CN102702556A - Ultraviolet-assisted surface modification method and product with surface formed thereby - Google Patents
Ultraviolet-assisted surface modification method and product with surface formed thereby Download PDFInfo
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Abstract
The invention relates to a polymer surface modification method by ultraviolet irradiation. The polymer surface modification method by ultraviolet irradiation includes allowing a photosensitive group X to chemically react under ultraviolet irradiation so as to introduce a functional group L into the surface of polymer material P, wherein the photosensitive group X contains at least one xanthone unit.
Description
Technical field
The goods that the present invention relates to the auxiliary polymer surface modifying method of a kind of surface modifying method, particularly UV-light and be used for the modification molecule of the auxiliary material surface modifying method of UV-light and have the material surface of the formation of method modification thus.
Background technology
Material with special surface properties has widely at printing, dyeing, bonding, obstruct and biological field etc. to be used.For example, it is good to have the hydrophilic PET film of surface of good tinctorial property, can print out the wrapping material of multiple design and color; Polymer materials with excellent surface biological property can be widely used in fields such as biosensor, biomaterial for medical purpose, biological rapid detection.
Usually can obtain to have the material of different surfaces performance through the method for surface-treated.Said method comprises wet chemistry method, chemical etching, corona method, plasma method, high-energy ray irradiation method and photochemical method etc.
Thereby ultraviolet surface graft is a kind of photochemical method that the modification molecule is fixed to material surface realization modification purpose through ultraviolet light irradiation with the mode of covalent linkage.Under ultraviolet light irradiation, the mode (coupling process) of mode (polymerization) or the surperficial coupling of modification molecule through surface grafting polymerization is accomplished covalently bound with material surface.The UV-light coupling process realizes that through the bridge linking effect of photosensitive group functional group is connected with material surface, the material that this method can obtain having the different surfaces characteristic through the kind that changes functional group.
In recent years, make the method for polymer surface modification cause researchist's interest to introducing functional group through the UV-light coupling process.
It is that photosensitive group, phosphorylcholine are that the modification molecule of functional group carries out surface-treated to urethane with the phenylazide that J.Biomed.Mater.Res.1997,37,282 – 290 disclose.The shortcoming of this method is: the activity of the nitrene radical that the phenylazide group generates under ultraviolet light irradiation is too strong, thereby it is easy to generate the efficient that side reaction reduces surface-treated; In addition, said species reactive high and can back journey or effect immediately take place with most compounds, organic solvent and water.
WO 96/31557 discloses the method for carrying out surface-treated with quinones as the synthetic a series of compounds of photosensitive group.The photosensitivity that the shortcoming of this method is the quinones group relatively a little less than, cause the ultraviolet light irradiation time longer relatively, be unfavorable for producing fast and practicing thrift cost.
Therefore, this area need be contained can produce the modification molecule that has certain active radical and have the photosensitive group of strong photosensitivity, to be used for the auxiliary surface modifying method of UV-light.
Summary of the invention
The present invention aims to provide a kind of method of modifying of material surface, and it can overcome the problems referred to above that prior art exists.This method issues third contact of a total solar or lunar eclipse chemical reaction and the surface of functional group L being introduced polymer materials P through containing the unitary photosensitive group X of at least one xanthone at ultraviolet light irradiation.
Can on the surface of polymer materials P, introduce molecule X-L and X-S-L through the inventive method, wherein X is for containing the unitary photosensitive group of at least one xanthone, and L is a functional group, and S is a connection chain.
In one embodiment, said photosensitive group X is connected through being selected from following mode with the surface of polymer materials P: P-X-L and P-X-S-L, wherein P, X, L and S again define.
With regard to the inventive method, mode of connection mentioned above can realize through for example following approach:
(1) synthetic molecules X-L or X-S-L; Make said molecule X-L or X-S-L and polymer materials P surface that photochemical reaction take place through ultraviolet light irradiation then; Thereby the surface with said molecule X-L or X-S-L introducing polymer materials P forms P-X-L or P-X-S-L.
(2) make photosensitive group X and polymer materials P surface that photochemical reaction take place through ultraviolet light irradiation and form P-X; With synthetic molecules S-L; Through photochemical reaction or thermal chemical reaction molecule S-L is connected to the polymer materials P surface that has formed P-X on its surface then, forms P-X-S-L.
(3) synthetic molecules X-S; Through photochemical reaction molecule X-S is connected to polymer materials P surface then; Form P-X-S, through photochemical reaction or thermal chemical reaction functional group L is connected to the polymer materials P surface that has formed P-X-S on its surface afterwards, form P-X-S-L.
(4) through photochemical reaction photosensitive group X is fixed to polymer materials P surface; Form P-X; Randomly connection chain S is connected to said photosensitive group X-shaped then and becomes P-X-S through photochemical reaction or thermal chemical reaction; Make functional group L be connected through photochemical reaction or thermal chemical reaction afterwards with the optional photosensitive group X that is connected with connection chain S that is fixed to polymer materials P surface; Thereby the surface with said molecule X-L or X-S-L introducing polymer materials P forms P-X-L or P-X-S-L.
Through above exemplary explanation, should be appreciated that to those skilled in the art other approach that forms mode of connection P-X-L and P-X-S-L is also included within the scope of the present invention under the condition that does not depart from inventive concept.
In another embodiment; Before on the surface of said molecule X-L and/or X-S-L being introduced said polymer materials P; Can randomly connection chain S ' be fixed to and treat modified polymeric material P surface through photochemical reaction or thermal chemical reaction; Form P-S ', introduce the polymer materials P surface that is connected with connection chain S ' through molecule X-L mentioned above or X-S-L then, thereby form P-S '-X-L or P-S '-X-S-L.Constitute the cell S of connection chain S '
i' can be identical independently of one another or different.The selection of connection chain S ' can be considered from aspects such as length, flexibility, reactive behavior, hydrophobicity/wetting abilities according to the character of treating modified surface.The selection of connection chain S ' can be with reference to the detailed description of hereinafter to connection chain S.
Above-mentioned approach can realize that existing is that example is described in greater detail with first kind of approach through different modes.
With regard to above-mentioned first kind of approach, said especially method of modifying can may further comprise the steps:
A. synthetic molecules X-S-L or X-L, wherein X is for containing the unitary photosensitive group of at least one xanthone, and L is a functional group, and S is a connection chain;
B. the modified solution that molecule X-S-L or X-L and suitable solvent is contained said molecule X-S-L with formation;
C. form said modified solution layer on the surface of the polymer materials P that is modified;
D. with the surface of the above-mentioned polymer materials P of ultraviolet light irradiation, on this surface, to introduce molecule X-S-L or X-L with said modified solution layer.
If desired, said method can also comprise after the E. irradiation, removes modification molecule X-S-L remaining on the said surface.
The modification molecule X-S-L that said method of modifying relates to can adopt following arbitrary method synthetic:
(1) radicals X and the cell S of forming connection chain S
iStep reaction makes the S chain length reach required length, obtains X-S, connects then and goes up group L, obtains X-S-L;
(2) cell S of composition connection chain S
iBetween react to each other, obtain meeting the connection chain S of length requirement, connection chain S and radicals X are reacted then, obtain X-S, connect to go up group L then, obtain X-S-L;
(3) cell S of composition connection chain S
iBetween react to each other, obtain meeting the S chain of length requirement, connection chain S and group L are reacted then, obtain S-L, S-L reacts with radicals X more then, obtains X-S-L;
(4) group L and the cell S of forming connection chain S
iStep reaction makes the S chain length reach required length, obtains S-L, connects then and goes up radicals X, obtains X-S-L.
In above-mentioned building-up process, being connected and can realizing between the growth of being connected between radicals X and the connection chain S, chain S, chain S and the group L through thermochemistry or photochemistry reaction paths such as (microwave radiation chemistry).Constitute the cell S of connection chain S
iCan be identical independently of one another or different.
The modification molecule X-L that said method of modifying relates to can obtain through the reaction between radicals X and the group L.In above-mentioned building-up process, being connected between radicals X and the group L can realize through thermochemistry or photochemistry reaction paths such as (microwave radiation chemistry).
The related photosensitive group X of this paper contains at least one xanthone unit.For example, photosensitive group X can be derived from and be selected from following material: replacement or unsubstituted single xanthone (for example formula 1), replacement or unsubstituted fused rings dioxa anthrone (fused ring dixanthone) be benzo oxa-pimelinketone and xanthone (for example formula 2) and xanthone and xanthone (for example formula 3), replacement or unsubstituted di-xanthone (for example formula 4-7) and replacement or unsubstituted oligomeric xanthone (for example formula 8) for example.Preferably, photosensitive group X is derived from and replaces or unsubstituted single xanthone.
In the di-xanthone group of formula 7 expressions, R " expression singly-bound or replacement or unsubstituted C
1-12Alkylene preferably replaces or unsubstituted C
1-4Alkylene is for example shown in the formula 9.
In the present invention, in order to realize being connected between X group and S chain and the L group, said single xanthone group can be substituted, shown in I:
formula I
Wherein R representes to be positioned at the substituting group on the respective rings independently of one another, and a and b independently are respectively the integer that is selected from 0-3, and a+b >=1.Preferably, a and b are respectively the integer that is selected from 0-2 independently, and a+b >=1, particularly preferably a+b=1 or 2.
In formula I, said substituent R can be temperature-sensitive functional group, replacement or not replace and/or by at interval chain alkylene of functional group, with respect to the unitary replacement of single xanthone or unsubstituted free ring structure, or annular atoms on single xanthone unit replacement or the unsubstituted condensed ring structure that form.The no any cyclosubstituted single xanthone of preferred use is as photosensitive group X in present method.Below these several kinds of situation have been made detailed description, but and do not mean that when having a plurality of R said R only limits to the substituting group of above-mentioned same type, just for convenience's sake, narrates respectively it.
Said temperature-sensitive functional group for example comprise carboxyl, hydroxyl, amido (primary amine, secondary amine, tertiary amine groups etc.), sulfydryl, sulfonic group, halogen atom, ester group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone; Carbonatoms on its skeleton is no more than 18 usually; Preferably be no more than 15; Especially preferably be no more than 8, more preferably no more than 5.When having said temperature-sensitive functional group, said photosensitive group X can be derived from for example xanthone-3-acyl chlorides, xanthone-2-hydroxyl, xanthone-4-hydroxyl, xanthone-2-formyloxy, xanthone-3-formyloxy, xanthone-4-formyloxy-7-hydroxyl, xanthone-3-amino etc.
Said chain alkylene can be to replace or do not replace and/or by the C at interval of functional group
1-18Chain alkylene, preferred C
1-8Chain alkylene, more preferably C
1-5Chain alkylene, preferred especially C
1-3Chain alkylene.Term as used herein " chain alkylene " comprises straight chain and side chain.According to the present invention, said C
1-18Chain alkylene can be C
1-18Alkyl, preferred C
1-8Alkyl, more preferably C
1-5Alkyl, preferred especially C
1-3Alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, hexyl; Perhaps C
2-18Unsaturated alkyl (like alkene, alkynes), preferred C
2-8Unsaturated alkyl, more preferably C
2-5Unsaturated alkyl, preferred especially C
3-5Unsaturated alkyl, for example vinyl, propenyl, n-butene base, butadienyl, butine, pentadienyl, 2-methyl-2-butene base.
As indicated above, chain alkylene can be substituted and/or by functional group at interval.For example, said chain substituent can be selected from following one or more functional groups and replace or be selected from following one or more functional groups interval: carboxyl, hydroxyl, amido (primary amine, secondary amine, tertiary amine groups etc.), imido grpup, sulfydryl, sulfonic group, halogen atom, ester functional group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone, epoxy, ether, thioether, carbonyl, sulfonyl, thionyl, nitro, cyanic acid, phosphinylidyne functional group, furans functional group, sugared functional group, acyl functional group.Said halogen atom for example is fluorine, chlorine, bromine, iodine.
When said chain alkylene was replaced by above-mentioned functional group, its non-limiting example was the amino amyl group of 2-aminopropyl, 3-, the amino hexenyl of 2-; 2-carboxyl-butyl, 4-carboxyl-heptyl, 3-carboxyl-decyl; Methanol-based, ethanol based, propyl alcohol base, pentanediol base; Chloromethyl, trifluoromethyl, chlorovinyl, chloroprene base; Acrylamido, hexanoyl amido, decoyl amido; 3-hexosamine group, 2-bromopropylene amide group; Vinyl cyanide; Group-4 ethyl formate; B carbonyl; Acrylic; Sec.-propyl sulfinyl etc.When said chain alkylene by above-mentioned functional group at interval the time, its non-limiting example be methoxyl group, oxyethyl group, the last of the ten Heavenly stems oxygen base, glycol ether base, dipropylene glycol base, diethylin, diethylenetriamine base, triethylene tetramine base, diethylolamine group etc.
Ring in the ring structure mentioned above for example is saturated cyclic hydrocarbons, unsaturated cyclic hydrocarbon, saturated heterocyclic hydrocarbon, unsaturated heterocycle hydrocarbon.Ring in the said ring structure preferably has 5-6 annular atoms.Annular atoms in the said ring structure can contain the heteroatoms of one or more O of being selected from, N, S.Heteroatomic number can be decided as required, for example is 2-3, is preferably 1-2.
Said saturated cyclic hydrocarbons comprises for example hexanaphthene, pentamethylene, ketopentamethylene, pimelinketone.Need to prove, be similar to the such hydro carbons of ketopentamethylene and pimelinketone and be included in the saturated cyclic hydrocarbons.Said unsaturated cyclic hydrocarbon comprises for example benzene, cyclopentenes, tetrahydrobenzene, cyclohexadiene.Said saturated heterocyclic hydrocarbon comprises for example tetrahydrofuran, amylene oxide, piperidines, dioxolane, dioxane, thiacyclopentane, thia hexanaphthene, hexanolactam, caprolactone, oxa-ketopentamethylene, oxa-pimelinketone.Said unsaturated heterocycle hydrocarbon comprises for example oxa-tetrahydrobenzene, thia tetrahydrobenzene, furan nucleus, pyrrole ring, thiphene ring, pyridine, pyrimidine, imidazoles, benzo pimelinketone, benzo oxa-pimelinketone, amylene oxide and benzo pimelinketone.Said ring structure can be distributed on single xanthone unit symmetrical or asymmetricly.Can know that by preceding text these ring structures itself can be substituted, for example by one or more following functional group's replacement: C that are selected from
1-18Chain alkylene, preferred C
1-8Chain alkylene, more preferably C
1-5Chain alkylene, preferred especially C
1-3Chain alkylene, it can be to replace or do not replace and/or by functional group at interval, the definition of said substituting group and functional group is directed against shown in the description of " chain alkylene " like preceding text; Halogen atom is like chlorine, bromine and iodine; Carboxyl, sulfonic group, ester group, nitro, carboxylic acid halides, amido, hydroxyl, acid amides, aldehyde, sulfonic group, sulfydryl, ketone, sulfonyl, thionyl; Carbonatoms on the wherein said skeleton is no more than 18 usually; Preferably be no more than 15, especially preferably be no more than 8, more preferably no more than 5.
For for simplicity, only show the instance of single xanthone below with no any substituent above-mentioned ring structure.
The above-mentioned substituent kind of mentioning, position and size should satisfy the photosensitivity that significantly do not reduce the X group, modification molecule in the sterically hindered requirement such as little of the coupling of surface of polymer material.In the method, said substituting group preferably replaces on 7 at 2, and the substituent volume on 1 and 8 should be less.
These also are suitable for for other xanthone class formations mentioned above substituent description.
Functional group L can be chemical group and biological group etc., chemical group for example comprises-COOH (carboxyl) ,-COOR ' (carboxylic acid ester groups comprises aliphatic hydrocarbon ester, ester OH, glycidyl ester or the like) ,-COO
-M
+(carboxylate salt, M
+Be the unit price positive ion, for example alkalimetal ion such as Li
+, Na
+, K
+And NH
4 +Deng) ,-SO
3H (sulfonic group) ,-SO
3R ' (sulfonate group comprises aliphatic hydrocarbon ester, ester OH, glycidyl ester or the like) ,-SO
3 -M
+(sulphonate, M
+Be the unit price positive ion, for example alkalimetal ion such as Li
+, Na
+, K
+And NH
4 +Deng) ,-COX (acid halide group, like acyl chlorides, acylbromide etc.) ,-CONHNH
2(hydrazides) ,-NHCONHNH
2(Urea,amino-) ,-NHCSNHNH
2(thiosemicarbazide) ,-CN (itrile group) ,-CHO (aldehyde radical) ,-COR ' (carbonyl: R ' comprises methyl, ethyl, propyl group etc.) ,-OH (hydroxyl) ,-SH (sulfydryl) ,-SSR ' (disulfide group, R ' comprise methyl, ethyl, propyl group etc.) ,-NH
2(amino comprises primary amine groups, secondary amine, tertiary amine groups etc.), ammonium salt group (comprise-NH
3 +X
-, as-NH
3 +Cl
-,-NH
3 +Br
-) ,-NHNH
2(diazanyl) ,-OR ' (ether: R ' comprises methyl, ethyl, propyl group etc.) ,-SR ' (thioether: R ' comprises methyl, ethyl, propyl group etc.), (the annular atoms number on its single ring generally is no more than 8 to epoxide group; For example be no more than 6; Perhaps be no more than 4, it can comprise oxyethane, propylene oxide, dioxetane, amylene oxide etc.) ,-X (halogen atom: comprise F, Cl, Br, I etc.) ,-NO
2(nitro) ,-R ' (alkyl) ,-R ' X
n(halo alkyl, X comprise F, Cl, Br, I etc., n≤(2 * R ' in carbonatoms+1)); Wherein said R ' expression alkyl, the chain alkylene of for example saturated or undersaturated, branching or non-branching, its carbonatoms can be no more than 20 as required; Preferably be no more than 15; More preferably no more than 10, be no more than 6 especially, for example methyl, ethyl, propyl group, the tertiary butyl, crotonyl or the like; And/or said functional group L is derived from the heterocycle molecule, and for example oxygen heterocyclic ring, nitrogen heterocyclic ring, sulfur heterocyclic ring are like pyrimidine, pyridine, piperidines, succsinic acid imide, hexanolactam, toxilic acid imide, furans, thiazole etc.; Metal complex, for example porphyrin complex, polypyridine complex compound and metallocene complex such as ferrocene type complex compound; Salt, for example oxonium salt, sulfosalt, nitrogen salt; Biological group is phosphorylcholine, theophylline, sugar (comprising monose, oligosaccharides, oligomeric polysaccharide etc.), microbiotic (comprising Synnematin B etc.), VITAMINs (comprising vitamin H etc.), toxin, weedicide, sterilant, steroid, polypeptide, nucleosides, polypeptide-nucleic acid, haptin etc. for example.
The selection of connection chain S should be taken all factors into consideration from three aspects such as the length of chain, flexibility, solubility properties.Usually, the length of connection chain S generally should be no more than 40nm; In some cases, the length of connection chain S should be not more than 10nm; The length of chain is long more, and the number of the functional group that can connect also increases thereupon.Chain flexibility has determined the mobility of functional group.In general, flexible big connection chain helps the motion of functional group, and flexible little connection chain then can limit to the motion of functional group.The solubility property of connection chain is the important factor of regulating the solubility property of the whole modification molecule that is synthesized.Generally, after photosensitive group and functional group were chosen, the two had just been confirmed solubility property influence of modification molecule.Therefore; In order to make the modification molecule possess the dissolving power of different solvents, just need to select to have the connection chain of different solubility properties, usually; Water-soluble strong connection chain can improve the water-soluble of modification molecule, and the connection chain that oil soluble is strong can improve the dissolving power of modification molecule in organic solvent.
Comprehensive above three aspects consider, the connection chain S that is suitable for replaces or do not replace and/or by the C at interval of functional group
1-20Alkyl, for example C
1-10Alkyl comprises saturated or undersaturated alkyl, and it is chosen wantonly has a small amount of side chain and/or aromatic group.Said alkyl is selected from following one or more functional groups and replaces or be selected from following one or more functional groups interval: carboxyl, hydroxyl, amido, imido grpup, sulfydryl, sulfonic group, halogen atom, ester functional group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone, epoxy, ether, thioether, carbonyl, sulfonyl, thionyl, nitro, cyanic acid, phosphinylidyne functional group, furans functional group, sugared functional group, acyl functional group.The connection chain S that is suitable for also comprise polyoxyethylene glycol, oligomeric/multi-polyamide as gather-Beta-alanine, gather glycocoll, polylysine, polypeptide, oligose, oligomeric/polyphosphate or phosphoric acid salt such as phosphate monoester, phosphodiester, mono phosphoric acid ester acid amides, di(2-ethylhexyl)phosphate acid amides, oligomeric/poly sulphonamide/sulphonate etc.In addition, connection chain S can be made up of the single above-mentioned unit of mentioning, and perhaps is made up of the above-mentioned unit combination of mentioning.
In the method; Select preparation to mix the used following factor of solvent considered with said molecule X-S-L or X-L: (1) has certain dissolving power to said molecule X-S-L or X-L, and said molecule X-S-L or X-L can dissolved states in solution or existed with the micella state; (2) be difficult for reacting with any functional group of said molecule X-S-L or X-L, no matter said molecule is under the state of ground state or excited state; (3) performance of not destroying functional group is biological property especially; (4) be the poor solvent of polymkeric substance of being modified.
The instance of the solvent that is suitable for comprises organic solvent such as methylene dichloride, THF, ethanol, methyl alcohol, acetone etc.; Water; Water and the formed mixed solvent of some organic solvent in certain ratio; And the aqueous solution of some inorganic salt etc.In the mixed solvent of water and organic solvent preparation, the shared volume(tric)fraction of water can be less than 97%, preferably is less than 5%, and organic solvent can be acetone, ethanol, methyl alcohol etc.When selecting for use inorganic salt solution to make solvent, can select for use sodium-chlor, Repone K etc. to make solute, the massfraction of solute can be less than 3%, preferably less than 0.5%.
In the method, the concentration of the solution of said molecule X-S-L or X-L and solvent acquisition can be 10
-7MM to 10
3In the scope of mM, preferred 10
-3The concentration range of mM to 3.0mM is most preferably in 0.1mM to 1.0mM concentration range.With the process of solvent needs according to reaction conditions, can be by adding damping fluid, acid or alkali, the pH of said solution is controlled in the scope of 0-7 or 7-12.
Present method institute modified polymeric material there is not special limitation, as long as said surface of polymer material has certain active atom.The instance that is suitable for the polymer materials of present method comprises polyolefine for example Vilaterm, Vestolen PP 7052, PS, SE; Rubber is styrene-butadiene rubber(SBR), paracril, SBS, ethylene-propylene rubber(EPR), X 050, Zylox, chlorohydrin rubber for example; Urethane; Polymeric amide is polycaprolactam for example; Polycarbonate is the polyhexamethylene carbonic ether for example; Polyimide; Polyester is polyethylene terephthalate, polycaprolactone for example; Fluoro-resin, for example tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer; Polyethers is ppe, polyoxyethylene glycol for example; Polyvinyl alcohol; PVA; Polyacrylate(s) is polymethylmethacrylate for example; Biopolymer is chitin, chitosan, polyamino acid, POLYACTIC ACID for example; Or their blend, matrix material.High density polyethylene, low density polyethylene (LDPE), cast polypropylene, BOPP Biaxially oriented polypropylene film, butyl rubber, styrene-butadiene rubber(SBR), tree elastomer-styrene-butadiene rubber(SBR) blend, chlorohydrin rubber, PS, tetrafluoraoethylene-hexafluoropropylene copolymer, polyimide, polycarbonate, the polyethylene terephthalate etc. of comprising commonly used.
In some cases; The shape of polymer materials of being modified should satisfy following requirement: surface of polymer material can form the modified solution layer with can be so that UV-light shines this surface of polymer material with certain intensity; Like sheet material, film, these materials can be solid polymkeric substance single-material, intermingling material, stacking material or the organic coating on nonmetal or metal species base of polymkeric substance.
The surface of polymer material that is modified evenly covers the method that the method for one deck modified solution can adopt those skilled in the art to be familiar with: drip casting (drop casting), pickling process, spin-coating method, spread coating, " sandwich " structure cladding process etc.For example, spin-coating method can find among the 9331-9337 at Lanmuir 2000,16.
But the equipment that the ultraviolet source low pressure that irradiation is used, middle pressure, high voltage mercury lamp or other can the emitted in ultraviolet optical bands preferably uses high voltage mercury lamp.The ultraviolet light wavelength is in the scope of 190-420nm, and irradiation intensity can be at 100.0mw/cm
2In the scope, preferred 1.0-20.0mw/cm
2Strength range (is that λ=254nm uitraviolet intensity is a reference standard with the wavelength).
According to factors such as the thermostability of the irradiation intensity of UV-light, the material that is modified and light stability, suitable light application time can generally be no more than 300 minutes, preferably in 30 minutes, most preferably in 2-15 minute scope.
In the method, can remove the molecule X-S-L or the X-L of remained on surface through washing.The following factor of selection considered of used washing lotion: (1) has certain dissolving power to said molecule, and said molecule can dissolved state in solution or existed with the micella state; (2) be that the be modified poor solvent (3) of polymkeric substance is difficult for reacting with the functional group that is incorporated on the modified surface, the performance of not destroying functional group is biological property especially; (4) boiling point is relatively low.The instance of the reagent that is suitable for comprises water, organic reagent such as methylene dichloride, THF, ethanol, methyl alcohol, acetone etc.
On the other hand, the invention provides the modification molecule that is used for the auxiliary modifying surface of polymer material method of UV-light, said modification molecule has photosensitive group X and functional group L, and wherein said photosensitive group X contains at least one xanthone unit.
In one embodiment, the structure of said modification molecule can be X-L or X-S-L, and wherein X is for containing the unitary photosensitive group of at least one xanthone, and L is a functional group, and S is a connection chain.Just describe in " method of modifying " part about the definition of photosensitive group X, functional group L, connection chain S, polymer materials P such as preceding text.
On the other hand, the invention provides the purposes of said modification molecule in the surface-treated of polymer materials.Polymer materials for example is polyolefine, rubber, urethane, polymeric amide, polycarbonate, polyimide, polyester, fluoro-resin, polyethers, polyvinyl alcohol, PVA, polyacrylate(s), biopolymer or their blend, matrix material.
Particularly, said polymer materials can be Vilaterm, Vestolen PP 7052, PS, SE, styrene-butadiene rubber(SBR), paracril, SBS, ethylene-propylene rubber(EPR), X 050, Zylox, chlorohydrin rubber, polycaprolactam, polyhexamethylene carbonic ether, polyethylene terephthalate, polycaprolactone, tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, ppe, polyoxyethylene glycol; Z 150PH, polymethylmethacrylate, chitin, chitosan, polyamino acid, POLYACTIC ACID or their blend, matrix material.
In addition, the present invention also provides the goods with the surface of polymer material that forms through method modification mentioned above.
The range of application of above-mentioned embodiment comprises the following aspects:
1. improve the biological property of polymkeric substance; Can be used as the carrier (like orifice plate etc.) of immunoassay; The carrier of cell cultures (like culture tube, culturing bottle, petridish etc.), the carrier of biological assay and bioseparation (like microballoon, microballon etc.), and as carrier of solid phase synthesis etc.
2. improve the surface hydrophilicity of polymer materials, specifically be used for: the novel nothing of (1) preparation is dripped type PE canopy film; (2) dyeability of raising fiber; (3) be used for preparing anti-static fabric; (4) be used to improve the dyeability of collision bumper.
3. improve the resistance oxygen water preventing ability of polymer surfaces, as be used for preparing novel wrapping material.
4. improve the cohesiveness of polymer surfaces, as be used for the range upon range of wrapping material that close of prepared layer, also can be used to improve the viscosifying power between polymer materials and other metal or the non-metallic material.
This method has following advantage: (1) can obtain good modified effect, and is simple to operate, quick, with low cost, environmental pollution is few; (2) functional group that is suitable for is in extensive range, and the structure of functional group is not subject to destruction in the operating process; (3) can on a surface, introduce the group of different performance simultaneously.
Description of drawings
Fig. 1. the concentration of change compound 6 and light application time are to the influence of PS finishing effect
Fig. 2. the effect of 2,4,6 pairs of PS finishinges of compound
Fig. 3. the synoptic diagram of " sandwich " structural response device
Fig. 4. the concentration of compound 7 is to the influence of BOPP membrane surface modification effect
Fig. 5. the ultraviolet light irradiation time is to the influence of BOPP membrane surface modification effect
Embodiment
Through concrete embodiment the present invention is carried out detailed introduction below, but be not limited to the content of embodiment.
The common compounds that relates among the embodiment and the abbreviation of proprietary name:
2-XTC: xanthone-2-formyloxy
Boc: tertbutyloxycarbonyl
DMF:N, N '-N
CDI:N, N '-carbonyl dimidazoles
TEA: triethylamine
DIEA: diisopropyl ethyl amine
NTA: nitrilotriacetic acid(NTA)
BOP: block special condensing agent
Boc-β-Ala-OH: tert-butoxycarbonyl-
DMSO: DMSO 99.8MIN.
OPD: o-phenylendiamine dihydrochloride
PEG300: polyoxyethylene glycol (molecular-weight average: 300)
Ph
3CCl: triphenylmethyl chloride
PEG300-CPh
3: polyoxyethylene glycol (300) trityl ether
PS: PS
BOPP: BOPP Biaxially oriented polypropylene film
LDPE: low density polyethylene (LDPE) film
F46: hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymerization film
IIR: butyl rubber
SBR: butylbenzene film
CHR: chloropharin film
NR/SBR: tree elastomer-styrene-butadiene rubber(SBR) blend
PC: polycarbonate
PI: polyimide
PET: ethylene glycol terephthalate
1H NMR: proton magnetic spectrum
Molecule X-S-L's is synthetic
Synthetic (compound 1) of N-[3-(xanthone-2-formamido group) propyl group]-carboxylamine tertiary butyl ester
(13.2g 55mmol) is dissolved among the DMF (120ml), 40 ℃ of stirred in water bath dissolvings with 2-XTC.Disposable adding CDI in the solution (9.25g, 57mmol), stirring reaction 4 hours 40 minutes.Reaction system is produced, in the cooling in 10 minutes of 20 ℃ of stirred in water bath.To singly replace tertbutyloxycarbonyl-1, (11.09g 67mmol) is dissolved in TEA/DMF (20ml to the 3-tn; 10%v/v) in the solution, mix, in the disposable reaction system that joins xanthone-2-formic acid and CDI; Add TEA (13ml) then, stir and be warmed up to 40 ℃, reacted 11 hours.Reaction system is cooled to 0 ℃, adds deionized water (700ml) and precipitate, suction filtration is dried the gained solid under 40 ℃, pact-0.09MPa vacuum condition.Productive rate 41.47% (is benchmark with 2-XTC).
1H?NMR（600MHz，DMSO-d
6）：δ8.76（1H），8.72（1H），8.32（1H），8.24（1H），7.93（1H），7.76（1H），7.71（1H），7.52（1H），6.79（1H），3.31（2H），3.00（2H），1.67（2H），1.38（9H）ppm.
Synthetic (compound 2) of 3-(xanthone-2-formamido group) propyl ammonium chloride
With compound 1 (4.06g, 10.25mmol) dispersed with stirring in the methyl alcohol (120ml), stir add after 20 minutes hydrochloric acid/methanol solution (5.4M, 20ml).Be heated to backflow 73 ℃ of stirred in water bath, reacted 2.5 hours.Above-mentioned reaction system is placed in the refrigeration chamber cools off, add anhydrous diethyl ether (300ml) deposition, suction filtration with anhydrous diethyl ether (150ml) washing, is dried the solid that obtains then under 40 ℃, pact-0.09MPa vacuum condition.Productive rate 88.02% (is benchmark with compound 1).
1H?NMR（600MHz，DMSO-d
6）：δ8.99（1H），8.74（1H），8.36（1H），8.24（1H），7.96-7.85（3H），7.94（1H），7.78（1H），7.72（1H），7.53（1H），3.40（2H），2.86（2H），1.86（2H）ppm。
Synthetic (compound 3) of N-[3-(xanthone-2-formamido group)-propyl group]-formamyl ethyl-carboxylamine tertiary butyl ester
With BOP (1.90g, 4.3mmol) with Boc-β-Ala-OH (0.89g, 4.7mmol) be dissolved into TEA/DMF (29ml, 10%v/v) in, stirred 10 minutes down at 20 ℃.(1.27g's disposable adding compound 2 4.3mmol), spends the night at 19 ℃ of-20 ℃ of stirring reactions.Add deionized water (350ml) and precipitate, suction filtration is dried the gained solid under 40 ℃, pact-0.085MPa vacuum.Productive rate 77.86% (is benchmark with compound 2).
1H?NMR（600MHz，DMSO-d
6）：δ8.76（1H），8.72（1H），8.32（1H），8.24（1H），7.92（1H），7.85（1H），7.77（1H），7.72（1H），7.52（1H），6.70（1H），3.32（2H），3.31(4H)，2.23（2H），1.69（2H），1.37（9H）ppm。
Synthetic (compound 4) of 3-(xanthone-2-formamido group) propyl group-formamyl ethyl ammonium chloride
(1.52g 3.25mmol) is dissolved in the methyl alcohol (70ml), and the hydrochloric acid/methyl alcohol of adding (5ml, 5.4M HCl) is heated to backflow 73 ℃ of stirred in water bath, reacts 2.5 hours with compound 3.High amounts of solvents is removed in decompression, toward resistates in, adds ether (100ml), and suction filtration washs the solid that obtains with ether (150ml), under 40 ℃, pact-0.09MPa vacuum condition, dries then.Productive rate 83.29% (is benchmark with compound 3).
1H?NMR（600MHz，DMSO-d
6）：δ8.82（1H），8.72（1H），8.33（1H），8.24（1H），8.13（1H），7.94（1H），7.90-7.60（3H），7.78（1H），7.72（1H），7.53（1H），3.34（2H），3.17（2H），3.00（2H），2.47（2H），1.72（2H）ppm。
N-{N-[3-(xanthone-2-formamido group)-propyl group]-formamyl ethyl }-synthetic (compound 5) of formamyl ethyl-carboxylamine tertiary butyl ester.
With BOP (2.86g, 4.54mmol) with Boc-β-Ala-OH (0.98g, 5.0mmol) be dissolved in TEA/DMF (53ml, 10%v/v) in, 20 ℃ of stirring in water bath reaction 10 minutes; (1.83g, 4.54mmol), (47ml, 10%v/v), stirring reaction spends the night disposable adding compound 4 to add TEADMF again.Add about deionized water (3000ml) deposition, suction filtration with deionized water wash gained solid, is dried under 75 ℃, pact-0.09MPa vacuum condition then.Productive rate 74.08% (is benchmark with compound 4).
1H?NMR（600MHz，DMSO-d
6）：δ8.78（1H），8.72（1H），8.32（1H），8.23（1H），7.92（1H），7.87（1H），7.86（1H），7.77（1H），7.72（1H），7.52（1H），6.67（1H），3.36（2H），3.24（2H），3.14（2H），3.09（2H），2.24（2H），2.20（2H），1.69（2H），1.36（9H）ppm。
N-{N-[3-(xanthone-2-formamido group)-propyl group]-formamyl ethyl }-synthetic (compound 6) of formamyl ethyl ammonium chloride
(2.10g 3.90mmol) is dissolved in the methyl alcohol (150ml), adds HCl/ methanol solution (11ml, 5.4M HCl), is heated to backflow 73 ℃ of stirred in water bath, reacts 2.5 hours with compound 5.Removal of solvent under reduced pressure obtains product.Productive rate 31.22% (is benchmark with compound 5).
1H?NMR（600MHz，DMSO-d
6）：δ8.82（1H），8.72（1H），8.34（1H），8.24（1H），8.14（1H），7.99（1H），7.94（1H），7.81（3H），7.77（1H），7.72（1H），7.53（1H），3.33（2H），3.29（2H），3.14（2H）2.98（2H），2.27（2H），2.45（2H），1.70（2H）ppm。
3{N-(3-(xanthone-2-formamido group)-propyl group) formamyl } synthetic (compound 7) of propionic acid
In 20 ℃ of water-baths, (0.50g 1.5mmol) stirs in DMF (40ml) and was uniformly dispersed in 10 minutes, and (0.30g 3.0mmol), adds triethylamine (2.0ml) again to add Succinic anhydried then with compound 2.Behind the stirring reaction 3 hours, (25ml 1.0M) and deionized water (315ml), stirs 4 hours depositions in ice-water bath, obtain white solid to add hydrochloric acid in the system; Suction filtration, (300ml) washes solid with deionized water, oven dry under 40 ℃, pact-0.09MPa vacuum condition.Productive rate 87.54% (is benchmark with compound 2).
1H?NMR（600MHz，DMSO-d
6）：δ12.04（1H），8.77（1H），8.72（1H），8.32（1H），8.24（1H），7.92（1H），7.77（1H），7.72（1H），7.52（1H），3.32（2H），3.13（2H），2.43（2H），2.32（2H），1.68（1H）ppm。
N-[3-(xanthone-2-formamido group)-propyl group]-amino thioformyl-hydrazine (compound 8)
(0.44g 1.0mmol) is dissolved among the DMF (20ml), adds CS successively with BOP
2(0.6ml, 10.0mmol), compound 2 (0.35g, 1.0mmol) and TEA (0.42ml, 3.0mmol), 20 ℃ of stirred in water bath reaction 1.5 hours.Under vacuum condition, remove remaining CS
2In ice-water bath, above-mentioned reaction soln is added drop-wise to Hydrazine Hydrate 80, and (0.8ml is in DMF solution 14.0mmol) (5.0ml); Spend the night 20 ℃ of stirred in water bath reactions then.Add deionized water (100ml) deposition, suction filtration, (200ml) washes solid with deionized water, under 40 ℃, pact-0.09MPa vacuum condition, dries then.Productive rate 67.43% (is benchmark with compound 2).
1H?NMR（600MHz，DMSO-d
6）：δ8.85（1H），8.72（1H），8.61（1H），8.32（1H），8.23（1H），8.04（1H），7.91（1H），7.77（1H），7.71（1H），7.51（1H），4.47（2H），3.54（2H），3.33（2H），1.76（2H）ppm。
2-chloroformyl-xanthone (compound 9)
(2.41g 10.0mmol) is distributed to SOCl with 2-XTC
2(50ml), stirring reaction 4hr under refluxad.Remaining SOCl is removed in the decompression of gained yellow-brownish solution
2, obtain the yellowish brown solid.Use sherwood oil (100ml) to wash solid at twice, sherwood oil is removed in decompression then.Oven dry under 40 ℃, pact-0.09MPa vacuum condition.Productive rate: 47.12% (is benchmark with 2-XTC).
1H?NMR（600MHz，DMSO-d
6）：δ9.15（1H），8.39（1H），8.36（1H），7.79（1H），7.61（1H），7.55（1H），7.46（1H）ppm。
FITR：ν1759.68cm
-1(C=O)，1671.99cm
-1(C=O)，1606.69cm
-1(C=C)，1315.17cm
-1(C-O-C)，757.88cm
-1(C-H)。
Synthetic (compound 10) of 6-(xanthone-2-formamido group)-caproic acid methyl ester
(4.80g 20.0mmol) is dissolved among the DMF (130ml), 40 ℃ of stirred in water bath dissolvings with 2-XTC.Disposable adding CDI in the solution (3.73g, 23.0mmol), stirring reaction 4 hours.Reaction system is produced, in the cooling in 10 minutes of 20 ℃ of stirred in water bath.(4.55g 25.0mmol) joins in the reaction system, adds TEA (7.0ml) then and spends the night 40 ℃ of stirred in water bath reactions with 6-aminocaprolc acid methyl esters HCl.In ice-water bath, add deionized water (250ml) and precipitate, suction filtration is dried the gained solid under 70 ℃ of normal pressures.Productive rate: 60.48% (is benchmark with 2-XTC).
1H?NMR（600MHz，DMSO-d
6）：δ8.78（1H），8.71（1H），8.31（1H），8.23（1H），7.91（1H），7.76（1H），7.71（1H），7.51（1H），3.56（3H），3.28（2H），2.31（2H），1.56（4H），1.32（2H）ppm。
Synthetic (compound 11) of 6-(xanthone-2-formamido group)-caproic acid
Under 80 ℃ of water bath condition, (3.95g, 10.7mmol) dispersed with stirring is even in THF (120ml) with compound 10.(1.35g 32.2mmol) is made into the solution of 0.5M, in the disposable system that joins the front, stirs 1.5 hours with LiOH.The THF in the system is removed in decompression, and (10.0ml 10.0M), stirred acid precipitation 1 hour to the hydrochloric acid that adds then.Suction filtration, (350ml) washes solid with deionized water, oven dry under 40 ℃, pact-0.09MPa vacuum condition.Productive rate: 96.78% (is benchmark with compound 10).
1H?NMR（600MHz，DMSO-d
6）：δ11.96（1H），8.78（1H），8.72（1H），8.32（1H），8.24（1H），7.92（1H），7.76（1H），7.52（1H），3.28（2H），2.22（2H），1.56（4H），1.34（2H）ppm。
Synthetic (compound 12) of 6-[xanthone-2-formamido group]-caproyl hydrazine
(0.37g 1.0mmol) is distributed to (20ml) in the methyl alcohol, and (1.2ml 21.0mmol), under refluxad reacted 6 hours disposable adding Hydrazine Hydrate 80 with compound 10.Be cooled to room temperature, removal of solvent under reduced pressure; Resistates is distributed in the frozen water (20ml) again, and suction filtration with the washing solid, is dried under 40 ℃, pact-0.09MPa vacuum condition.Productive rate: 34.33% (is benchmark with compound 10).
1H?NMR（600MHz，DMSO-d
6）：δ8.95（1H），8.77(1H)，8.72（1H），8.32（1H），8.24（1H），7.92（1H），7.76（1H），7.72（1H），7.52（1H），4.39（2H），3.28（2H），2.03（2H），1.60-1.51（4H），1.30（2H）ppm。
Synthetic (compound 13) of N-[3-(xanthone-2-formamido group)-propyl group] N-[(4-O-(α-D-glucopyranosyl)-β-D-glucopyranosyl)] N-ethanoyl ammonia
With compound 2 (0.50g, 1.5mmol) and SANMALT-S (1.54g 4.5mmol) is dissolved in the anhydrous methanol (80ml).(0.35ml, 2.0mmol), stirring reaction spends the night in 60 ℃ of water-baths, nitrogen atmosphere to add DIEA.Then system is placed on and stirs cooling in the ice bath, add diacetyl oxide (3.5ml).At room temperature stir hold over night.Removal of solvent under reduced pressure, resistates is water-soluble, filters and lyophilize; Use column chromatography chromatogram that the gained solid is separated, silica gel (100-200 order) phase that fixes uses water as eluent and isolates remaining SANMALT-S, and (v/v=50/50) isolates compound 13 as eluent with acetonitrile/water, and lyophilize obtains title product.Productive rate: 53.26% (with respect to compound 2).
1H?NMR（600MHz，DMSO-d
6）：δ8.76（1H），8.72（1H），8.32（1H），8.24（1H），7.93（1H），7.77（1H），7.72（1H），7.52（1H），6.79（1H），5.79（1H），5.04（1H），4.43-4.42（7H），4.03（1H），4.00（1H），3.77（1H），3.74（2H），3.49（1H），3.40（1H），3.31（2H），3.02（1H），3.00（2H），2.02（3H），1.67（2H）ppm。
Synthetic (compound 14)
of xanthone-2-formamido group-propyl group amino-6-ketoestradiol-6-(O-ethyloic)-oxime
With compound 2 (0.50g, 1.5mmol), BOP (0.95g 1.5mmol) is dissolved among the DMF (50ml), add 6-ketoestradiol-6-(O-ethyloic)-oxime (0.54g, 1.5mmol), DIEA (0.53mL, 3.0mmol).Stirring reaction is 4 hours under 20 ℃ of water-baths, adds deionized water (10ml) then, and suction filtration is used Na successively
2CO
3The aqueous solution (3 * 10ml, 10%wt), 10%KHSO
4The aqueous solution (3 * 10ml, 10%wt) and deionized water (3 * 10ml) wash solid, oven dry under 40 ℃, pact-0.09MPa vacuum condition.Productive rate 85.26% (is benchmark with compound 2).
1H?NMR（600MHz，DMSO-d
6）：δ8.82（1H），8.72（1H），8.33（1H），8.24（1H），8.13（1H），7.94（1H），7.78（1H），7.72（1H），7.53（1H），7.21（1H），7.14（1H），6.78（1H），4.42（2H），3.31-1.16（22H），0.64（3H）ppm。
2-formic acid macrogol ester-xanthone (compound 15)
(3.0g 10.0mmol) is dissolved in the pyridine (20ml), and about 1/3rd pyridine (azeotropic drying) is removed in distillation with PEG300.With Ph
3(0.28g 1.0mmol) is dissolved in the pyridine (6ml) CCl, at room temperature is added drop-wise in the solution of PEG300, and the dropping time is no less than 3 hours.At room temperature continue stirring reaction 18hr.Underpressure distillation removes and desolvates; In system, add toluene (2 * 25ml) distillations subsequently.Residual liquid is dissolved in dichloromethane (100ml) alkane, adds 0.1M Hydrocerol A, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt successively and wash.Get organic phase and carry out concentrating under reduced pressure, liquid concentrator is carried out post separate: silica gel (100-200 order) is stationary phase, and ethyl acetate/petroleum ether (v:v=50:50) ~ ETHYLE ACETATE (100%) is as moving phase.Products therefrom is a colourless oil liquid.Productive rate 85.31%.
1H?NMR（600MHz，CDCl
3）：δ7.48（5H），7.28（5H），7.20（5H），3.65（20H），3.58（2H），3.25（2H），2.95（1H）ppm。
With PEG300-CPh
3(0.4g, 0.74mmol) (0.19g 0.74mmol) is dissolved in the pyridine (15ml), and stirring reaction 16 hours distills and removes pyridine, adds toluene (2 * 25ml) distillations then with compound 9.Residual liquid is dissolved in the methylene dichloride (50ml), adds 0.1M Hydrocerol A, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt successively and wash.Get organic phase and carry out concentrating under reduced pressure, liquid concentrator is carried out post separate: silica gel (100-200 order) is stationary phase, and ethyl acetate/petroleum ether (v:v=90:10) is as moving phase.The intermediate product that obtains is a yellow oily liquid, productive rate 72.46% (0.41g).Intermediate product is dissolved in methylene chloride (10ml v:v=80:20) mixed solvent, adds ZnBr
2(0.5g, 2.18mmol) stirring reaction is 20 minutes, and evaporation removes and desolvates.Liquid concentrator is carried out post to be separated: silica gel (100-200 order) is stationary phase, and ethyl acetate/petroleum ether (v:v=80:20) is as moving phase.The intermediate product that obtains is pale brown look oily liquids, productive rate 85%.
1H?NMR（600MHz，DMSO-d
6）：δ8.74（1H），8.23（1H），8.26（1H），7.93（1H），7.78（1H），7.72（1H），7.53（1H），3.63（20H），3.56（2H），3.24（2H），2.97（1H）ppm。
The uv-absorbing of six kinds of compounds of table 1
Compound 6 being dissolved in the zero(ppm) water, being mixed with the solution that starting point concentration is 0.58mM, is benchmark with above-mentioned concentration, carries out 5 times dilution, is made into a series of modified solution.Before the use, all logical nitrogen deoxygenation in 10 minutes of the solution of each concentration.Get the not PS of surface modification (PS) 96 hole enzyme plates, use absolute ethyl alcohol and washed with de-ionized water hole surface three times respectively, in 50 ℃ of bakings 45 minutes, dry for standby.The modified solution of the above-mentioned preparation liquid volume added with 100 μ L/ holes is joined in each hole of enzyme plate one by one, enzyme plate is placed into carries out illumination under the 1000W high voltage mercury lamp, light intensity is 3.55mW/cm
2(λ=254nm), light application time was respectively 5 minutes, 7 minutes and 10 minutes.After illumination finishes, incline and fall modified solution, with deionized water rinsing three times, dried by the fire 45 minutes at 50 ℃ then, it is subsequent use to keep in Dark Place after the oven dry.Add vitamin H-succsinic acid imide ester (biotin-OSu ester) solution (PBS of pH=7.2 makees solvent) of 3.94 μ g/mL in the hole of modification by the liquid volume added in 100 μ L/ holes, be placed into then to cultivate in the 21-23 ℃ of baking oven and spend the night; It is inferior to give a baby a bath on the third day after its birth with Covabuffer, and Covabuffer kept in the hole 10 minutes when last; (PBS of pH=7.2 makees solvent to the mixing solutions of the affinity plain (HRP-avidin) of adding affinity plain (avidin) and horseradish peroxidase-labeled; Contain avidin 4 μ g/mL; Contain HRP-avidin 0.13 μ g/mL) 100 μ L/ holes, in 21-23 ℃ of baking oven, cultivated 2 hours; Wash secondary with Covabuffer, Covabuffer kept in the hole 10 minutes when last; Topple over and fall washing lotion, (pH=5.0 contains 0.015% (v/v) H to add citrate buffer
2O
2OPD with 0.6mg/mL) coupling reaction is carried out in 100 μ L/ holes, adds the sulfuric acid termination reaction of 2.0N after 6 minutes; Use the Multiskan MK3 type ELIASA of Thermo company to measure the absorbancy of modification hole at the 492nm place.The result is as shown in Figure 1.Discovery is when lower concentration, and light application time does not play decisive influence to the effect of finishing; When concentration is increased to 4.64 * 10
-3After the mM, along with the increase of light application time, the finishing effect of PS is improved, the modified effect of illumination in the time of 10 minutes is best.
The repeatability of 4 pairs of PS finishinges of table 2 compound
| Mean light absorbency (492nm) | Error | Percentage error % |
| 0.324 | 0.011 | 3.4 |
Be illustrated in figure 3 as the synoptic diagram that uses " sandwich " structural response device in the present embodiment; Details are as follows for each characteristics of components function: parts 1 are last quartz plate; UV-light sees through its downward irradiation and causes the photochemical reaction between parts 2, parts 3 and the parts 4; And 1 pair of parts 2 of parts, parts 3 and parts 4 also provide certain pressure, make the combination between the three tightr; Parts 2 are last base material, must have enough UV-light penetrance, and the UV-light of the needed characteristic wavelength of UV-light surface-treated is not had sorption, itself also can be the polymer materialss that is modified; Parts 3 are modified solution, under the inducing of UV-light, parts 2 and 4 are carried out modification; Parts 4 are the polymer materialss that is modified for following base material; Parts 5 play the carrying effect for following quartz plate to above-mentioned four parts.According to actual needs, can give up in parts 1,2 or 5 any one, select complete " sandwich " structural response device of forming by above-mentioned five parts in the present embodiment for use.
Get BOPP film and PS plate and be base material up and down, use above-mentioned modified solution to be made into the reactor drum of " sandwich " structure as shown in Figure 3.In normal temperature environment, it is that (light intensity at λ=254nm place is 7.0mw/cm to the 1000W high voltage mercury lamp that the reactor drum of " sandwich " structure is placed into power
2) carry out illumination, light application time was respectively 0.5,2.0,5.0 and 10.0 minute.PS plate after handling and BOPP film with big water gaging flushing, with the absolute ethyl alcohol flushing, are removed the moisture that substrate surface adheres to earlier then, are placed on to leave standstill in the air more than 15 minutes absolute ethyl alcohol is volatilized fully.
PS plate and BOPP film to modification carry out air contact angle (CA) mensuration, and these data are used for the wetting ability on characterize polymers surface, and the more little wetting ability of numerical value is good more.Concrete grammar is: use the OCA20 type contact angle measurement of German Dataphysics instruments company at normal temperatures, get the reading that 1 μ l deionized water writes down the air contact angle after vertically dropping on the surface to be measured at once at every turn.Each sample is surveyed 6 points (down together) at least.The result sees table 3.
The surface water contact angle of table 3 compound 6 modification PS plates and BOPP film changes
Embodiment 7
Method by embodiment 3 is mixed with the modified solution of 0.58mM with compound 6 and carries out the deoxygenation processing.With method construct " sandwich " the structural response device of being mentioned among the embodiment 6, be last base material with the BOPP film, LDPE film, F46 film, IIR sheet material, SBR sheet material, CHR sheet material, the conduct of NR/SBR sheet material be base material down.In normal temperature environment, it is that (light intensity at λ=254nm place is 3.55mw/cm to the 1000w high voltage mercury lamp that the reactor drum of " sandwich " structure is placed into power
2) down illumination 10.0 minutes.Base materials such as the LDPE film after the modification, F46 film, IIR sheet material, SBR sheet material, CHR sheet material, NR/SBR sheet material are earlier with big water gaging flushing; Wash with absolute ethyl alcohol then; Remove the moisture that substrate surface adheres to, be placed in the 21-23 ℃ of baking oven baking and more than 10 minutes absolute ethyl alcohol volatilized fully.
Identical to air measurement of contact angle method before and after the base material modifications such as LDPE film, F46 film, IIR sheet material, SBR sheet material, CHR sheet material, NR/SBR sheet material with embodiment 6.The result is as shown in table 4.Through the contrast of each base material water contact angle before and after the modification, find that all there is modified effect preferably on 6 pairs of different substrate materials surfaces of compound.
The contrast of water contact angle before and after the modification on 6 pairs of different substrate materials surfaces of table 4 compound
| ?F46 | LDPE | IIR | SBR | CHR | NR/SBR | |
| Before the modification | ?114.2° | 104.0° | 108.5° | 109.7° | 115.6° | 116.8° |
| After the modification | ?69.6° | 70.7° | 65.8° | 84.7° | 94.3° | 82.6° |
Identical to air measurement of contact angle method before and after the base material modifications such as BOPP film, PS plate with embodiment 6.The result is as shown in table 5.Through the contrast of each base material water contact angle before and after the modification, when finding to adopt different solvents, compound 4 all can play good modified effect to various polymerization thing material surface.
The surface water contact angle of table 5 compound 4 modification PS plates and BOPP film changes
Embodiment 9
Identical to air measurement of contact angle method before and after the base material modifications such as PC plate, PI film, PET film with embodiment 6.The result is as shown in table 6.Through the contrast of each base material water contact angle before and after the modification, compound 4 all can play certain modified effect to various polymerization thing material surface.
The contrast of water contact angle before and after the modification on 4 pairs of different substrate materials surfaces of table 6 compound
| PC | PI | PET | |
| Before the modification | 88.1° | 69.5° | 76.3° |
| After the modification | 72.6° | 59.4° | 54.8° |
Compound 7 is dissolved in the LiOH aqueous solution of 0.1M, is mixed with the modified solution of 5.0mM, carry out the twice dilution and obtain a series of modified solution, the oxygen that logical nitrogen was removed in each solution in 10 minutes.Get the BOPP film and be base material up and down, according to method construct " sandwich " the structural response device of being mentioned among the embodiment 6.The method of UV-light photoirradiation modification is identical with embodiment 7, and light application time is 10 minutes.With BOPP film after the deionized water rinsing modification, being dipped into concentration then is in the 100mL Viola crystallina aqueous solution of 0.15mg/mL, in 22-23 ℃ of baking oven, cultivates 30 minutes.Take out,, in 22-23 ℃ of baking oven, dry then with deionized water rinsing BOPP film surface.
The modified solution that with concentration is 5.0mM is the basis, changes light application time and is respectively 0.5,2.0,5.0,7.0 and 10.0 minute, and the BOPP film is carried out surface treatment.The method that ultraviolet light irradiation modification, aftertreatment and Viola crystallina are adsorbed is identical with the front.
Use GBC Cintra 20 ultraviolet-visible spectrophotometric spectras (Australia) to measure the adsorption effect of modification BOPP film to Viola crystallina, the result sees Fig. 4 and Fig. 5 respectively.Can know that by Fig. 4 along with the increase of compound 7 concentration, BOPP membrane surface modification effect strengthens; Can know by Fig. 5, prolong the surface modification effect that light application time helps 7 pairs of BOPP films of compound.
Claims (19)
1. the method for modifying of a surface of polymer material, this method comprise through photosensitive group X and issue third contact of a total solar or lunar eclipse chemical reaction and surface that functional group L is introduced polymer materials P at ultraviolet light irradiation, and wherein said photosensitive group X contains at least one xanthone unit,
Wherein said functional group L is selected from-COOH ,-COOR ' ,-COO
-M
+,-SO
3H ,-SO
3R ' ,-SO
3 -M
+,-COX ,-CONHNH
2,-NHCONHNH
2,-NHCSNHNH
2,-CN ,-CHO ,-COR ' ,-OH ,-SH ,-SSR ', amino, ammonium salt group, diazanyl ,-OR ' ,-SR ', epoxide group ,-X ,-NO
2,-R ' ,-R ' X
n, R ' representes alkyl, M
+Expression unit price positive ion or NH
4 +, X representes halogen atom, n≤(2 * R ' in carbonatoms+1); And/or said functional group L is derived from phosphorylcholine, heterocycle molecule, metal complex, theophylline, salt, sugar, microbiotic, VITAMINs, toxin, weedicide, sterilant, steroid, polypeptide, nucleosides, polypeptide-nucleic acid, haptin,
Wherein on the surface of polymer materials P, introduce molecule X-L and/or X-S-L, wherein X is for containing the unitary photosensitive group of at least one xanthone, and L is a functional group, and S is connection chain,
Wherein said method comprises that making photosensitive group X and polymer materials P surface that photochemical reaction take place through ultraviolet light irradiation forms P-X; With synthetic molecules S-L; Through photochemical reaction or thermal chemical reaction molecule S-L is connected to the polymer materials P surface that has formed P-X on its surface then, forms P-X-S-L.
2. method according to claim 1, wherein said photosensitive group X is derived from following material: replace or unsubstituted single xanthone, replacement or unsubstituted fused rings dioxa anthrone, replacement or unsubstituted di-xanthone and replacement or unsubstituted oligomeric xanthone.
3. method according to claim 2, wherein said photosensitive group X is derived from and replaces or unsubstituted single xanthone.
4. method according to claim 3, wherein said photosensitive group X is derived from the single xanthone of replacement of formula I,
Wherein R representes to be positioned at the substituting group on the respective rings independently of one another, and a and b are respectively the integer that is selected from 0-3 independently, and a+b >=1.
5. method according to claim 4; Wherein said substituent R is selected from temperature-sensitive functional group, replacement or does not replace and/or by at interval chain alkylene of functional group, with respect to replacement or unsubstituted condensed ring structure that the unitary replacement of single xanthone or unsubstituted free ring structure and the annular atoms on single xanthone unit form, wherein said temperature-sensitive functional group be selected from carboxyl, hydroxyl, amido, sulfydryl, sulfonic group, halogen atom, ester group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone.
6. method according to claim 5, wherein said chain alkylene are C
1-18Chain alkylene.
7. method according to claim 6, wherein said chain alkylene are C
1-8Alkyl or C
2-8Unsaturated alkyl.
8. method according to claim 6, wherein said chain alkylene are C
1-5Alkyl or C
2-5Unsaturated alkyl.
9. method according to claim 6, wherein said chain alkylene are selected from following one or more functional groups and replace or be selected from following one or more functional groups interval: carboxyl, hydroxyl, amido, imido grpup, sulfydryl, sulfonic group, halogen atom, ester functional group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone, epoxy, ether, thioether, carbonyl, sulfonyl, thionyl, nitro, cyanic acid, phosphinylidyne functional group, furans functional group, sugared functional group, acyl functional group.
10. method according to claim 5, the ring in the wherein said ring structure are the saturated cyclic hydrocarbons with 5-6 annular atoms, unsaturated cyclic hydrocarbon, saturated heterocyclic hydrocarbon, unsaturated heterocycle hydrocarbon.
11. method according to claim 10, the annular atoms in the wherein said ring structure contains the heteroatoms of one or more O of being selected from, N, S.
12. method according to claim 10, the ring in the wherein said ring structure are selected from pentamethylene, hexanaphthene, ketopentamethylene, pimelinketone, benzene, cyclopentenes, tetrahydrobenzene, cyclohexadiene, tetrahydrofuran, amylene oxide, piperidines, dioxolane, dioxane, thiacyclopentane, thia hexanaphthene, hexanolactam, caprolactone, oxa-ketopentamethylene, oxa-pimelinketone, oxa-tetrahydrobenzene, thia tetrahydrobenzene, furan nucleus, pyrrole ring, thiphene ring, pyridine, pyrimidine, imidazoles, benzo pimelinketone, benzo oxa-pimelinketone, amylene oxide and benzo pimelinketone.
13. being selected from following one or more functional groups, method according to claim 12, wherein said ring structure replace: C
1-18Chain alkylene, halogen atom, carboxyl, sulfonic group, ester group, nitro, carboxylic acid halides, amido, hydroxyl, acid amides, aldehyde, sulfonic group, sulfydryl, ketone, sulfonyl, thionyl.
14. method according to claim 1, wherein said connection chain S is selected from and replaces or do not replace and/or by the C at interval of functional group
1-20The combination of alkyl, polyoxyethylene glycol, oligomeric/multi-polyamide, oligose, oligomeric/polyphosphate or phosphoric acid salt, oligomeric/poly sulphonamide/sulphonate and said units.
15. method according to claim 14, wherein said C
1-20Alkyl is selected from following one or more functional groups and replaces or be selected from following one or more functional groups interval: carboxyl, hydroxyl, amido, imido grpup, sulfydryl, sulfonic group, halogen atom, ester functional group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone, epoxy, ether, thioether, carbonyl, sulfonyl, thionyl, nitro, cyanic acid, phosphinylidyne functional group, furans functional group, sugared functional group, acyl functional group.
16. method according to claim 15, the length of wherein said connection chain S is no more than 40nm.
17. method according to claim 1, wherein said polymer materials are selected from polyolefine, rubber, urethane, polymeric amide, polycarbonate, polyimide, polyester, fluoro-resin, polyethers, polyvinyl alcohol, PVA, polyacrylate(s), biopolymer or their blend, matrix material.
18. method according to claim 17, wherein said polymer materials is selected from: Vilaterm, Vestolen PP 7052, PS, SE, styrene-butadiene rubber(SBR), paracril, SBS, ethylene-propylene rubber(EPR), X 050, Zylox, chlorohydrin rubber, polycaprolactam, polyhexamethylene carbonic ether, polyethylene terephthalate, polycaprolactone, tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, ppe, polyoxyethylene glycol; Z 150PH, polymethylmethacrylate, chitin, chitosan, polyamino acid, POLYACTIC ACID or their blend, matrix material.
19. have the goods of the surface of polymer material that forms through each described method modification of claim 1-18.
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Cited By (5)
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| CN103233274A (en) * | 2013-05-06 | 2013-08-07 | 北京化工大学 | Preparation method of polymer based three-dimensional (3D) biochip |
| CN104694036A (en) * | 2015-02-15 | 2015-06-10 | 滁州云林数码影像耗材有限公司 | Anti-scratch paint protecting film and preparation method thereof |
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| CN111548489A (en) * | 2020-04-28 | 2020-08-18 | 中山大学 | Photosensitive material, application of photosensitive material in preparation of flexible circuit board and preparation method of photosensitive material |
| CN112708129A (en) * | 2019-10-24 | 2021-04-27 | 中国科学技术大学 | Ionomer with micropores, preparation method thereof, ionomer membrane with micropores and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233274A (en) * | 2013-05-06 | 2013-08-07 | 北京化工大学 | Preparation method of polymer based three-dimensional (3D) biochip |
| CN103233274B (en) * | 2013-05-06 | 2014-12-31 | 北京化工大学 | Preparation method of polymer based three-dimensional (3D) biochip |
| CN104694036A (en) * | 2015-02-15 | 2015-06-10 | 滁州云林数码影像耗材有限公司 | Anti-scratch paint protecting film and preparation method thereof |
| CN104693777A (en) * | 2015-02-15 | 2015-06-10 | 滁州云林数码影像耗材有限公司 | Scratch-resistant polyurethane film and preparation method thereof |
| CN104693777B (en) * | 2015-02-15 | 2017-06-13 | 滁州云林数码影像耗材有限公司 | A kind of anti-scratch polyurethane film and preparation method thereof |
| CN112708129A (en) * | 2019-10-24 | 2021-04-27 | 中国科学技术大学 | Ionomer with micropores, preparation method thereof, ionomer membrane with micropores and application |
| CN111548489A (en) * | 2020-04-28 | 2020-08-18 | 中山大学 | Photosensitive material, application of photosensitive material in preparation of flexible circuit board and preparation method of photosensitive material |
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