CN106905158B - Benzophenone type molecule for directly modifying substrate and application thereof - Google Patents

Benzophenone type molecule for directly modifying substrate and application thereof Download PDF

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CN106905158B
CN106905158B CN201710061679.9A CN201710061679A CN106905158B CN 106905158 B CN106905158 B CN 106905158B CN 201710061679 A CN201710061679 A CN 201710061679A CN 106905158 B CN106905158 B CN 106905158B
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benzophenone
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杨小牛
袁黎光
吕红英
李金歌
屈宝留
秦泽昭
俞晓峰
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Changchun Institute of Applied Chemistry of CAS
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Abstract

A benzophenone molecule directly modifying a substrate and application thereof, belonging to the technical field of material modification. Solves the technical problems of complex process, harsh conditions, low modification efficiency, small application range and difficult large-scale application of the surface modification method of the material in the prior art. The benzophenone type molecule of the direct modified substrate has the following structure: (A-B)a‑(C‑B)b‑(A‑B)c‑(C‑B)d‑C‑(B‑A)eIn the formula, a, b, c, d and e are respectively nonnegative integers and are not zero at the same time; a represents formula I, 1-10 represent substituted positions, B represents a connecting group, B is connected at any substituted position of A, C is a modifying group, if a plurality of A are contained, a plurality of A have the same or different structures, if a plurality of B are contained, a plurality of B have the same or different structures, and if a plurality of C are contained, a plurality of C have the same or different structures. The surface modification method based on benzophenone type molecules has simple process and high efficiency, and is suitable forAnd (4) large-scale application.
Figure DDA0001219728310000011

Description

Benzophenone type molecule for directly modifying substrate and application thereof
Technical Field
The invention belongs to the technical field of material modification, and particularly relates to a benzophenone type molecule for directly modifying a substrate and application thereof.
Background
At present, polymer materials are widely applied to various fields, the performance of the polymer materials cannot meet a plurality of special requirements, or the original excellent performance of some polymers can be weakened after the special performance is endowed by a bulk method, and the surface modification can endow the materials with special surface performance on the basis of keeping the bulk performance of the materials, so that the method is a widely used modification method.
Generally, the surface modification is to fix molecules which can bring specific properties to a material on the surface of a substrate by a chemical or physical method in a chemical bond or non-chemical bond acting manner; however, the fixing of the non-chemical bond acting force is not stable due to the inherent properties of the modified molecules, and the formed modified layer is easy to damage and lose the effect; the acting force of chemical bonds is firmer, but the problem is that the surface of the material is generally inert, so that the formation of new chemical bonds is difficult, and many surface modification methods introduce modified molecules by complicated means at present; starting from the modified molecule, designing and synthesizing a feasible modified molecular structure is not only a difficult point, but also a way for fundamentally improving the surface modification method. For example, Ren, x.chem.soc.rev.2015, 44, 5680 reviews a series of techniques for chemically fixing functional molecules on the surface of a substrate material, such as (1) nucleophilic substitution with a catalyst under special conditions, (2) surface grafting of modified molecules by isocyanate treatment, and (3) in-situ ATRP grafting under severe conditions of sealing, oxygen-free, and the like. None of these methods except the one requires harsh conditions for chemical reaction, resulting in complex process and difficult large-scale and wide application. For example, Mahouche-cherui, s.chem.soc.rev.2011,40,4143, reviews the wide application of diazonium salt groups to fix functional molecules on substrate materials, and the surface modification method based on diazonium salt groups is relatively simple and achieves good modification effect in laboratory research. However, the use condition of the diazonium salt is limited due to the explosive problem of the diazonium salt under the drying condition, and the diazonium salt has potential safety hazard in the aspect of large-scale application, thereby preventing the extensive application of the modification method starting from the diazonium salt group.
The ultraviolet initiated surface grafting polymerization method is a relatively convenient surface modification method, and the current general method comprises the following steps: exciting a specific molecular monomer to self-initiate polymerization of the molecular monomer; or a photosensitizer is coated on the surface of the substrate material, and then the unsaturated bond monomer is initiated to be polymerized into a polymer chain. However, this type of process is either only applicable to a small range of monomers, or requires the selection of a suitable pre-coating solvent; and the problems of few kinds of applicable monomers with the same process parameters and the like exist, and the modification efficiency and the application range are directly influenced.
Disclosure of Invention
The invention provides a benzophenone molecule, a preparation method and application thereof, and aims to solve the technical problems that the surface modification method of materials in the prior art is complex in process, harsh in conditions, low in modification efficiency, small in application range and difficult to apply on a large scale.
A benzophenone-type molecule for directly modifying a substrate, having the structure:
(A-B)a-(C-B)b-(A-B)c-(C-B)d-C-(B-A)e
in the formula, a, b, c, d and e are respectively nonnegative integers and are not zero at the same time;
a represents
Figure BDA0001219728290000021
1-10 all represent substituted positions;
b represents a linking group, and B is connected to any substitution position of A;
c is a modifying group containing one or more functional groups;
if a plurality of A's are contained, the plurality of A's may be the same or different in structure, if a plurality of B's are contained, the plurality of B's may be the same or different in structure, and if a plurality of C's are contained, the plurality of C's may be the same or different in structure.
Preferably, a, b, c, d and e are integers of 0 to 10.
Preferably, a derivative group is connected at one or more positions of 1-10 substitution positions of A which are not connected with B, the derivative groups on different substitution positions are the same or different, and the derivative group is an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group, a diamine group or a halogen group; more preferably, a hydroxyl group, a carboxyl group or a diamine group.
Preferably, the derivatising group and B are attached to the 1, 3, 5, 6, 8 or 10 substitution position of a, respectively. More preferably, the derivatizing group is attached at the 1, 5, 6 or 10 substitution position of a and B is attached at the 3 or 8 substitution position of a.
Preferably, B contains one or more of an ether bond, an ester bond, an amide bond, an urethane bond, a urea bond, a peptide bond, an imine bond, a mercaptide, a thioketal, a mercapto group, a sulfonic group, a phosphoryl group, a thiosemicarbazide group, a thioether group, a thioacyl group, and a sulfinyl group. More preferably, B contains a heteroatom having a C-H bond alpha to the heteroatom.
Preferably, C contains one or more of an alkane chain, a carboxyl group and its derivative group, a sulfonic group and its derivative, a urethane group, a urea group, a cyano group, an aldehyde group, a ketone group, a hydroxyl group, a mercapto group, an amino group, an ammonium salt group, a phosphorylcholine group, a fluoro group, a metal complex group, a alkaloid group, a carbohydrate group, an antibiotic group, a vitamin group, a toxin group, a herbicidal functional group, an insecticidal functional group, a steroid group, a polypeptide group, a nucleoside group, a polypeptide nucleic acid group, a hapten group.
Preferably, the structure of the benzophenone-type molecule that directly modifies the substrate is one of the following structures:
Figure BDA0001219728290000031
Figure BDA0001219728290000041
the invention also provides the application of the benzophenone molecule of the direct modified substrate, wherein the benzophenone molecule of the direct modified substrate is covered on the substrate to be modified, and then the ultraviolet spectrum is used for irradiation grafting to complete the modification of the substrate.
Preferably, the polymer is one or a mixture of more of polyurethane, polyamide, polycarbonate, polyester, fluorine-containing polymer, polyether, polyvinyl alcohol, polyvinyl acetate and polyacrylate, and the polymer contains heteroatoms, and the heteroatoms have hydrogen on alpha-C.
Compared with the prior art, the invention has the beneficial effects that:
the benzophenone type molecule of the direct modified substrate of the invention connects at least one benzophenone structure with a functional group through a chain containing hetero atoms to obtain the benzophenone type molecule which can directly modify the substrate; the structure ensures that the benzophenone group effectively takes hydrogen and ensures the grafting rate on one hand and the functional part is effectively expressed on the other hand; benzophenone molecules can be coated on the surface of a material in a certain mode, and functional groups are directly fixed on the surface of a substrate material under the ultraviolet irradiation condition;
the benzophenone type molecule of the directly modified substrate has wide applicable functional group range, the structure of the functional group in the operation is not easy to be damaged, the benzophenone type molecule can be effectively expressed, the operation in the whole process is simple and quick, the environmental pollution is less, and the benzophenone type molecule is suitable for industrial application, such as: improve the anti-platelet adhesion of polymer materials to be used as blood contact materials; the hydrophilicity of the surface of the polymer material is improved, so that the polymer material can be used for improving the fiber dyeing type or preparing antistatic fabrics; endows the polymer with biological performance, and makes the polymer become a more suitable cell culture carrier and the like.
Drawings
FIG. 1 is a graph showing the UV absorption curves of example 4 for starting material 4-HBP and Compound 4;
FIG. 2 is a graph showing platelet adhesion in the modified and control groups of example 10;
FIG. 3 shows the results of culturing human endothelial cells in a modified well plate in DMEM complete medium after 48 hours in example 11;
FIG. 4 is a graph showing the adhesion of mouse fibroblasts by the modified and control groups of example 12.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the detailed description, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention, and not to limit the claims to the invention.
The benzophenone type molecule of the direct modified substrate has the following structure:
(A-B)a-(C-B)b-(A-B)c-(C-B)d-C-(B-A)e
in the formula, a, b, c, d and e are respectively nonnegative integers and are not zero at the same time; a. b, c, d, e represent the number of repeat groups, indicating that the repeat unit is absent when the lower angle is marked zero, a simple example: and when a is 1, B is C, d is e, and 0, the structure is a-B-C. A, b, c, d, e are each preferably a non-negative integer from 0 to 10, more preferably a non-negative integer from 0 to 2, and particularly preferably c is 1 or 2, and a, b, d, e is 0 or 1.
A represents1-10 all represent substituted positions, and A is taken as a photoreaction group;
b represents a linking group which is a group established after the chemical reaction of the raw materials, and B is connected to any substituted position of A, preferably B is connected to 1, 3, 5, 6, 8 or 10 substituted positions of A, and more preferably connected to 3 or 8 substituted positions.
C is a modified group containing a functional group, and endows the substrate with required performance;
in a benzophenone-type molecule directly modifying a substrate, if a plurality of a exist, a plurality of a may be the same structure or different structures, if a plurality of B exist, a plurality of B may be the same structure or different structures, and if a plurality of C exist, a plurality of C may be the same structure or different structures.
B contains one or more of the following structures: ether bond, ester bond, amide bond, urethane bond, urea bond, peptide bond, imide bond, thioaldehyde, thioketal, mercapto group, sulfonic group, phosphoryl group, thiosemicarbazide group, thioether group, sulfuryl group, sulfinyl group, etc., and B is preferably a structure in which the α -position of a heteroatom (i.e., an atom other than carbon and hydrogen) has a C-H bond.
C contains one or more of the following structures: the pesticide composition comprises one or more of alkane chains, carboxyl groups and derivative groups thereof, sulfonic groups and derivative groups thereof, carbamate groups, carbamido groups, cyano groups, aldehyde groups, ketone groups, hydroxyl groups, sulfhydryl groups, amino groups, ammonium salt groups, phosphorylcholine groups, fluoro groups, metal complex groups, alkaloid groups, carbohydrate groups, antibiotic groups, vitamin groups, toxin-containing groups, groups with a weeding function, groups with an insecticidal function, steroid groups, polypeptide groups, nucleoside groups, polypeptide nucleic acid groups and hapten groups.
And (3) removing the substitution position connected with B from 1-10 substitution positions of A, connecting derivative groups to one or more other substitution positions, wherein the derivative groups on different substitution positions can be the same or different, and the derivative groups are alkyl, alkoxy, hydroxyl, carboxyl, diamino or halogen groups, preferably hydroxyl, carboxyl or diamino. Typically the derivatising group is attached at the 1, 3, 5, 6, 8 or 10 substitution of A, preferably at the 1, 5, 6 or 10 substitution of A.
The preparation method of the benzophenone-type molecule directly modifying the substrate of the invention is based on the known benzophenone-type molecular structure directly modifying the substrate, and the skilled person can design the corresponding preparation method according to the molecular structure, and is the routine technique of the skilled person.
The application of the benzophenone molecule of the direct modified substrate is to cover the benzophenone molecule of the modified substrate on the substrate to be modified after cleaning the substrate to be modified, and the covering method is not limited, such as a dripping coating method, a dipping method, a spin coating method, a blade coating method, a sandwich structure method and the like, and is determined according to the physical state of the molecule; then using ultraviolet spectrum to make irradiation grafting, making benzophenone group produce hydrogen-capturing free radical reaction, making it produce photochemical reaction with base material to form chemical bond so as to make the molecule be fixed on the base material to implement modification of base material, generally making the irradiated ultraviolet light wave band be in the range of 200-400nm, and making the ultraviolet light source be mercury lamp or other equipment capable of emitting ultraviolet light wave band, and its irradiation intensity be 200.0mW/cm2In the range of preferably 1.0 to 50.0mw/cm2(ii) intensity range (ultraviolet intensity at a wavelength of 254nm as a reference standard); the irradiation time is 1-300min, preferably 1-60 min.
The material of the substrate is a polymer material, and is usually polyolefin, rubber, polyurethane, polyamide, polycarbonate, polyester, fluoropolymer, polyether, polyvinyl alcohol, biopolymer, polyvinyl acetate, polyacrylate or their blends, or composite material. In selecting the benzophenone-type molecule to directly modify the substrate, taking into account the nature of the substrate, it is preferable to choose an amorphous polymeric substrate or a polymeric substrate containing heteroatoms, and having hydrogen on the heteroatom α -C. The benzophenone-type modifying molecule should be capable of being spread in contact on the surface of the substrate sufficiently for effective grafting under ultraviolet light.
The substrate is sufficiently cleaned with a solvent to remove any contaminants that may be present to avoid affecting grafting with A, the cleaning solvent does not damage the substrate material, is volatile or is easily removed, and even a small amount of residue does not cause significant damage to the surface modification. Generally, ethanol or water is preferred as a cleaning solvent for the polymer material; where there are particular contaminants, solvents are sought that will dissolve the contaminants, but will not damage the substrate.
After the substrate has been modified, if a modified article with stable properties is to be obtained, residual molecules that may physically adhere to the surface can be removed by washing after the cut-off, and finally a chemically bonded surface coating is obtained. The cleaning solution has certain dissolving capacity on benzophenone type modified molecules, and can effectively dissolve and wash off the modified molecules which are not chemically grafted; is a poor solvent for the substrate material and does not damage the substrate or react with the substrate; the functional groups in the modified groups are not easy to react, and the expression of the functional groups is not damaged or influenced; the washing liquid is easy to remove. The general washing liquid can be water, ethanol, ethyl acetate, acetone, etc.
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples. In the examples, 4-HBP: 4-hydroxybenzophenone, DMAP: 4-dimethylaminopyridine, CDI: n, N' -carbonyldiimidazole, TEA: triethylamine, PST: 1, 3-propane sultone, mPEG 2000: polyethylene glycol having an average molecular weight of 2000, HDI: hexamethylene diisocyanate, BDA: benzophenone-4, 4' -dicarboxylic acid, EDC. HCl: 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, GPC: glycerophosphorylcholine DMF: n, N-dimethylformamide, DIEA: diisopropylethylamine, BOP: carter condensation agent, NHS: n-hydroxysuccinimide.
Example 1
Benzophenone type molecules (monocarboxylbenzophenone molecules) directly modifying the substrate: (Compound 1)
Figure BDA0001219728290000071
The synthesis method of the benzophenone type molecule of the directly modified substrate comprises the following steps: DMAP (0.02mol, 2.4g) and succinic anhydride (0.4mol, 40g) were dissolved in dry dichloromethane and stirred at 25 ℃ for 30 min; then 4-HBP (0.1mol, 19.8g) is dissolved in dry dichloromethane, added into the reaction system, and then the reaction is heated to 40 ℃ and stirred for reaction for 12 hours under the protection of nitrogen. After the reaction, the precipitate was precipitated in a 1% wt aqueous solution of citric acid, filtered, recrystallized, and the product was dried at 50 ℃ under a vacuum of about 0.1 MPa. The yield was 40.1% (based on 4-HBP).
To give birth toThe material was subjected to nuclear magnetic resonance and the result was NMR (400MHz, H)1-DMSO): 7.76(4H), 7.60(3H), 7.39(2H), 2.65(4H) ppm, demonstrate the synthesis of Compound 1.
Example 2
Benzophenone type molecules (monoaminobenzophenone molecules) directly modifying the substrate: (Compound 2)
Figure BDA0001219728290000081
Synthesis of benzophenone-type molecules of the above directly modified substrate: compound 1(0.1mol, 29.8g) was dissolved in methylene chloride and dissolved with stirring at 25 ℃. Adding CDI (0.15mol, 29.7g) into the solution in one step, and stirring overnight under the protection of nitrogen; 1, 4-butanediamine (0.3mol, 26.4g) and 10ml of TEA were then dissolved in dichloromethane and added to the reaction and stirring was continued for 12 h. And then, removing part of the solvent by rotary evaporation, precipitating the system in deionized water, precipitating, filtering, and drying the solid at 25 ℃ under the vacuum condition of about 0.1MPa to obtain the product. The yield was 82.4% (based on compound 1).
The product was subjected to nuclear magnetic resonance and the result was NMR (400MHz, H)1-DMSO): 7.75(4H), 7.60(3H), 7.39(2H), 3.02(2H), 2.72(2H), 2.60(2H), 2.45(2H), 1.52(4H) ppm, demonstrate that Compound 2 is synthesized.
Example 3
Benzophenone type molecules (sulfonic benzophenone molecules) directly modifying the substrate: (Compound 3)
Synthesis of benzophenone-type molecules of the above directly modified substrate: compound 2(0.1mol, 36.8g) was dissolved in anhydrous dichloromethane, under nitrogen protection at 60 ℃ and PST (0.12mol, 14.6g) was added and reacted for 5 h. Precipitating in product ether after the reaction is finished, filtering, and drying the solid at 30 ℃ under the vacuum condition of about 0.1MPa to obtain the product. Yield 89.6% (based on compound 2).
The nuclear magnetic detection is carried out on the product,the result was NMR (400MHz, H)1-DMSO): 7.80(4H), 7.63(3H), 7.40(2H), 3.50(2H), 3.02(2H), 2.72(2H), 2.55(4H), 2.48(2H), 1.97(2H), 1.52(2H), 1.38(2H) ppm, demonstrating that Compound 3 was synthesized.
Example 4
Benzophenone type molecules (polyethylene glycol monomethyl ether-terminated benzophenones) that directly modify the substrate: (Compound 4)
Figure BDA0001219728290000091
Synthesis of benzophenone-type molecules of the above directly modified substrate: mPEG2000(0.1mol, 200g) was dissolved in tetrahydrofuran solvent at room temperature, and then 0.1mol (17.4g) HDI was dissolved in tetrahydrofuran at room temperature. Dropwise adding a solution of mPEG2000 into a solution of HDI at the rate of 1ml per second at 60 ℃, and stirring for reacting for 3 hours; 0.1mol (19.8g) of 4-HBP was dissolved in methylene chloride at room temperature, and the resulting solution was added to the above mixture, and the reaction was stirred while maintaining 60 ℃ for 3 hours. After the reaction is finished, the mixed solution is precipitated in ether, then solid precipitate is filtered out, and the product is dried under the vacuum condition of 30 ℃ and about 0.1MPa to obtain the product. The yield was 92.7% (based on 4-HBP).
Hydroxyl peak (3450 cm) by infrared detection-1) To amino peak N-H (3305 cm)-1) Transformation of (2) and NCO peak of isocyanate group (2270 cm)-1) The reaction was complete to give the product.
Dissolving the raw material 4-HBP and the compound 4 into absolute ethyl alcohol to prepare a 0.01mmol solution, and then measuring the absorption spectrum of the solution in the wavelength range of 250-500nm by using an ultraviolet-visible spectrophotometer. Results as shown in fig. 1, it can be seen from fig. 1 that the attachment of the benzophenone group to the modifying group in this way does not affect its uv absorbing activity.
Example 5
Benzophenone type molecules (alkane chain double-capped benzophenones) directly modifying the substrate: (Compound 5)
Synthesis of benzophenone-type molecules of the above directly modified substrate: n-dodecyl alcohol (0.03mol, 5.6g) was dissolved in chloroform, EDC. HCl (0.012mol, 2.3g) and DMAP (0.01mol, 1.22g) were added thereto, and the mixture was stirred at room temperature for 30min, after which BDA (0.01mol, 2.7g) was dissolved in chloroform, and then the mixture was added to the reaction system to react overnight. Precipitating the product in ether at low temperature, filtering, and drying at 30 deg.C under about 0.1MPa vacuum to obtain the product. Yield 64.3% (based on BDA).
The product was subjected to infrared detection, and the peak of carbonyl vibration was found to be from carboxyl (1700 cm)-1) To ester group (1730 cm)-1) The reaction was confirmed to be completed to obtain compound 5.
Example 6
Benzophenone type molecules (bis-benzophenone capped phosphorylcholine) directly modifying the substrate: (Compound 6)
Figure BDA0001219728290000102
Synthesis of benzophenone-type molecules of the above directly modified substrate: GPC (0.01mol, 2.57g) was dissolved in DMF, and HDI (0.02mol, 3.36g) was added under stirring at 80 ℃ to react for 3h under nitrogen protection; then, the temperature was lowered to room temperature, and Compound 2(0.02mol, 5.96g) was dissolved in DMF and slowly added dropwise to the reaction system to react overnight. Adding deionized water for precipitation, performing suction filtration, and drying at 37 ℃ under the vacuum condition of about 0.1MPa to obtain a product. Yield 46.3% (based on GPC).
The product was detected by time-of-flight mass spectrometry at m/z 1329.6, consistent with the target molecular weight, confirming the synthesis of compound 6.
Example 7
Benzophenone-type molecules (ketoestradiol-terminated benzophenones) that directly modify the substrate: (Compound 7)
Figure BDA0001219728290000103
Synthesis of benzophenone-type molecules of the above directly modified substrate: dissolving compound 2(1.0mmol, 0.37g) and BOP (1.0mmol, 0.63g) in DMF, adding 6-ketoestradiol-6- (0-carboxymethyl) -oxime (1.0mmol, 0.36g) and DIEA (0.35g, 2.0mmol), stirring at 20 deg.C for 5h, precipitating in deionized water, and filtering; then the solid is washed by 10 percent of sodium carbonate aqueous solution, 10 percent of sodium bisulfate aqueous solution and deionized water in sequence, and is dried under the vacuum condition of 37 ℃ and about 0.1 MPa. Yield 71.3% (based on compound 2).
The product was subjected to nuclear magnetic resonance and the result was NMR (400MHz, H)1-DMSO): 7.78(4H), 7.60(3H), 7.40(2H), 7.38(1H), 7.18(1H), 6.94(1H), 4.87(2H), 3.02-1.31(26H), 1.03(3H) ppm, demonstrate that Compound 7 is synthesized.
Example 8
Benzophenone type molecules (chitosan-terminated benzophenones) that directly modify the substrate: (Compound 8)
Figure BDA0001219728290000111
Synthesis of benzophenone-type molecules of the above directly modified substrate: dissolving compound 1(0.1mol, 29.8g) in DMF, adding NHS (0.15mol, 17.3g) and EDC & HCl (0.15mol, 28.7g), and stirring at room temperature for 12h under nitrogen protection; chitosan (0.01mol, 10.7g) with average degree of polymerization of 6 is dissolved in DMF, then added into the reaction system, heated to 40 ℃ and reacted for 8 h. The reaction product was dialyzed in a dialysis bag having Mw of 500 and then freeze-dried to obtain the objective product. The yield was 83.4% (based on chitosan).
The product was subjected to nuclear magnetic resonance and the result was NMR (400MHz, H)1-DMSO): the peaks 7.78(4H), 7.59(3H) and 7.40(2H) ppm are obviously existed, and the corresponding nuclear magnetic peak of the original chitosan is still remained, which indicates that the benzophenone group grafted on the chitosan is successful.
Example 9
Dissolving a compound 4 and a compound 5 in chloroform to prepare a 1 wt% solution, and spin-coating the solution on a polyurethane film substrate; the sample was placed under 400w UV light for 10min and then the surface non-grafted molecules were washed off sufficiently. The effect of modifying the hydrophilicity of the surface of a material was determined by measuring the static water contact angle of the surface before and after modification of polyurethane using a DSA30 model video optical contact angle measuring instrument from KRUSS, Germany. Each group of at least four samples was repeated three times to ensure the reproducibility of the results. The results are shown in Table 1.
Table 1 shows the hydrophilicity of the front and rear surfaces of the polymer modification in example 9
Figure BDA0001219728290000121
As can be seen from Table 1, the contact angle changes significantly, indicating that the hydrophilicity of the polymer surface changes, demonstrating successful modification.
Example 10
Dissolving the compound 3 in ethanol to prepare a 10 wt% solution, and dripping the solution on a polyurethane film substrate; and (3) placing the sample under 400w of ultraviolet light for irradiating for 10min, and then fully washing off molecules which are not grafted on the surface to obtain the modified polyurethane film substrate.
The obtained modified polyurethane film substrate is marked as a modified group, and simultaneously, the unmodified polyurethane film substrate is taken for comparison and marked as a control group for carrying out a platelet adhesion experiment. Wherein the platelet source is supernatant platelet enrichment solution obtained after centrifugation of whole blood of healthy rabbits. The platelet adhesion was significantly reduced in the modified group compared to the control group, indicating that the material was endowed with an anti-platelet adhesion function, the results are shown in fig. 2.
Example 11
Dissolving the compound 8 in water to prepare a solution with the weight of 5%, taking a polystyrene pore plate, soaking the polystyrene pore plate in the solution for 30s, taking out the polystyrene pore plate, then placing the polystyrene pore plate under 400w of ultraviolet light for irradiating for 6min, and then fully washing off molecules which are not grafted on the surface. The results of culturing human endothelial cells in the modified well plate in DMEM complete medium after 48 hours are shown in FIG. 3, and it can be seen from FIG. 3 that the cells have good growth and better modification effect.
Example 12
Dissolving the compound 6 in ethanol to prepare a 10 wt% solution, coating the solution on the surface of a polyamide substrate, irradiating for 5min by a 400w ultraviolet lamp, sufficiently washing off molecules which are not grafted on the surface, marking the obtained modified material as a modified group, simultaneously taking the material of the unmodified group for comparison, marking the material as a control group, and carrying out a mouse fiber cell adhesion experiment. The results are shown in FIG. 4, and it can be seen from FIG. 4 that the cell adhesion of the modified group is significantly reduced compared to the control group, indicating that the material is endowed with the anti-cell adhesion function.

Claims (3)

1. A benzophenone-type molecule for direct modification of a substrate, characterized in that the structure is one of the following:
Figure FDA0002158794570000011
2. the use of benzophenone-type molecules for directly modifying a substrate as claimed in claim 1, wherein the modification of the substrate is performed by covering the benzophenone-type molecules for directly modifying a substrate to be modified with the molecules and then irradiating the resulting product with ultraviolet radiation for grafting;
the material of the substrate to be modified is a polymer material.
3. Use of a benzophenone-type molecule according to claim 2 for the direct modification of a substrate, wherein said polymer is a mixture of one or more of polyurethanes, polyamides, polycarbonates, polyesters, fluoropolymers, polyethers, polyvinyl alcohols, polyvinyl acetates, polyacrylates and wherein the polymer contains heteroatoms and the heteroatoms have hydrogen in the α -C.
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