing the membrane to remove unreacted HDI so as to obtain a polyurethane surface isocyanate grafted membrane (PU-NCO);
(3) and (2) dissolving the pure product modified curcumin prepared in the step (1) in 15mL of anhydrous toluene solution, mixing the PEU-NCO film prepared in the step (2) with the solution, stirring and reacting at 45 ℃ for 20h, washing with anhydrous toluene (measuring washing liquid), washing with ethanol, and drying in a vacuum drying oven for 24h to prepare the degradable polyurethane film with the surface grafted with curcumin modified.
Example 4
(1) 0.368g of curcumin, 0.2g of 2- (-4-isobutylphenyl) propionic acid (ibuprofen), 0.2g of 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC.HCL) and 0.12g of 4-Dimethylaminopyridine (DMAP) were added to 15mL of dichloromethane respectively and mixed, and the mixture was stirred at 25 ℃ for 1.5 hours and cooled NaHCO was used3Extracted from dichloromethane and then passed through Na2SO4Drying, concentrating under reduced pressure, purifying by silica gel chromatography, and drying to obtain pure modified curcumin;
(2) 0.5mL of Hexamethylene Diisocyanate (HDI) was added to 10mL of anhydrous toluene, and 1X 1cm was added2After the modified polyurethane material is washed by anhydrous toluene until the surface is clean, the anhydrous toluene and Hexamethylene Diisocyanate (HDI) are addedDripping 1-2 drops of catalyst DBTDL into the mixed solution, carrying out oscillation reaction for 4 hours at 40 ℃, taking out the membrane for repeated washing after the reaction is finished, so as to remove unreacted HDI and prepare a film (PU-NCO) with the surface of polyurethane grafted with isocyanate;
(3) and (2) dissolving the pure product modified curcumin prepared in the step (1) in 10mL of anhydrous toluene solution, mixing the PEU-NCO film prepared in the step (2) with the solution, stirring and reacting at 40 ℃ for 20h, washing with anhydrous toluene (measuring washing liquid), washing with ethanol, and drying in a vacuum drying oven for 24h to prepare the degradable polyurethane film with the surface grafted with curcumin modified.
Example 5
0.552g of curcumin, 0.4g of 2- (-4-isobutylphenyl) propionic acid (ibuprofen), 0.4g of 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC.HCL) and 0.24g of 4-Dimethylaminopyridine (DMAP) were added to 20mL of dichloromethane respectively and mixed, and the mixture was stirred at 25 ℃ for 2 hours and cooled NaHCO was used3Extracted from dichloromethane and then passed through Na2SO4Drying, concentrating under reduced pressure, purifying by silica gel chromatography, and drying to obtain pure modified curcumin;
(2) 0.8mL of Hexamethylene Diisocyanate (HDI) was added to 10mL of anhydrous toluene, and 1X 1cm2After the modified polyurethane material is washed by anhydrous toluene until the surface is clean, putting the modified polyurethane material into a mixed solution of the anhydrous toluene and Hexamethylene Diisocyanate (HDI), dropwise adding 1-2 drops of catalyst dibutyl tin dilaurate, carrying out oscillation reaction at 45 ℃ for 6h, taking out a membrane and repeatedly washing to remove unreacted HDI, and obtaining a polyurethane surface isocyanate grafted membrane (PU-NCO);
(3) and (2) dissolving the pure product modified curcumin prepared in the step (1) in 15mL of anhydrous toluene solution by using a PEU-NCO membrane, mixing the PEU-NCO membrane prepared in the step (2) with the solution, stirring and reacting for 20h at 45 ℃, washing with anhydrous toluene (measuring washing liquid), washing with ethanol, and drying in a vacuum drying oven for 24h to prepare the degradable polyurethane membrane with the curcumin modified surface grafted.
Example 6
(1) 0.368g of curcumin, 0.2g of 2- (-4-isobutylphenyl) propionic acid (ibuprofen), 0.2g of 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC.HCL) and 0.12g of 4-Dimethylaminopyridine (DMAP) were added to 15mL of dichloromethane respectively and mixed, and the mixture was stirred at 25 ℃ for 1.5 hours and cooled NaHCO was used3Extracted from dichloromethane and then passed through Na2SO4Drying, concentrating under reduced pressure, purifying by silica gel chromatography, and drying to obtain pure product modified curcumin;
(2) 0.5mL of Hexamethylene Diisocyanate (HDI) was added to 10mL of anhydrous toluene, and 1X 1cm2After the modified polyurethane material is washed by anhydrous toluene until the surface is clean, putting the modified polyurethane material into a mixed solution of the anhydrous toluene and Hexamethylene Diisocyanate (HDI), dropwise adding 1-2 drops of catalyst dibutyl tin dilaurate, carrying out oscillation reaction at 40 ℃ for 2h, taking out a membrane and repeatedly washing to remove unreacted HDI, and obtaining a polyurethane surface isocyanate grafted membrane (PU-NCO);
(3) dissolving the pure product modified curcumin prepared in the step (1) in 10mL of anhydrous toluene solution, then mixing the PEU-NCO film prepared in the step (2) with the solution, stirring and reacting at 45 ℃ for 16h, washing with anhydrous toluene (measuring washing liquid), washing with ethanol, and drying in a vacuum drying oven for 24h to prepare the degradable polyurethane film with the surface grafted with curcumin modified;
(4) the polyurethane film prepared above was put into a centrifuge tube containing 0.1mol/L of PBS solution with pH 4 and pH 8, the temperature was set at 25 ℃, and the ibuprofen content in the solution was measured by sampling at 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 and 24 hours, and the stability of ibuprofen in solutions with different pH values was examined.
As shown in fig. 6, the surface-grafted curcumin modified degradable polyurethane film shows better ibuprofen slow release performance in PBS solution at room temperature, and the cumulative release rate is about 65% at about 20 h.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (15)

1. A surface-grafted curcumin modified degradable polyurethane composite material is characterized in that: the modified curcumin is connected with the polyurethane material with the surface grafted with the isocyanic acid radical through a-CONH-chemical bond, and the polyurethane material is a polyurethane material with a carbamate structure in the molecular formula;
the chemical structural formula of the modified curcumin is shown as a formula II:
Figure FDA0003561025890000011
wherein R is a straight chain or branched chain alkyl of C3-C4;
the polyurethane material is a polyurethane film, polyurethane foam or polyurethane spinning material.
2. The surface-grafted curcumin-modified degradable polyurethane composite material as claimed in claim 1, wherein: the chemical structural formula of the polyurethane is shown as formula I:
Figure FDA0003561025890000012
wherein n is 3 to 13, p is 12 to 192, and the number average molecular weight is 40000 to 220000 g/mol.
3. The method for preparing the surface-grafted curcumin modified degradable polyurethane composite material as claimed in any one of claims 1 to 2, which is characterized by comprising the following steps:
the method comprises the following steps:
reacting a polyurethane material with hexamethylene diisocyanate to obtain polyurethane with the surface grafted with isocyanate groups;
reacting curcumin with the compound 2 to obtain modified curcumin;
reacting polyurethane with surface grafted isocyanic acid radical group with modified curcumin to obtain a surface grafted curcumin modified degradable polyurethane composite material;
wherein the polyurethane material is a polyurethane film;
the structural formula of the compound 2 is shown as the formula III:
Figure FDA0003561025890000021
wherein R is a straight chain or branched chain alkyl of C3-C4.
4. The preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the compound 2 is a compound 3, a compound 4, a compound 5 and a compound 6, and the structural formulas are respectively as follows:
Figure FDA0003561025890000022
5. the preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the method for modifying curcumin comprises adding curcumin and compound 2, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 4-dimethylaminopyridine into solvent A respectively, mixing, reacting, and using NaHCO3Extracting, drying and purifying to obtain the modified curcumin.
6. The method for preparing the surface-grafted curcumin-modified degradable polyurethane composite material as claimed in claim 5, wherein the method comprises the following steps: the mass ratio of curcumin to the compound 2 to EDC.HCL to DMAP is 1: 0.8-1.2: 0.8-1.2: 1 to 1.2;
the solvent A is dichloromethane, and the mixed mass of curcumin, the compound 2, EDC, HCL and DMAP dissolved in 1mL of dichloromethane is 0.01-1 g;
the reaction conditions are as follows: the temperature is 20-25 ℃, and the reaction time is 0.8-2 h.
7. The preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the structural formula of the modified curcumin is shown as a formula II:
Figure FDA0003561025890000031
wherein R is a straight chain or branched chain alkyl of C3-C4.
8. The method for preparing the surface-grafted curcumin-modified degradable polyurethane composite material as claimed in claim 3, wherein the method comprises the following steps: the preparation method of the polyurethane with the surface grafted with the isocyanic acid radical comprises the following steps: adding hexamethylene diisocyanate into the solvent B, adding a polyurethane material and a catalyst, and reacting to obtain the polyurethane with the surface grafted with isocyanate groups.
9. The preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 8, wherein the preparation method comprises the following steps: each 1X 1cm2Adding 0.1-1 mL of HDI into the polyurethane material to be modified, and adding 10-20 mL of anhydrous toluene; the polyurethane material to be modified is the polyurethane material of claim 3.
10. The preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 8, wherein the preparation method comprises the following steps: the dropping catalyst is dibutyl tin dilaurate or stannous octoate.
11. The preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 8, wherein the preparation method comprises the following steps: the reaction conditions are as follows: the temperature is 40-45 ℃, and the reaction time is 2-6 h.
12. The preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the polyurethane grafted with isocyanate group and modified curcumin are added into toluene to react, and the polyurethane grafted with isocyanate group and the modified curcumin are washed and dried to obtain the surface-grafted curcumin modified degradable polyurethane composite material.
13. The preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 12, wherein the method comprises the following steps: each 1X 1cm2Adding 0.1-2 mmol of modified curcumin into the polyurethane material to be modified; the polyurethane material to be modified is the polyurethane material of claim 3.
14. The preparation method of the surface-grafted curcumin modified degradable polyurethane composite material as claimed in claim 12, wherein the method comprises the following steps: the reaction conditions are as follows: the temperature is 40-45 ℃, and the reaction time is 10-20 h.
15. The surface-grafted curcumin modified degradable polyurethane composite material as claimed in any one of claims 1 to 2, and applications thereof in the fields of textile printing and dyeing, medical devices, chemical building materials, medical intermediates and radiation-proof materials.
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