CN106905158A - A kind of diphenyl ketone type molecule of direct modified substrate and its application - Google Patents
A kind of diphenyl ketone type molecule of direct modified substrate and its application Download PDFInfo
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- CN106905158A CN106905158A CN201710061679.9A CN201710061679A CN106905158A CN 106905158 A CN106905158 A CN 106905158A CN 201710061679 A CN201710061679 A CN 201710061679A CN 106905158 A CN106905158 A CN 106905158A
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- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
Abstract
A kind of diphenyl ketone type molecule of direct modified substrate and its application, belong to technical field of material modification.Solve the surface modifying method complex process of material in the prior art, condition is harsh, modification efficiency is low, the scope of application is small, be difficult to the technical problem of large-scale application.The diphenyl ketone type molecule of direct modified substrate of the invention, structure is as follows：(A‑B)a‑(C‑B)b‑(A‑B)c‑(C‑B)d‑C‑(B‑A)e, in formula, a, b, c, d, e are respectively nonnegative integer, and are asynchronously zero；A expressions Ι, 1 10 represent substitution position, B represents linking group, and B is connected to any one substitution position of A, and C is modified group, if containing multiple A, multiple A structures are identical or difference, if containing multiple B, multiple B structures are identical or different, if containing multiple C, multiple C-structure are identical or difference.Surface modifying method process is simple, efficiency high based on diphenyl ketone type molecule, it is adaptable to large-scale application.
Description
Technical field
The invention belongs to technical field of material modification, and in particular to a kind of diphenyl ketone type molecule of direct modified substrate and
Its application.
Background technology
Current polymeric material is widely used in every field, and polymeric material performance cannot meet many special in itself
Requirement, or some polymer can cause the weakening of original excellent properties after substance law assigns property, and surface
Modified to give material special surface property on the basis of reserved materials bulk properties, being that one kind is widely used changes
Property method.
It is that, by chemistry or physical method, will can bring the molecule of material property with chemistry that usual surface is modified
The mode of key or non-bonding active force is fixed on substrate surface；But it is limited to modified molecules intrinsic property in itself, one
As non-bonding active force fixation it is more unstable, the modified layer of formation is easy to damage, so that ineffective；Chemical bond is made
Firmly then than stronger, there is problems in that material surface is usually inert so that the formation of new chemical bond is relatively difficult, mesh
Preceding many surface modifying methods are all to introduce modified molecules by cumbersome means；Start with itself from modified molecules, design and close
It is both difficult point into feasible modified molecular structure, is also an approach for fundamentally improving surface modifying method.Such as Ren,
X.Chem.Soc.Rev.2015,44,5680. review a series of skill of fixing function molecules chemical on substrate material surface
Art, such as (1) carry out nucleophilic displacement of fluorine under specific condition using catalyst, and (2) first carry out isocyanates treatment surface and are grafted again
Modified molecules, (3) carry out ATRP grafting in situ etc. under the harsh conditions such as sealing anaerobic.These methods need more without exception
Harsh condition is chemically reacted, and causes process complicated, it is difficult to extensive extensive use.For another example Mahouche-
Chergui, S.Chem.Soc.Rev.2011,40,4143. are reviewed using diazonium salt groups fixing function on base material
The extensive use of molecule, the surface modifying method based on diazonium salt groups is relatively easy and is achieved in laboratory research good
Good modified effect.But due to problem explosive under diazol drying condition, its use condition is received limitation, and big
The application aspect of scale has a potential safety hazard, and obstruction is set out the extensive use of method of modifying with diazonium salt groups.
Ultraviolet initiation surface grafting polymerization method is a kind of eaily surface modifying method, and current universal method is：
Using specific molecular monomer is excited, such molecule monomer self-initiating is set to be polymerized；Or sensitising agent is coated on substrate material surface,
Then unsaturated bond monomer is triggered to aggregate into polymer chain.But such method or the monomer of small range is only applicable to, or
Need to select suitable precoating solvent；And there are problems that same technological parameter suitable monomers species, directly affect modified
Efficiency and the scope of application.
The content of the invention
The present invention to solve that the surface modifying method complex process of material, condition in the prior art are harsh, modification efficiency is low,
The scope of application is small, be difficult to the technical problem of large-scale application, there is provided a kind of diphenyl ketone type molecule and preparation method and application.
A kind of diphenyl ketone type molecule of direct modified substrate, structure is as follows：
(A-B)a-(C-B)b-(A-B)c-(C-B)d-C-(B-A)e
In formula, a, b, c, d, e are respectively nonnegative integer, and are asynchronously zero；
A is represented1-10 represents substitution position；
B represents linking group, and B is connected on any one substitution position of A；
C is modified group, contains one or more functions group；
If containing multiple A, multiple A structures are identical or difference, if containing multiple B, multiple B structures are identical or not
Together, if containing multiple C, multiple C-structure are identical or difference.
Preferably, described a, b, c, d, e are respectively the integer of 0-10.
Preferably, the A not being connected with B 1-10 substitution position one at or many places connection deriveding group, it is different
Replace the deriveding group on position identical or difference, the deriveding group is alkyl, alkoxy, hydroxyl, carboxyl, two amidos or halogen
Base；It is further preferred that hydroxyl, carboxyl or two amidos.
Preferably, the deriveding group and B are connected on 1,3,5,6, the 8 or 10 substitutions position of A.More preferably
, the deriveding group is connected on 1,5, the 6 or 10 substitutions position of A, and B is connected on the 3 or 8 substitutions position of A.
Preferably, the B contains ehter bond, ester bond, amido link, ammonia ester bond, urea bond, peptide bond, imine linkage, mercaptal, contracting
One or more in thioketones, sulfydryl, sulfonic group, phosphoryl, thiosemicarbazides base, thioether group, sulfonyl, sulfinyl.It is more excellent
Choosing, the B contains hetero atom, and heteroatomic α has c h bond.
Preferably, the C contain alkane chain, carboxyl and its derivatives group, sulfonic group and its derivative, urethano,
Urea groups, cyano group, aldehyde radical, ketone group, hydroxyl, sulfydryl, amino, ammonium salt groups, Phosphorylcholine group, fluoro group, metal complex
Group, alkaloid group, carbohydrate group, antibioticses group, vitamins group, endotoxin group, weeding function group, kill
One kind or many in worm functional group, steroids group, peptide group, nucleosides group, polypeptide-nucleic acid group, haptenic group
Kind.
Preferably, the structure of the diphenyl ketone type molecule of direct modified substrate is the one kind in following structure：
The present invention also provides a kind of application of the diphenyl ketone type molecule of above-mentioned direct modified substrate, in substrate to be modified
The diphenyl ketone type molecule of direct modified substrate is covered, ultraviolet spectra irradiation grafting is then used, the modified of substrate is completed.
Preferably, the polymer is polyurethane, polyamide, makrolon, polyester, fluoropolymer, polyethers, poly- second
One or more in enol class, polyvinyl acetate class, polyacrylate of mixing, and polymer contains hetero atom, miscellaneous original
There is hydrogen on the α-C of son.
Compared with prior art, the beneficial effects of the invention are as follows：
The diphenyl ketone type molecule of direct modified substrate of the invention is by least one benzophenone structural and functional group
Coupled together by containing heteroatomic chain, obtain can direct modified substrate diphenyl ketone type molecule；The structure is on the one hand
Ensure that benzophenone group is effectively carried out " taking hydrogen by force ", it is ensured that grafting rate, on the other hand ensure that funtion part effective expression；Energy
Diphenyl ketone type molecule is enough coated on by material surface by certain way, and then under the conditions of ultraviolet light irradiation, directly by work(
Energy group is fixed on substrate material surface；
The applicable functional group of the diphenyl ketone type molecule of direct modified substrate of the invention is in extensive range, in operation
Functional group structure is difficult to be destroyed, can be with effective expression, and whole process is simple to operate, quick, environmental pollution is few, and its suitable
Industrial applications are closed, for example：The antiplatelet adhesiveness of polymeric material is improved, to make contacting blood material；Improve polymer
Material surface hydrophily, for improving stock-dye type or preparing anti-static fabric；Polymer biological performance is assigned, makes polymerization
Thing turns into cell culture vector preferably etc..
Brief description of the drawings
Fig. 1 is embodiment 4 by raw material 4-HBP and the ultraviolet absorption curve of compound 4；
Fig. 2 is modified group of embodiment 10 and the platelet adhesion reaction figure of control group；
Fig. 3 is cultivated with DMEM complete medium culture HECs, after 48h in modified orifice plate for embodiment 11 and tied
Really；
Fig. 4 is that modified group of embodiment 12 and control group are adhered to mouse fibrocyte and schemed.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are retouched with reference to specific embodiment
State, but it is to be understood that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to patent of the present invention
It is required that limitation.
The diphenyl ketone type molecule of direct modified substrate of the invention, structure is as follows：
(A-B)a-(C-B)b-(A-B)c-(C-B)d-C-(B-A)e
In formula, a, b, c, d, e are respectively nonnegative integer, and are asynchronously zero；A, b, c, d, e represent recurring group number,
When subscript is zero, show that the repeat unit does not exist, simple example：When a=1, b=c=d=e=0, represent that structure is
A-B-C.It is preferred that a, b, c, d, e are respectively the nonnegative integer of 0-10, the more preferably respectively nonnegative integer of 0-2, particularly preferred c=
1 or 2, a, b, d, e=0 or 1.
A is represented1-10 represents substitution position, and A is used as photoreactive groups；
B represents linking group, is the group of foundation after raw material chemical reaction, and B is connected to any one substitution position of A, excellent
Select B to be connected on 1,3,5,6, the 8 or 10 substitutions position of A, be more preferably connected on 3 or 8 substitutions position.
C is modified group, containing functional group, assigns the performance that substrate needs；
In one diphenyl ketone type molecule of direct modified substrate, if multiple A, multiple A can for identical structure or
Person's different structure, if multiple B, multiple B can be identical structure or different structure, and if multiple C, multiple C can be with
It is identical structure or different structure.
B contains one or more in following structure：Ehter bond, ester bond, amido link, ammonia ester bond, urea bond, peptide bond, imine linkage,
Mercaptal, thioketal, sulfydryl, sulfonic group, phosphoryl, thiosemicarbazides base, thioether group, sulfonyl, sulfinyl etc., B is preferably miscellaneous
α of atom (atom i.e. in addition to carbon, hydrogen) has the structure of c h bond.
C contains one or more in following structure：Alkane chain, carboxyl and its derivatives group, sulfonic group and its derivative
Thing group, urethano, urea groups, cyano group, aldehyde radical, ketone group, hydroxyl, sulfydryl, amino, ammonium salt groups, Phosphorylcholine group, fluoro base
Group, metal complex group, alkaloids group, carbohydrate group, antibioticses group, vitamins group, containing toxic radicals,
Have weeding function group, possess insecticidal function group, steroids group, peptide group, nucleosides group, polypeptide-nucleic acid group, half
One or more in antigen group.
On the substitution position of the 1-10 of A, the substitution position that removing be connected with B, other at one or many places replace the position can to connect
Connect deriveding group, the deriveding groups on difference substitution positions can with identical or difference, deriveding group be alkyl, alkoxy, hydroxyl,
Carboxyl, two amidos or halogen, preferably hydroxyl, carboxyl or two amidos.General deriveding group is connected to 1,3,5,6,8 or the 10 of A
On substitution position, it is preferably connected on 1,5, the 6 or 10 substitutions position of A.
The preparation method of the diphenyl ketone type molecule of direct modified substrate of the invention, the two of known direct modified substrate
On the basis of Benzophenone type molecular structure, those skilled in the art can be according to the corresponding preparation method of Molecular Design
Those skilled in the art's routine techniques.
The application of the diphenyl ketone type molecule of direct modified substrate of the invention, is to wait to change after substrate to be modified is cleaned
Property substrate on cover the diphenyl ketone type molecule of modified substrate, covering method do not limit, such as drop-coating, infusion process, spin-coating method,
Knife coating, sandwich structure method etc., determine according to molecular physics state；Then ultraviolet spectra irradiation grafting, hexichol first are used
Ketone groups take hydroperoxyl radical reaction by force, and photochemical reaction occurs with base material forms chemical bond, so that molecule is fixed on
On base material, the modified of substrate is completed, generally in the range of 200-400nm, ultraviolet source can for the ultraviolet light wave band of irradiation
Be mercury lamp or other can be with the equipment of emitting ultraviolet light wave band, irradiation intensity is in 200.0mW/cm2In the range of, preferably 1.0-
50.0mw/cm2Strength range (being 254nm uitraviolet intensities as normative reference with wavelength)；Irradiation time 1-300min it
Between, preferably between 1-60min.
The material of substrate is polymeric material, it is conventional for polyolefin, it is rubber, polyurethane, polyamide, makrolon, poly-
Ester, fluoropolymer, polyethers, polyvinyl alcohol, boiomacromolecule, polyvinyl acetate class, polyacrylate or they
Blend or composite.Selecting the diphenyl ketone type molecule of direct modified substrate, it is necessary to consider substrate characteristics, preferably
Amorphous polymer substrate contains the polymeric substrates for having hydrogen on heteroatomic polymer, and hetero atom α-C.Diphenyl ketone type
Modified molecules should fully sprawl contact in substrate surface, to be effectively grafted under ultraviolet light.
Substrate is fully cleaned using solvent, to remove pollutant that may be present, in order to avoid influence it to be grafted with A,
Cleaning solvent does not destroy base material, volatile or easy removing, even if a small amount of residual also modified to surface will not cause serious
Destruction.General polymerization thing material preferred alcohol or water are used as cleaning solvent；There is specific pollutant, should find can dissolve pollution
Thing, but the solvent of substrate will not be destroyed cleaned.
Modified is completed to substrate, if to obtain modified product stable in properties, can be by washing after cut-off
The remaining molecules of the possible physical adherence in surface are removed, the face coat of chemical bond fixation is finally given.Cleaning solution is selected to hexichol
Ketone type modified molecules have certain solvability, effectively can wash away the modified molecules dissolving of non-chemical graft；It is base
The poor solvent of bottom material, will not destroy substrate or be reacted with substrate；It is difficult to be sent out with the functional group in modified group etc.
Raw reaction, does not destroy or influences the expression of functional group；Washing lotion is easily removed.General cleaning solution uses water, ethanol, acetic acid second
Ester, acetone etc..
The present invention is described in detail below by specific embodiment, but is not limited to the content of embodiment.It is real
In applying example, 4-HBP：4- dihydroxy benaophenonels, DMAP：DMAP, CDI：N, N'- carbonyl dimidazoles, TEA：Three second
Amine, PST：PS, mPEG2000：Mean molecule quantity is 2000 polyethylene glycol, HDI：The isocyanide of hexa-methylene two
Acid esters, BDA：UVINUL MS 40,4 '-dioctyl phthalate, EDCHCl：1- (3- dimethylamino-propyls) -3- ethyl carbodiimide hydrochlorides
Salt, GPC：Glyceryl phosphoryl choline DMF：DMF, DIEA：Diisopropyl ethyl amine, BOP：The special condensing agent of card,
NHS：N-hydroxy-succinamide.
Embodiment 1
The diphenyl ketone type molecule (mono carboxylic benzophenone molecule) of direct modified substrate：(compound 1)
The synthetic method of the diphenyl ketone type molecule of above-mentioned direct modified substrate：By DMAP (0.02mol, 2.4g) and fourth two
Acid anhydrides (0.4mol, 40g) is dissolved in dry dichloromethane, and 30min is stirred at 25 DEG C；Then by 4-HBP (0.1mol,
19.8g) it is dissolved in dry methylene chloride, adds reaction system, then reaction is warmed up to 40 degree, stirred under nitrogen atmosphere reaction
12h.Reaction terminate after be deposited in 1%wt aqueous citric acid solutions, filter afterwards, recrystallize, product 50 DEG C, about 0.1MPa it is true
Dried under empty condition.Yield 40.1% (on the basis of 4-HBP).
Nuclear-magnetism detection is carried out to product, is as a result NMR (400MHz, H1-DMSO)：7.76 (4H), 7.60 (3H), 7.39
(2H), 2.65 (4H) ppm, it was demonstrated that synthesis compound 1.
Embodiment 2
The diphenyl ketone type molecule (mono amino benzophenone molecule) of direct modified substrate：(compound 2)
The synthesis of the diphenyl ketone type molecule of above-mentioned direct modified substrate：Compound 1 (0.1mol, 29.8g) is dissolved in
In dichloromethane, stirring and dissolving at 25 DEG C.CDI (0.15mol, 29.7g), stirred under nitrogen atmosphere are added to disposable in solution
Overnight；Then the TEA of Putriscine (0.3mol, 26.4g) and 10ml is dissolved in dichloromethane, adds reaction system, after
Continuous stirring 12h.Then revolving remove partial solvent, system is deposited in deionized water, precipitate, suction filtration, by solid 25 DEG C,
Dried under about 0.1MPa vacuum conditions, obtain product.Yield 82.4% (on the basis of compound 1).
Nuclear-magnetism detection is carried out to product, is as a result NMR (400MHz, H1-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, it was demonstrated that synthesized compound 2.
Embodiment 3
The diphenyl ketone type molecule (sulfonic group benzophenone molecule) of direct modified substrate：(compound 3)
The synthesis of the diphenyl ketone type molecule of above-mentioned direct modified substrate：Compound 2 (0.1mol, 36.8g) is dissolved in nothing
Water dichloromethane, in 60 degree of lower nitrogen protections, adds PST (0.12mol, 14.6g), reacts 5h.Reaction is deposited in product after terminating
In thing ether, solid is dried in filtering under 30 DEG C, about 0.1MPa vacuum conditions, obtains product.Yield 89.6% is (with chemical combination
On the basis of thing 2).
Nuclear-magnetism detection is carried out to product, is as a result NMR (400MHz, H1-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, it was demonstrated that synthesized compound 3.
Embodiment 4
The diphenyl ketone type molecule (poly glycol monomethyl ether end benzophenone) of direct modified substrate：(compound 4)
The synthesis of the diphenyl ketone type molecule of above-mentioned direct modified substrate：By mPEG2000 (0.1mol, 200g) in room temperature
Under be dissolved in tetrahydrofuran solvent, then 0.1mol (17.4g) HDI is dissolved in tetrahydrofuran at room temperature.At 60 DEG C, by every
Be added drop-wise to the solution of mPEG2000 in the solution of HDI by the second speed of 1ml, stirring reaction 3 hours；By 0.1mol (19.8g) 4-
HBP is dissolved in dichloromethane at room temperature, is added in above-mentioned mixed liquor, continues 60 DEG C of holding stirring reaction 3 hours.Reaction knot
Shu Hou, mixed solution is deposited in ether, after being then filtered off solids of sedimentation, is dried under 30 DEG C, about 0.1MPa vacuum conditions
It is dry, obtain product.Yield 92.7% (is defined) by 4-HBP.
By infrared detection hydroxyl peak (3450cm-1) to amino peak N-H (3305cm-1) transformation and isocyanate groups
NCO correspondences peak (2270cm-1) disappearance, it was demonstrated that reaction complete, obtain product.
Raw material 4-HBP and compound 4 are dissolved into absolute ethyl alcohol, the solution of 0.01mmol is configured to, immediately with it is ultraviolet-
Visible spectrophotometer measures absorption spectrum of the solution in 250-500nm wave-length coverages.Shown in result figure 1, can from Fig. 1
Go out benzophenone group be connected with modified group in this way have no effect on its UV absorption activity.
Embodiment 5
The diphenyl ketone type molecule (the double end-blocking benzophenone of alkane chain) of direct modified substrate：(compound 5)
The synthesis of the diphenyl ketone type molecule of above-mentioned direct modified substrate：Dodecyl alcohol (0.03mol, 5.6g) is molten
Solution adds EDCHCl (0.012mol, 2.3g) and DMAP (0.01mol, 1.22g) in chloroform, stirs at room temperature
, then be dissolved in BDA (0.01mol, 2.7g) in chloroform by 30min, adds afterwards in reaction system, and reaction is overnight.Produce
It is deposited in ether under thing low temperature, is filtered, dried under 30 DEG C, about 0.1MPa vacuum conditions, obtains product.Yield 64.3%
(on the basis of BDA).
Infrared detection is carried out to product, carbonyl vibration peak from carboxyl (1700cm is found-1) arrive ester group (1730cm-1) turn
Become, it was demonstrated that reaction is completed, and obtains compound 5.
Embodiment 6
The diphenyl ketone type molecule (double benzophenone end-blocking Phosphorylcholines) of direct modified substrate：(compound 6)
The synthesis of the diphenyl ketone type molecule of above-mentioned direct modified substrate：GPC (0.01mol, 2.57g) is dissolved in DMF
In, then under 80 DEG C of stirrings, add HDI (0.02mol, 3.36g), the lower reaction 3h of nitrogen protection；Room temperature is down to afterwards, by chemical combination
Thing 2 (0.02mol, 5.96g) is dissolved in DMF, is slowly added dropwise in reaction system, and reaction is overnight.Deionized water is added to be precipitated,
Suction filtration, then at 37 DEG C, dries under about 0.1MPa vacuum conditions, obtains product.Yield 46.3% (on the basis of GPC).
Product is detected into m/z=1329.6 by flight time mass spectrum, is consistent with target molecular weight, it was demonstrated that compound 6 is closed
Into.
Embodiment 7
The diphenyl ketone type molecule (ketoestradiol end benzophenone) of direct modified substrate：(compound 7)
The synthesis of the diphenyl ketone type molecule of above-mentioned direct modified substrate：By compound 2 (1.0mmol, 0.37g), BOP
(1.0mmol, 0.63g) is dissolved in DMF, adds 6- ketoestradiols -6- (0- carboxymethyls)-oxime (1.0mmol, 0.36g), DIEA
(0.35g, 2.0mmol), stirring reaction 5h, is then deposited in deionized water at 20 DEG C, suction filtration；Then successively with 10%wt's
Aqueous sodium carbonate, the sodium bisulphate solution of 10%wt and deionization washing solid, under 37 DEG C, about 0.1MPa vacuum conditions
Drying.Yield 71.3% (on the basis of compound 2).
Nuclear-magnetism detection is carried out to product, is as a result NMR (400MHz, H1-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, it was demonstrated that synthesis
Compound 7.
Embodiment 8
The diphenyl ketone type molecule (shitosan end benzophenone) of direct modified substrate：(compound 8)
The synthesis of the diphenyl ketone type molecule of above-mentioned direct modified substrate：Compound 1 (0.1mol, 29.8g) is dissolved in
DMF, is subsequently adding NHS (0.15mol, 17.3g) and EDCHCl (0.15mol, 28.7g), is stirred at room temperature under nitrogen protection
12h；The shitosan (0.01mol, 10.7g) that average degree of polymerization is 6 is dissolved in DMF, is subsequently adding in reaction system, heated up
To 40 degree of reaction 8h.Product is dialysed in the bag filter of Mw=500, then freeze-drying obtains target product.Yield
83.4% (on the basis of shitosan).
Nuclear-magnetism detection is carried out to product, is as a result NMR (400MHz, H1-DMSO)：It is clearly present peak 7.78 (4H), 7.59
(3H), 7.40 (2H) ppm, while original corresponding nuclear-magnetism peak of shitosan still retains, show to be grafted benzophenone on shitosan
Group success.
Embodiment 9
Compound 4 and compound 5 are dissolved in chloroform, the solution of 1%wt is configured to, polyurethane film substrate is spun on
On；Sample is positioned under the ultraviolet light of 400w and irradiates 10min, then fully wash away the non-grafted molecule in surface.Using Germany
The DSA30 type video optics contact angle measurements of KRUSS companies, are contacted by determining polyurethane-modified front and rear surface static water
Angle, judges to the hydrophilic modified effect of material surface.Every group of at least four samples, in triplicate, it is ensured that result reappearance.Knot
Fruit is as shown in table 1.
Table 1 is polymer modification front and rear surfaces hydrophily in embodiment 9
As it can be seen from table 1 contact angle significant change, represents polymer surface hydrophilic change, it was demonstrated that be modified successfully.
Embodiment 10
Compound 3 is dissolved in ethanol, the solution of 10%wt is configured to, drop coating is in polyurethane film substrate；By sample
Product irradiate 10min under being positioned over the ultraviolet light of 400w, then fully wash away the non-grafted molecule in surface, obtain modified polyurethane thin
Film substrate.
Gained modified polyurethane film substrate is labeled as modified group, at the same take unmodified polyurethane film substrate carry out it is right
According to labeled as control group, carrying out platelet attachment experiment.Wherein blood platelet source is supernatant blood platelet after healthy rabbit whole blood centrifugation
Pregnant solution.Compared with control group, the platelet adhesion reaction of modified group is significantly reduced, and shows that material is endowed antiplatelet adhesion work
Can, as a result as shown in Figure 2.
Embodiment 11
Compound 8 is dissolved in the water, the solution of 5%wt is configured to, 30s in polystyrene plates dipping solution is taken, so
After take out, be positioned over immediately under the ultraviolet light of 400w and irradiate 6min, then fully wash away the non-grafted molecule in surface.In modified hole
With DMEM complete medium culture HECs in plate, cultivation results after 48h are as shown in figure 3, from figure 3, it can be seen that cell
Grow fine, go out preferable modified effect.
Embodiment 12
Compound 6 is dissolved in ethanol, the solution of 10%wt is configured to, polyamide-based basal surface is coated on, 400w is purple
Outer light shines 5min, then fully washes away the non-grafted molecule in surface, and the material modified mark of gained is group, while take not changing
Property group material is compareed, and labeled as control group, carries out mouse fibrocyte adhesion experiment.Result is as shown in figure 4, can from Fig. 4
To find out, compared with control group, the cell adherence of modified group is significantly reduced, and can be shown that material is endowed Anti cell adhesion function.
Claims (10)
1. a kind of diphenyl ketone type molecule of direct modified substrate, it is characterised in that structure is as follows：
(A-B)a-(C-B)b-(A-B)c-(C-B)d-C-(B-A)e
In formula, a, b, c, d, e are respectively nonnegative integer, and are asynchronously zero；
A is represented1-10 represents substitution position；
B represents linking group, and B is connected on any one substitution position of A；
C is modified group, contains one or more functions group；
If containing multiple A, multiple A structures are identical or difference, if containing multiple B, multiple B structures are identical or different, such as
Fruit contains multiple C, and multiple C-structure are identical or difference.
2. the diphenyl ketone type molecule of a kind of direct modified substrate according to claim 1, it is characterised in that a, b,
C, d, e are respectively the integer of 0-10.
3. the diphenyl ketone type molecule of a kind of direct modified substrate according to claim 1, it is characterised in that not with B
The 1-10 of the A of connection substitution position one at or many places connection deriveding group, difference substitution positions on deriveding groups it is identical or
Person is different, and the deriveding group is alkyl, alkoxy, hydroxyl, carboxyl, two amidos or halogen.
4. a kind of diphenyl ketone type molecule of direct modified substrate according to claim 1, it is characterised in that the derivative
Group and B are connected on 1,3,5,6, the 8 or 10 substitutions position of A.
5. the diphenyl ketone type molecule of a kind of direct modified substrate according to claim 1, it is characterised in that the B contains
Have ehter bond, ester bond, amido link, ammonia ester bond, urea bond, peptide bond, imine linkage, mercaptal, thioketal, sulfydryl, sulfonic group, phosphoryl,
One or more in thiosemicarbazides base, thioether group, sulfonyl, sulfinyl.
6. the diphenyl ketone type molecule of a kind of direct modified substrate according to claim 1, it is characterised in that the B contains
There is hetero atom, heteroatomic α has c h bond.
7. the diphenyl ketone type molecule of a kind of direct modified substrate according to claim 1, it is characterised in that the C contains
Have alkane chain, carboxyl and its derivatives group, sulfonic group and its derivative, urethano, urea groups, cyano group, aldehyde radical, ketone group, hydroxyl,
Sulfydryl, amino, ammonium salt groups, Phosphorylcholine group, fluoro group, metal complex group, alkaloid group, carbohydrate group,
It is antibioticses group, vitamins group, endotoxin group, weeding function group, insecticidal function group, steroids group, many
One or more in peptide group, nucleosides group, polypeptide-nucleic acid group, haptenic group.
8. the diphenyl ketone type molecule of a kind of direct modified substrate according to claim 1, it is characterised in that structure be with
One kind in lower structure：
9. the application of the diphenyl ketone type molecule of a kind of direct modified substrate described in claim 1-8 any one, its feature
It is the diphenyl ketone type molecule that direct modified substrate is covered in substrate to be modified, then uses ultraviolet spectra irradiation grafting, it is complete
Into the modified of substrate；
The material of the substrate to be modified is polymeric material.
10. the application of the diphenyl ketone type molecule of direct modified substrate according to claim 9, it is characterised in that described
Polymer be polyurethane, polyamide, makrolon, polyester, fluoropolymer, polyethers, polyvinyl alcohol, polyvinyl acetate class,
One or more in polyacrylate of mixing, and polymer contains hetero atom, has hydrogen on heteroatomic α-C.
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| CN110092737A (en) * | 2018-01-31 | 2019-08-06 | 深圳大学 | The surface treatment method and modified material of a kind of antistatic compound, material |
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| CN110514507A (en) * | 2019-08-30 | 2019-11-29 | 中国科学院长春应用化学研究所 | A kind of 3D surface topography test board and the preparation method and application thereof |
| CN111808206A (en) * | 2020-08-18 | 2020-10-23 | 江南大学 | Modified biomass with ultraviolet absorption function, preparation method and application |
| WO2022057367A1 (en) * | 2020-09-18 | 2022-03-24 | 何建雄 | Photostable tpu composite material and preparation method therefor |
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