CN102702556B - Ultraviolet-assisted surface modification method and product with surface formed thereby - Google Patents

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

The surface modifying method that UV-light is auxiliary and there are the surperficial goods that method thus forms

Technical field

The present invention relates to the auxiliary polymer surface modifying method of a kind of surface modifying method, particularly UV-light and for the modification molecule of the auxiliary material surface modifying method of UV-light and the goods with the material surface that method modification thus forms.

Background technology

The material with special surface properties has a wide range of applications at printing, dyeing, bonding, obstruct and biological field etc.For example, the PET film tinctorial property with good surface hydrophilicity is good, can print out the wrapping material of multiple color and pattern; The polymer materials with excellent surface biological property can be widely used in the fields such as biosensor, biomaterial for medical purpose, biological rapid detection.

Conventionally can obtain by the method for surface modification the material with different surfaces performance.Described method comprises wet chemistry method, chemical etching, corona method, plasma method, high-energy ray irradiation method and photochemical method etc.

Ultraviolet surface graft is a kind of thereby modification molecule to be fixed to the photochemical method that material surface is realized modification object by ultraviolet light irradiation in the mode of covalent linkage.Under ultraviolet light irradiation, modification molecule completes covalently bound with material surface by the mode (polymerization) of surface grafting polymerization or the mode (coupling process) of surperficial coupling.UV-induced coupling method is by the bridge linking effect of photosensitive group, and practical function group is connected with material surface, and this method can obtain having by changing the kind of functional group the material of different surfaces characteristic.

In recent years, to introducing functional group by UV-induced coupling method, make the method for polymer surface modification cause researchist's interest.

J.Biomed.Mater.Res.1997,37,282 – 290 disclose take the modification molecule that phenylazide is functional group as photosensitive group, phosphorylcholine urethane is carried out to surface modification.The shortcoming of the method is: the activity of the nitrene free radical that phenylazide group generates under ultraviolet light irradiation is too strong, thereby it easily produces the efficiency that side reaction reduces surface modification; In addition, the reactivity of described species high and can occur with most compounds, organic solvent and water after journey or effect immediately.

WO 96/31557 discloses usings quinones and as the synthetic a series of compounds of photosensitive group, carries out the method for surface modification.The photosensitivity that the shortcoming of the method is quinones group relatively a little less than, cause the ultraviolet light irradiation time relatively long, be unfavorable for producing fast and cost-saving.

Therefore, the modification molecule that can produce the photosensitive group that has the free radical of certain activity and have stronger photosensitivity need to be contained in this area, 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.The photosensitive group X of the method by containing at least one xanthone unit issues third contact of a total solar or lunar eclipse chemical reaction and the surface of functional group L being introduced to polymer materials P at ultraviolet light irradiation.

By the inventive method, can on the surface of polymer materials P, introduce molecule X-L and X-S-L, wherein X is the photosensitive group that contains at least one xanthone unit, and L is functional group, and S is connection chain.

In one embodiment, described photosensitive group X is connected by 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 are with defined above.

With regard to the inventive method, mode of connection mentioned above can realize by for example following approach:

(1) synthetic molecules X-L or X-S-L, then by ultraviolet light irradiation, make described molecule X-L or X-S-L and polymer materials P surface that photochemical reaction occur, thereby the surface by described molecule X-L or X-S-L introducing polymer materials P, forms P-X-L or P-X-S-L.

(2) by ultraviolet light irradiation, make photosensitive group X and polymer materials P surface that photochemical reaction occur and form P-X, with synthetic molecules S-L, then by 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, forms P-X-S-L.

(3) synthetic molecules X-S, then by photochemical reaction, molecule X-S is connected to polymer materials P surface, form P-X-S, by 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) by photochemical reaction, photosensitive group X is fixed to polymer materials P surface, form P-X, then optionally by photochemical reaction or thermal chemical reaction, connection chain S is connected to described photosensitive group X-shaped and becomes P-X-S, by photochemical reaction or thermal chemical reaction, functional group L is connected with the photosensitive group X that is optionally connected with connection chain S that is fixed to polymer materials P surface afterwards, thereby the surface by described molecule X-L or X-S-L introducing polymer materials P, forms P-X-L or P-X-S-L.

By 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 scope of the present invention under the condition that does not depart from inventive concept.

In another embodiment, before on the surface of described molecule X-L and/or X-S-L being introduced to described polymer materials P, can optionally by photochemical reaction or thermal chemical reaction, connection chain S ' be fixed to the polymer materials P surface for the treatment of modification, form P-S ', then by molecule X-L mentioned above or X-S-L, introduce the polymer materials P surface that is connected with connection chain S ', thereby form P-S '-X-L or P-S '-X-S-L.Form the cell S of connection chain S ' _i' can be identical or different independently of one another.The selection of connection chain S ' can be according to the character for the treatment of modified surface from the viewpoint of length, flexibility, reactive behavior, hydrophobicity/wetting ability etc.The selection of connection chain S ' can be with reference to the detailed description to connection chain S below.

Above-mentioned approach can realize by different modes, existing take the first approach and is described in greater detail as example.

With regard to above-mentioned the first approach, described method of modifying can comprise the following steps especially:

A. synthetic molecules X-S-L or X-L, wherein X is the photosensitive group that contains at least one xanthone unit, L is functional group, and S is connection chain;

B. by molecule X-S-L or X-L and suitable solvent to form the modified solution that contains described molecule X-S-L;

C. on the surface of the polymer materials P that is modified, form described modified solution layer;

D. with the surface with described modified solution layer of the above-mentioned polymer materials P of ultraviolet light irradiation, to introduce molecule X-S-L or X-L on this surface.

If need, after described method can also comprise E. irradiation, remove modification molecule X-S-L remaining on described surface.

The modification molecule X-S-L that described method of modifying relates to can adopt following either method synthetic:

(1) radicals X and the cell S that forms connection chain S _istep reaction, makes S chain length reach required length, obtains X-S, then connects upper group L, obtains X-S-L;

(2) form the cell S of connection chain S _ibetween react to each other, obtain meeting the connection chain S of length requirement, then connection chain S reacts with radicals X, obtains X-S, then connects group L, obtains X-S-L;

(3) form the cell S of connection chain S _ibetween react to each other, obtain meeting the S chain of length requirement, then connection chain S reacts with group L, obtains S-L, then S-L reacts with radicals X again, obtains X-S-L;

(4) group L and the cell S that forms connection chain S _istep reaction, makes S chain length reach required length, obtains S-L, then connects upper radicals X, obtains X-S-L.

In above-mentioned building-up process, being connected and can realizing by reaction paths such as thermochemistry or photochemistry (microwave radiation chemistry) between the growth of being connected between radicals X and connection chain S, chain S, chain S and group L.Form the cell S of connection chain S _ican be identical or different independently of one another.

The modification molecule X-L that described method of modifying relates to can obtain by reacting between radicals X and group L.In above-mentioned building-up process, being connected between radicals X and group L can realize by reaction paths such as thermochemistry or photochemistry (microwave radiation chemistry).

Related photosensitive group X contains at least one xanthone unit herein.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 xanthone (for example formula 2) and xanthone 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 representing in formula 7, R " expression singly-bound or replacement or unsubstituted C _1-12alkylene, preferably replaces or unsubstituted C _1-4alkylene, example as shown in Equation 9.

formula 9

In the present invention, in order to realize being connected between X group and S chain and L group, described single xanthone group can replace, shown in I:

formula I

Wherein R represents to be positioned at the substituting group in respective rings independently of one another, and a and b are respectively independently for being selected from the integer of 0-3, and a+b >=1.Preferably, a and b are respectively independently for being selected from the integer of 0-2, and a+b >=1, particularly preferably a+b=1 or 2.

In formula I, described substituent R can be temperature-sensitive functional group, replacement or do not replace and/or by the chain alkylene at functional group interval, with respect to the replacement of single xanthone unit or unsubstituted free ring structure or with the replacement or the unsubstituted condensed ring structure that together with annular atoms on single xanthone unit, form.In present method, preferably use without any cyclosubstituted single xanthone as photosensitive group X.Below these several situations are described in detail, but and described in not meaning that when there is a plurality of R R only limit to the substituting group of above-mentioned same type, just for convenience's sake, it is narrated respectively.

Described temperature-sensitive functional group comprise such as 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 conventionally, preferably be no more than 15, particularly preferably be no more than 8, more preferably no more than 5.When having described temperature-sensitive functional group, described photosensitive group X can be derived from such as 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.

Described chain alkylene can be to replace or do not replace and/or by the C at functional group interval _1-18chain alkylene, preferably C _1-8chain alkylene, more preferably C _1-5chain alkylene, particularly preferably C _1-3chain alkylene.Term as used herein " chain alkylene " comprises straight chain and side chain.According to the present invention, described C _1-18chain alkylene can be C _1-18alkyl, preferably C _1-8alkyl, more preferably C _1-5alkyl, particularly preferably C _1-3alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, hexyl; Or C _2-18unsaturated alkyl (as alkene, alkynes), preferably C _2-8unsaturated alkyl, more preferably C _2-5unsaturated alkyl, particularly preferably C _3-5unsaturated alkyl, for example vinyl, propenyl, n-butene base, butadienyl, butine, pentadienyl, 2-methyl-2-butene base.

As described above, chain alkylene can be replace and/or by functional group interval.For example, described 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 ,Zhi functional group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone, epoxy, ether, thioether, carbonyl, sulfonyl, thionyl, nitro, cyano group, phosphinylidyne functional group, ,Xian functional group of ,Tang functional group of furans functional group.Described halogen atom is for example fluorine, chlorine, bromine, iodine.

When described chain alkylene is replaced by above-mentioned functional group, its non-limiting example is 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 described chain alkylene is during by above-mentioned functional group interval, 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, diethanolamine group etc.

Ring in ring structure mentioned above is for example saturated cyclic hydrocarbons, unsaturated cyclic hydrocarbon, saturated heterocyclic hydrocarbon, unsaturated heterocycle hydrocarbon.Ring in described ring structure preferably has 5-6 annular atoms.Annular atoms in described ring structure can contain the heteroatoms of one or more O of being selected from, N, S.Heteroatomic number can be determined as required, for example, be 2-3, is preferably 1-2.

Described saturated cyclic hydrocarbons comprises for example hexanaphthene, pentamethylene, cyclopentanone, pimelinketone.It should be noted that, be similar to the such hydro carbons of cyclopentanone and pimelinketone and be included in saturated cyclic hydrocarbons.Described unsaturated cyclic hydrocarbon comprises for example benzene, cyclopentenes, tetrahydrobenzene, cyclohexadiene.Described saturated heterocyclic hydrocarbon comprises for example tetrahydrofuran, amylene oxide, piperidines, dioxolane, dioxane, thiacyclopentane, thia hexanaphthene, hexanolactam, caprolactone, oxa-cyclopentanone, oxa-pimelinketone.Described unsaturated heterocycle hydrocarbon comprises for example oxa-tetrahydrobenzene, thia tetrahydrobenzene, furan nucleus, pyrrole ring, thiphene ring, pyridine, pyrimidine, imidazoles, benzo ring hexanone, benzo oxa-pimelinketone, amylene oxide benzo pimelinketone.Described ring structure can be symmetrical or be distributed in asymmetrically on single xanthone unit.By known these ring structures above, itself can be substituted, for example, by one or more, are selected from following functional group and replace: C _1-18chain alkylene, preferred C _1-8chain alkylene, more preferably C _1-5chain alkylene, C particularly preferably _1-3chain alkylene, it can be to replace or do not replace and/or by functional group interval, the definition of described substituting group and functional group is as above for as shown in the description of " chain alkylene "; Halogen atom, as 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 wherein said skeleton is no more than 18 conventionally, preferably be no more than 15, be particularly preferably no more than 8, more preferably no more than 5.

For for simplicity, only show the example having without single xanthone of any substituent above-mentioned ring structure below.

The above-mentioned substituent kind of mentioning, position and size should meet the photosensitivity that significantly do not reduce X group, modification molecule in the sterically hindered requirement such as little of the coupling of surface of polymer material.In the method, described substituting group preferably replaces on 7 at 2, and the substituent volume on 1 and 8 should be less.

These are also applicable for other xanthone class formations mentioned above to substituent description.

Functional group L can be chemical group and biological group etc., for example comprise-COOH(of chemical group carboxyl) ,-COOR ' (carboxylic acid ester groups comprises aliphatic hydrocarbon ester, hydroxy ester, glycidyl ester etc.) ,-COO ^-m ⁺(carboxylate salt, M ⁺be unit price positive ion, for example alkalimetal ion is as Li ⁺, Na ⁺, K ⁺and NH ₄ ⁺deng) ,-SO ₃h(sulfonic group) ,-SO ₃r ' (sulfonate group comprises aliphatic hydrocarbon ester, hydroxy ester, glycidyl ester etc.) ,-SO ₃ ^-m ⁺(sulfonate, M ⁺be unit price positive ion, for example alkalimetal ion is as Li ⁺, Na ⁺, K ⁺and NH ₄ ⁺deng) ,-COX(acid halide group, as 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 ' comprises 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 is generally no more than 8 to epoxide group, for example be no more than 6, or 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 comprises F, Cl, Br, I etc., n≤(2 * R ' in carbonatoms+1)), wherein said R ' represents alkyl, the chain alkylene of saturated or undersaturated, branching or non-branching for example, and 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 especially 6, for example methyl, ethyl, propyl group, the tertiary butyl, butenyl etc.; And/or described functional group L is derived from heterocycle molecule, for example oxygen heterocyclic ring, nitrogen heterocyclic ring, sulfur heterocyclic ring, as 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 are as ferrocene type complex compound; Salt, for example oxonium salt, sulfosalt, nitrogen salt; Biological group such as phosphorylcholine, theophylline, sugar (comprising monose, oligosaccharides, oligomeric polysaccharide etc.), microbiotic (comprising penicillin etc.), VITAMIN (comprising vitamin H etc.), toxin, weedicide, sterilant, steroid, polypeptide, nucleosides, polypeptide-nucleic acid, haptens etc.

Three aspects such as the length of the selection Ying Conglian of connection chain S, flexibility, solubility property consider.Conventionally, 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 longer, 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 large connection chain is conducive to the motion of functional group, and flexible little connection chain can limit to the motion of functional group.The solubility property of connection chain is the important factor that regulates the solubility property of the whole modification molecule being synthesized.Generally, after photosensitive group and functional group are chosen, the two impact of the solubility property on modification molecule has just been determined.Therefore, in order to make modification molecule possess the dissolving power of different solvents, just need to select to have the connection chain of different solubility properties, conventionally, 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, applicable connection chain S replaces or do not replace and/or by the C at functional group interval _1-20alkyl, for example C _1-10alkyl, comprises saturated or undersaturated alkyl, and it optionally has a small amount of side chain and/or aromatic group.Described 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 ,Zhi functional group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone, epoxy, ether, thioether, carbonyl, sulfonyl, thionyl, nitro, cyano group, phosphinylidyne functional group, ,Xian functional group of ,Tang functional group of furans functional group.Applicable connection chain S also comprises that polyoxyethylene glycol, oligomeric/multi-polyamide are if poly--Beta-alanine, poly-glycocoll, polylysine, polypeptide, oligose, oligomeric/polyphosphate or phosphoric acid salt are 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 by the single above-mentioned cell formation of mentioning, or consists of the above-mentioned unit combination of mentioning.

In the method, select preparation to mix solvent used with described molecule X-S-L or X-L and should consider following factor: (1) has certain dissolving power to described molecule X-S-L or X-L, described molecule X-S-L or X-L can dissolved states in solution or are existed with micella state; (2) be difficult for reacting with any functional group of described molecule X-S-L or X-L, no matter under the state of described molecule in 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 example of applicable solvent comprises that organic solvent is as methylene dichloride, tetrahydrofuran (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 fraction of water can be less than 97%, is preferably less than 5%, and organic solvent can be acetone, ethanol, methyl alcohol etc.While selecting inorganic salt solution to make solvent, can select sodium-chlor, Repone K etc. to make solute, the massfraction of solute can be less than 3%, is preferably less than 0.5%.

The concentration of the solution that in the method, described molecule X-S-L or X-L and solvent obtain can be 10 ^-7mM to 10 ³in the scope of mM, preferably 10 ^-3the concentration range of mM to 3.0mM, most preferably in 0.1mM to 1.0mM concentration range.With the process of the solvent needs according to reaction conditions, can, by adding damping fluid, acid or alkali, the pH of described solution be controlled in the scope of 0-7 or 7-12.

Polymer materials to the modification of present method institute does not have special restriction, as long as described surface of polymer material has the atom of certain activity.The example that is suitable for the polymer materials of present method comprises polyolefine for example polyethylene, polypropylene, polystyrene, polyvinyl chloride; Rubber is styrene-butadiene rubber(SBR), paracril, SBS, ethylene-propylene rubber(EPR), chloroprene rubber, silicon rubber, chlorohydrin rubber for example; Urethane; Polymeric amide is polycaprolactam for example; Polycarbonate is polyhexamethylene carbonic ether for example; Polyimide; Polyester is polyethylene terephthalate, polycaprolactone for example; Fluoro-resin, for example tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer; Polyethers is polyphenylene oxide, polyoxyethylene glycol for example; Polyvinyl alcohol; Polyvinyl acetate (PVA); Polyacrylate(s) is polymethylmethacrylate for example; Biopolymer is chitin, chitosan, polyamino acid, poly(lactic acid) for example; Or their blend, matrix material.Conventional high density polyethylene, low density polyethylene (LDPE), cast polypropylene, Biaxially oriented polypropylene film (BOPP), isoprene-isobutylene rubber, styrene-butadiene rubber(SBR), natural rubber-SBR Blends, chlorohydrin rubber, polystyrene, tetrafluoraoethylene-hexafluoropropylene copolymer, polyimide, polycarbonate, the polyethylene terephthalate etc. of comprising.

In some cases, the shape of polymer materials of being modified should meet following requirement: surface of polymer material can form modified solution layer and can be so that UV-light is irradiated to this surface of polymer material with certain intensity, as 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 method of surface of polymer material uniform fold one deck modified solution of being modified can adopt the familiar method of those skilled in the art: drip casting (drop casting), pickling process, spin-coating method, spread coating, " sandwich " structure cladding process etc.For example, spin-coating method can, at Lanmuir 2000,16, find in 9331-9337.

But the equipment that the ultraviolet source low pressure that irradiation is used, middle pressure, high voltage mercury lamp or other can emitting ultraviolet light wave bands, is preferably used high voltage mercury lamp.Ultraviolet light wavelength is in the scope of 190-420nm, and irradiation intensity can be at 100.0mw/cm ²in scope, preferred 1.0-20.0mw/cm ²strength range (take wavelength be reference standard for λ=254nm uitraviolet intensity).

According to factors such as the thermostability of the irradiation intensity of UV-light, the material that is modified and light stability, applicable light application time can generally be no more than 300 minutes, preferably in 30 minutes, most preferably within the scope of 2-15 minute.

In the method, can remove by washing molecule X-S-L or the X-L of remained on surface.The selection of washing lotion used should be considered following factor: (1) has certain dissolving power to described molecule, and described molecule can dissolved state in solution or existed with micella state; (2) be that the be modified poor solvent (3) of polymkeric substance is difficult for reacting with the functional group being incorporated on modified surface, the performance of not destroying functional group is biological property especially; (4) boiling point is relatively low.The example of applicable reagent comprises that water, organic reagent are as methylene dichloride, tetrahydrofuran (THF), ethanol, methyl alcohol, acetone etc.

On the other hand, the invention provides the modification molecule for the auxiliary modifying surface of polymer material method of UV-light, described 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 described modification molecule can be X-L or X-S-L, and wherein X is the photosensitive group that contains at least one xanthone unit, and L is functional group, and S is connection chain.About the definition of photosensitive group X, functional group L, connection chain S, polymer materials P as above just described in " method of modifying " part.

On the other hand, the invention provides the purposes of described modification molecule in the surface modification of polymer materials.Polymer materials is for example polyolefine, rubber, urethane, polymeric amide, polycarbonate, polyimide, polyester, fluoro-resin, polyethers, polyvinyl alcohol, polyvinyl acetate (PVA), polyacrylate(s), biopolymer or their blend, matrix material.

Particularly, described polymer materials can be polyethylene, polypropylene, polystyrene, polyvinyl chloride, styrene-butadiene rubber(SBR), paracril, SBS, ethylene-propylene rubber(EPR), chloroprene rubber, silicon rubber, chlorohydrin rubber, polycaprolactam, polyhexamethylene carbonic ether, polyethylene terephthalate, polycaprolactone, tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, polyphenylene oxide, polyoxyethylene glycol; Polyvinyl alcohol, polymethylmethacrylate, chitin, chitosan, polyamino acid, poly(lactic acid) or their blend, matrix material.

In addition, the present invention also provides the goods with the surface of polymer material forming by 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 (as orifice plate etc.) of immunoassay, the carrier of cell cultures (as culture tube, culturing bottle, culture dish etc.), the carrier of biological assay and bioseparation (as microballoon, microballon etc.), and as carrier of solid phase synthesis etc.

2. improve the surface hydrophilicity of polymer materials, specifically for: (1) prepares novel without dripping a type PE canopy film; (2) improve the dyeability of fiber; (3) be used for preparing anti-static fabric; (4) for improving the dyeability of collision bumper.

3. improve the resistance oxygen water preventing ability of polymer surfaces, as being used for, prepare novel wrapping material.

4. improve the cohesiveness of polymer surfaces, as be used for the stacked wrapping material that close of prepared layer, also can be used to improve the viscosifying power between polymer materials and other metal or non-metallic material.

This method has following advantage: (1) can obtain good modified effect, simple to operate, quick, with low cost, environmental pollution is few; (2) applicable functional group is in extensive range, and in operating process, the structure of functional group is not subject to destruction; (3) can on a surface, introduce the group of different performance simultaneously.

Accompanying drawing explanation

Fig. 1. change concentration and the impact of light application time on PS finishing effect of compound 6

Fig. 2. the effect of 2,4,6 pairs of PS finishinges of compound

Fig. 3. the schematic diagram of " sandwich " structural response device

Fig. 4. the impact of the concentration of compound 7 on BOPP membrane surface modification effect

Fig. 5. the impact of ultraviolet light irradiation time on BOPP membrane surface modification effect

Embodiment

Below by specific embodiment, the present invention is described in detail, but is not limited to the content of embodiment.

The common compounds relating in embodiment and the abbreviation of proprietary name:

2-XTC: xanthone-2-formyloxy

Boc: tertbutyloxycarbonyl

DMF:N, N '-dimethyl formamide

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-β-alanine

DMSO: dimethyl sulfoxide (DMSO)

OPD: o-phenylendiamine dihydrochloride

PEG300: polyoxyethylene glycol (molecular-weight average: 300)

Ph ₃cCl: triphenylmethyl chloride

PEG300-CPh ₃: polyoxyethylene glycol (300) trityl ether

PS: polystyrene

BOPP: Biaxially oriented polypropylene film (BOPP)

LDPE: low density polyethylene (LDPE) film

F46: hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymerization film

IIR: isoprene-isobutylene rubber

SBR: butylbenzene film

CHR: chloropharin film

NR/SBR: natural rubber-SBR Blends

PC: polycarbonate

PI: polyimide

PET: ethylene glycol terephthalate

¹h NMR: proton magnetic spectrum

Embodiment 1

Molecule X-S-L's is synthetic

N-[3-(xanthone-2-formamido group) propyl group] synthetic (compound 1) of-carboxylamine tertiary butyl ester

By 2-XTC(13.2g, 55mmol) be dissolved in DMF(120ml) in, 40 ℃ of stirred in water bath, dissolve.Toward disposable CDI(9.25g, the 57mmol of adding in solution), stirring reaction 4 hours 40 minutes.Reaction system is produced, cooling 20 ℃ of stirred in water bath 10 minutes.By monosubstituted tertbutyloxycarbonyl-1,3-propylene diamine (11.09g, 67mmol) be dissolved in TEA/DMF(20ml, 10%v/v) in solution, mix, in the disposable reaction system that joins xanthone-2-formic acid and CDI, then add TEA (13ml), stirring is warmed up to 40 ℃, reacts 11 hours.Reaction system is cooled to 0 ℃, adds deionized water (700ml) to precipitate, suction filtration is dried gained solid under 40 ℃, approximately-0.09MPa vacuum condition.Productive rate 41.47%(be take 2-XTC as benchmark).

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

By compound 1(4.06g, 10.25mmol) dispersed with stirring is in methyl alcohol (120ml), and stir after 20 minutes and add hydrochloric acid/methanol solution (5.4M, 20ml).73 ℃ of stirred in water bath, be heated to reflux, react 2.5 hours.Above-mentioned reaction system is placed in refrigeration chamber cooling, adds anhydrous diethyl ether (300ml) precipitation, suction filtration, washs anhydrous diethyl ether solid for (150ml) obtaining, and then under 40 ℃, approximately-0.09MPa vacuum condition, dries.Productive rate 88.02%(be take compound 1 as benchmark).

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。

N-[3-(xanthone-2-formamido group)-propyl group] synthetic (compound 3) of-formamyl ethyl-carboxylamine tertiary butyl ester

By BOP(1.90g, 4.3mmol) with Boc-β-Ala-OH(0.89g, 4.7mmol) be dissolved into TEA/DMF(29ml, 10%v/v) in, at 20 ℃, stir 10 minutes.Disposable compound 2(1.27g, the 4.3mmol of adding), at 19 ℃ of-20 ℃ of stirring reactions, spend the night.Add deionized water (350ml) to precipitate, suction filtration is dried gained solid under 40 ℃, approximately-0.085MPa vacuum.Productive rate 77.86%(be take compound 2 as benchmark).

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

By compound 3(1.52g, 3.25mmol) be dissolved in methyl alcohol (70ml), the hydrochloric acid/methyl alcohol adding (5ml, 5.4M HCl), is heated to reflux 73 ℃ of stirred in water bath, reacts 2.5 hours.A large amount of solvents are removed in decompression, toward resistates in, add ether (100ml), and suction filtration washs the ether for solid (150ml) that obtains, then under 40 ℃, approximately-0.09MPa vacuum condition, dry.Productive rate 83.29%(be take compound 3 as benchmark).

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.

By 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 reactions 10 minutes; Disposable compound 4(1.83g, the 4.54mmol of adding), then add TEADMF(47ml, 10%v/v), stirring reaction spends the night.Add about deionized water (3000ml) precipitation, suction filtration with deionized water wash gained solid, is then dried under 75 ℃, approximately-0.09MPa vacuum condition.Productive rate 74.08%(be take compound 4 as benchmark).

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

By compound 5(2.10g, 3.90mmol) be dissolved in methyl alcohol (150ml), add HCl/ methanol solution (11ml, 5.4M HCl), 73 ℃ of stirred in water bath, be heated to reflux, react 2.5 hours.Removal of solvent under reduced pressure, obtains product.Productive rate 31.22%(be take compound 5 as benchmark).

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, by compound 2(0.50g, 1.5mmol) at DMF(40ml) in stir and be uniformly dispersed for 10 minutes, then add Succinic anhydried (0.30g, 3.0mmol), then add triethylamine (2.0ml).After stirring reaction 3 hours, in system, add hydrochloric acid (25ml, 1.0M) and deionized water (315ml), in ice-water bath, stir 4 hours precipitations, obtain white solid; Suction filtration, washes solid with deionized water (300ml), under 40 ℃, approximately-0.09MPa vacuum condition, dries.Productive rate 87.54%(be take compound 2 as benchmark).

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)

By BOP(0.44g, 1.0mmol) be dissolved in DMF(20ml) in, add successively CS ₂(0.6ml, 10.0mmol), compound 2(0.35g, 1.0mmol) and TEA(0.42ml, 3.0mmol), 20 ℃ of stirred in water bath reactions 1.5 hours.Under vacuum condition, remove remaining CS ₂.In ice-water bath, above-mentioned reaction soln is added drop-wise in the DMF solution of hydrazine hydrate (0.8ml, 14.0mmol) (5.0ml); Then 20 ℃ of stirred in water bath reactions, spend the night.Add deionized water (100ml) precipitation, suction filtration, washes solid with deionized water (200ml), then under 40 ℃, approximately-0.09MPa vacuum condition, dries.Productive rate 67.43%(be take compound 2 as benchmark).

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)

By 2-XTC(2.41g, 10.0mmol) be distributed to SOCl ₂(50ml) in, stirring reaction 4hr under reflux conditions.The decompression of gained yellow-brownish solution is removed to remaining SOCl ₂, obtain yellowish brown solid.Use at twice sherwood oil (100ml) to wash solid, then sherwood oil is removed in decompression.Under 40 ℃, approximately-0.09MPa vacuum condition, dry.Productive rate: 47.12%(be take 2-XTC as benchmark).

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

By 2-XTC(4.80g, 20.0mmol) be dissolved in DMF(130ml) in, 40 ℃ of stirred in water bath, dissolve.Toward disposable CDI(3.73g, the 23.0mmol of adding in solution), stirring reaction 4 hours.Reaction system is produced, cooling 20 ℃ of stirred in water bath 10 minutes.By 6-aminocaprolc acid methyl esters HCl(4.55g, 25.0mmol) join in reaction system, then add TEA(7.0ml) 40 ℃ of stirred in water bath reactions, spend the night.In ice-water bath, add deionized water (250ml) to precipitate, suction filtration is dried gained solid under 70 ℃ of normal pressures.Productive rate: 60.48%(be take 2-XTC as benchmark).

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, by compound 10(3.95g, 10.7mmol) at THF(120ml) in dispersed with stirring even.By LiOH(1.35g, 32.2mmol) be made into the solution of 0.5M, in the disposable system joining above, stir 1.5 hours.The THF in system is removed in decompression, and the hydrochloric acid (10.0ml, 10.0M) then adding stirs acid precipitation 1 hour.Suction filtration, washes solid with deionized water (350ml), under 40 ℃, approximately-0.09MPa vacuum condition, dries.Productive rate: 96.78%(be take compound 10 as benchmark).

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。

6-[xanthone-2-formamido group] synthetic (compound 12) of-caproyl hydrazine

By compound 10(0.37g, 1.0mmol) be distributed to (20ml) in methyl alcohol, the disposable hydrazine hydrate (1.2ml, 21.0mmol) that adds, under reflux conditions reacts 6 hours.Be cooled to room temperature, removal of solvent under reduced pressure; Resistates is re-dispersed in frozen water (20ml), and suction filtration, washes solid with water, under 40 ℃, approximately-0.09MPa vacuum condition, dries.Productive rate: 34.33%(be take compound 10 as benchmark).

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。

N-[3-(xanthone-2-formamido group)-propyl group] N-[(4-O-(α-D-glucopyranosyl)-β-D-glucopyranosyl)] synthetic (compound 13) of N-ethanoyl ammonia

By compound 2(0.50g, 1.5mmol) and maltose (1.54g, 4.5mmol) be dissolved in anhydrous methanol (80ml).Add DIEA(0.35ml, 2.0mmol), in 60 ℃ of water-baths, nitrogen atmosphere, stirring reaction spends the night.Then system is placed on and in ice bath, stirs coolingly, add diacetyl oxide (3.5ml).At room temperature stir standing over night.Removal of solvent under reduced pressure, resistates is water-soluble, filters and lyophilize; Use column chromatography chromatogram to carry out separation to gained solid, silica gel (100-200 order) phase that fixes, uses water as eluent and isolates remaining maltose, by acetonitrile/water (v/v=50/50), as eluent, isolates compound 13, and lyophilize obtains target product.Productive rate: 53.26%(is 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。

Xanthone-2-formamido group-propyl group amino-6-ketoestradiol-6-(O-carboxymethyl) synthetic (compound 14) of-oxime

By compound 2(0.50g, 1.5mmol), BOP(0.95g, 1.5mmol) be dissolved in DMF(50ml) in, add 6-ketoestradiol-6-(O-carboxymethyl)-oxime (0.54g, 1.5mmol), DIEA (0.53mL, 3.0mmol).Under 20 ℃ of water-baths, stirring reaction is 4 hours, then adds deionized water (10ml), and suction filtration, uses Na successively ₂cO ₃the aqueous solution (3 * 10ml, 10%wt), 10%KHSO ₄the aqueous solution (3 * 10ml, 10%wt) and deionized water (3 * 10ml) are washed solid, under 40 ℃, approximately-0.09MPa vacuum condition, dry.Productive rate 85.26%(be take compound 2 as benchmark).

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)

By PEG300(3.0g, 10.0mmol) be dissolved in pyridine (20ml), approximately 1/3rd pyridine (azeotropic drying) is removed in distillation.By Ph ₃cCl(0.28g, 1.0mmol) be dissolved in pyridine (6ml), be at room temperature added drop-wise in the solution of PEG300, time for adding is no less than 3 hours.At room temperature continue stirring reaction 18hr.Underpressure distillation, except desolventizing; In system, add toluene (2 * 25ml) distillation subsequently.Residual liquid is dissolved in dichloromethane (100ml) alkane, adds successively 0.1M citric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt to wash.Get organic phase and carry out concentrating under reduced pressure, concentrated solution is carried out to post separation: silica gel (100-200 order) is stationary phase, and ethyl acetate/petroleum ether (v:v=50:50) ~ ethyl acetate (100%) is as moving phase.Products therefrom is 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。

By PEG300-CPh ₃(0.4g, 0.74mmol) and compound 9(0.19g, 0.74mmol) be dissolved in pyridine (15ml), stirring reaction 16 hours, pyridine is removed in distillation, then adds toluene (2 * 25ml) distillation.Residual liquid is dissolved in methylene dichloride (50ml), adds successively 0.1M citric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt to wash.Get organic phase and carry out concentrating under reduced pressure, concentrated solution is carried out to post separation: silica gel (100-200 order) is stationary phase, and ethyl acetate/petroleum ether (v:v=90:10) is as moving phase.The intermediate product obtaining is yellow oily liquid, productive rate 72.46%(0.41g).Intermediate product is dissolved in methylene chloride/methanol (10ml v:v=80:20) mixed solvent, adds ZnBr ₂(0.5g, 2.18mmol) stirring reaction 20 minutes, evaporation is except desolventizing.Concentrated solution is carried out to post separation: silica gel (100-200 order) is stationary phase, and ethyl acetate/petroleum ether (v:v=80:20) is as moving phase.The intermediate product obtaining is brown color 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。

Embodiment 2

Compound 2, compound 4, compound 6, compound 7 are dissolved in pure water (specific conductivity=0.8 μ s/cm), are mixed with the solution of 0.05mM.2-XTC, BP are dissolved in dehydrated alcohol, are made into respectively the solution that concentration is 0.064mM and 0.053mM.The UV spectrum of measurement in 190-400nm wavelength region.Shown in table 1, be the characteristic absorption wavelength (λ of six kinds of compounds _max) and molar absorptivity (ε).

The uv-absorbing of six kinds of compounds of table 1

Embodiment 3

Compound 6 is dissolved in distilled water, is mixed with the solution that starting point concentration is 0.58mM, take above-mentioned concentration as benchmark, carry out the dilution of 5 times, be made into a series of modified solution.Before use, the solution of each concentration is logical nitrogen deoxygenation in 10 minutes all.Get the not polystyrene of surface modification (PS) 96 hole enzyme plates, use respectively dehydrated alcohol and washed with de-ionized water hole surface three times, at 50 ℃, dry 45 minutes dry for standby.Liquid volume added by the modified solution of above-mentioned preparation with 100 μ L/ holes successively joins in each hole of enzyme plate, and enzyme plate is placed under 1000W high voltage mercury lamp and carries out illumination, and light intensity is 3.55mW/cm ²(λ=254nm), light application time is respectively 5 minutes, 7 minutes and 10 minutes.After illumination finishes, incline and fall modified solution, use deionized water rinsing three times, then at 50 ℃, dry 45 minutes, after oven dry, keep in Dark Place standby.Toward 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 then placed in 21-23 ℃ of baking oven and cultivate and spend the night; With Covabuffer, wash three times, when last, Covabuffer retains 10 minutes in hole; (PBS of pH=7.2 makees solvent to add the mixing solutions of affinity plain (HRP-avidin) of affinity element (avidin) and horseradish peroxidase-labeled, containing avidin 4 μ g/mL, containing HRP-avidin 0.13 μ g/mL) 100 μ L/ holes, in 21-23 ℃ of baking oven, cultivate 2 hours; With Covabuffer, wash secondary, when last, Covabuffer retains 10 minutes in hole; Topple over and fall washing lotion, add citrate buffer (pH=5.0, containing 0.015%(v/v) H ₂o ₂oPD with 0.6mg/mL) color 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 microplate reader of Thermo company to measure modification hole in the absorbancy at 492nm place.Result as shown in Figure 1.Discovery is when lower concentration, and the effect that light application time effects on surface is modified does not play conclusive impact; When concentration is increased to 4.64 * 10 ^-3after 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.

Embodiment 4

Compound 2,4,6 is dissolved in to distilled water, is mixed with the modified solution that concentration is 0.1mM.The pre-treating process of the deoxygenation operation of modified solution and not the PS96 orifice plate of surface modification is identical with embodiment 3.Above-mentioned three kinds of modified solutions are joined respectively in each hole of enzyme plate (100 μ L/ hole), illumination and post processing mode are identical with embodiment 3.Compound concentration is that the PBS of the biotin-OSu ester(pH=7.2 of 126 μ g/mL makees solvent) solution, carries out doubling dilution and obtains a series of solution.The solution of each concentration is joined respectively in the hole of compound 2,4,6 modifications to the method for follow-up cleaning, avidin absorption, color reaction and absorbance measurement and embodiment 3.Result as shown in Figure 2.The modified effect of finding 4 pairs of PS enzyme plates of compound is best, and the modified effect of compound 6 and compound 2 is relative poor.

Embodiment 5

Compound 4 is mixed with to the modified solution of 0.1mM, compound method and deoxygenation working method are identical with embodiment 3.Get 5 PS96 hole enzyme plates, pre-treating process is identical with embodiment 3.The modified solution that adds respectively compound 4, carries out finishing by the method for embodiment 3.Then toward adding concentration in modification hole, be biotin-OSu este play (PBS of pH=7.2 makees solvent) solution of 126 μ g/mL, the method for follow-up cleaning, avidin absorption, color reaction and absorbance measurement is identical with embodiment 3.Result is as shown in table 2.Discovery is carried out finishing at different PS96 hole enzyme plates and is had good repeatability.

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

Embodiment 6

Compound 6 is dissolved in pure water (specific conductivity=0.8 μ s/cm), and being mixed with concentration is the solution modification solution of 1.0mmol/L.

Be illustrated in figure 3 the schematic diagram that uses " sandwich " structural response device in the present embodiment, details are as follows for each characteristics of components function: parts 1 are upper quartz plate, UV-light sees through its downward irradiation and causes the photochemical reaction between parts 2, parts 3 and parts 4, and 1 pair of parts 2 of parts, parts 3 and parts 4 also provide certain pressure, make the combination between three tightr; Parts 2 are upper base material, must have enough UV-light penetrance, and the UV-light of the needed characteristic wavelength of UV-light surface modification is not had to sorption, itself can be also the polymer materialss that is modified; Parts 3 are modified solution, under the induction of UV-light, parts 2 and 4 are carried out to modification; Parts 4 are lower base material, are the polymer materialss that is modified; Parts 5 are lower quartz plate, and above-mentioned four parts are played to carrying effect.According to actual needs, can give up any one in parts 1,2 or 5, select in the present embodiment complete " sandwich " structural response device being formed by above-mentioned five parts.

Get BOPP film and PS plate is upper and lower base material, use above-mentioned modified solution to be made into the reactor 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 1000W high voltage mercury lamp that the reactor of " sandwich " structure is placed into power ²) carry out illumination, light application time is respectively 0.5,2.0,5.0 and 10.0 minute.PS plate after processing and BOPP film first rinse with large water gaging, then with dehydrated alcohol, rinse, and remove the moisture that substrate surface adheres to, and are placed in air standing 15 minutes and make above dehydrated alcohol volatilize completely.

The PS plate of modification and BOPP film are carried out to air/water contact angle (CA) mensuration, and these data are for the wetting ability on characterize polymers surface, and the less wetting ability of numerical value is better.Concrete grammar is: use at normal temperatures the OCA20 type contact angle measurement of German Dataphysics instruments company, get the reading that 1 μ l deionized water records air/water contact angle after vertically dropping on surface to be measured at once at every turn.Each sample is at least surveyed 6 points (lower same).The results are shown in Table 3.

The surface water contact angle of table 3 compound 6 modification PS plates and BOPP film changes

Embodiment 7

By the method for embodiment 3, compound 6 is mixed with to the modified solution of 0.58mM and carries out deoxygenation processing.With method construct " sandwich " the structural response device of being mentioned in embodiment 6, take BOPP film as upper base material, LDPE film, F46 film, IIR sheet material, SBR sheet material, CHR sheet material, NR/SBR sheet material are as lower base material.In normal temperature environment, it is that (light intensity at λ=254nm place is 3.55mw/cm to 1000w high voltage mercury lamp that the reactor of " sandwich " structure is placed into power ²) lower illumination 10.0 minutes.The base materials such as the LDPE film after modification, F46 film, IIR sheet material, SBR sheet material, CHR sheet material, NR/SBR sheet material first rinse with large water gaging, then with dehydrated alcohol, rinse, remove the moisture that substrate surface adheres to, be placed in 21-23 ℃ of baking oven and dry and within 10 minutes, make above dehydrated alcohol volatilize completely.

Measuring method to air/water contact angle 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 is identical with embodiment 6.Result is as shown in table 4.By the contrast of each base material water contact angle before and after modification, find that all there is good modified effect 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 modification

114.2°

104.0°

108.5°

109.7°

115.6°

116.8°

After modification

69.6°

70.7°

65.8°

84.7°

94.3°

82.6°

Embodiment 8

Compound 4 is mixed with to the modified solution of 2.0mM, solvent is selected respectively deionized water, sodium chloride aqueous solution (0.02%wt), water/ethanol (v:v=50:50) mixture etc.With method construct " sandwich " the structural response device of being mentioned in embodiment 6, take BOPP film as upper base material, PS plate is lower base material.In normal temperature environment, it is that (light intensity at λ=254nm place is 7.0mw/cm to 1000w high voltage mercury lamp that the reactor of " sandwich " structure is placed into power ²) lower illumination 10.0 minutes.The base materials such as the BOPP film after modification, PS plate first rinse with large water gaging, then with dehydrated alcohol, rinse, and remove the moisture that substrate surface adheres to, and at room temperature dry, and dehydrated alcohol is volatilized completely.

Measuring method to air/water contact angle before and after the base material modifications such as BOPP film, PS plate is identical with embodiment 6.Result is as shown in table 5.By the contrast of each base material water contact angle before and after modification, while finding to adopt different solvents, compound 4 all can play good modified effect to different surface of polymer material.

The surface water contact angle of table 5 compound 4 modification PS plates and BOPP film changes

Embodiment 9

Compound 4 is mixed with to the modified solution of 0.58mM, uses ethanol to make solvent.With method construct " sandwich " the structural response device of being mentioned in embodiment 6, take BOPP film as upper base material, take respectively PC plate, PI film, PET film is lower base material.In normal temperature environment, it is that (light intensity at λ=254nm place is 7.0mw/cm to 1000w high voltage mercury lamp that the reactor of " sandwich " structure is placed into power ²) lower illumination 10.0 minutes.PC plate after modification, PI film, PET film first rinse with large water gaging, then with dehydrated alcohol, rinse, and remove the moisture that substrate surface adheres to, and at room temperature dry, and dehydrated alcohol is volatilized completely.

Measuring method to air/water contact angle before and after the base material modifications such as PC plate, PI film, PET film is identical with embodiment 6.Result is as shown in table 6.By the contrast of each base material water contact angle before and after modification, compound 4 all can play certain modified effect to different surface of polymer material.

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 modification	88.1°	69.5°	76.3°
After modification	72.6°	59.4°	54.8°

Embodiment 10

Compound 7 is dissolved in to the LiOH aqueous solution of 0.1M, is mixed with the modified solution of 5.0mM, carry out twice dilution and obtain a series of modified solution, the oxygen that logical nitrogen is removed in each solution for 10 minutes.Getting BOPP film is upper and lower base material, according to the method construct of mentioning in embodiment 6 " sandwich " structural response device.The method of UV-light photoirradiation modification is identical with embodiment 7, and light application time is 10 minutes.With BOPP film after deionized water rinsing modification, being then dipped into concentration is in the 100mL Viola crystallina aqueous solution of 0.15mg/mL, in 22-23 ℃ of baking oven, cultivates 30 minutes.Take out, with deionized water rinsing BOPP film surface, then in 22-23 ℃ of baking oven, dry.

The modified solution that the concentration of take is 5.0mM is basis, changes light application time and is respectively 0.5,2.0,5.0,7.0 and 10.0 minute, and BOPP film is carried out to surface treatment.The method of ultraviolet light irradiation modification, aftertreatment and Viola crystallina absorption is with identical above.

Use GBC Cintra 20 ultraviolet-visible spectrophotometric spectras (Australia) to measure the adsorption effect of modification BOPP film to Viola crystallina, result is shown in respectively Fig. 4 and Fig. 5.As shown in Figure 4, along with the increase of compound 7 concentration, BOPP membrane surface modification effect strengthens; As shown in Figure 5, the prolonging light time is conducive to the surface modification effect of 7 pairs of BOPP films of compound.

Claims (20)

1. a method of modifying for surface of polymer material, the method comprises by photosensitive group X and issues third contact of a total solar or lunar eclipse chemical reaction and the surface of functional group L being introduced to polymer materials P at ultraviolet light irradiation, wherein said photosensitive group X contains at least one xanthone unit,

Wherein said be selected from-COOH of functional group L ,-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 ' represents alkyl, M ⁺represent unit price positive ion, group-COX ,-X and-R ' X _nin X represent halogen atom, n≤(2 * R ' in carbonatoms+1); And/or described functional group L is derived from phosphorylcholine, heterocycle molecule, metal complex, theophylline, salt, sugar, microbiotic, VITAMIN, toxin, weedicide, sterilant, steroid, polypeptide, nucleosides, polypeptide-nucleic acid, haptens,

Wherein on the surface of polymer materials P, introduce molecule X-S-L, wherein X is the photosensitive group that contains at least one xanthone unit, and L is functional group, and S is connection chain,

Wherein said method comprises that by ultraviolet light irradiation, making photosensitive group X and polymer materials P surface that photochemical reaction occur forms P-X, with synthetic molecules S-L, then by 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, forms P-X-S-L.

2. method according to claim 1, wherein said M ⁺represent NH ₄ ⁺.

3. method according to claim 1 and 2, 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.

4. method according to claim 3, wherein said photosensitive group X is derived from and replaces or unsubstituted single xanthone.

5. method according to claim 4, wherein said photosensitive group X is derived from the replacement list xanthone of formula I,

Wherein R represents to be positioned at the substituting group in respective rings independently of one another, and a and b are respectively independently for being selected from the integer of 0-3, and a+b >=1.

6. method according to claim 5, wherein said substituent R is selected from temperature-sensitive functional group, replacement or does not replace and/or by the chain alkylene at functional group interval, with respect to the replacement of single xanthone unit or unsubstituted free ring structure and the replacement or the unsubstituted condensed ring structure that form together with annular atoms with on single xanthone unit, 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.

7. method according to claim 6, wherein said chain alkylene is C _1-18chain alkylene.

8. method according to claim 7, wherein said chain alkylene is C _1-8alkyl or C _2-8unsaturated alkyl.

9. method according to claim 7, wherein said chain alkylene is C _1-5alkyl or C _2-5unsaturated alkyl.

10. method according to claim 7, wherein said chain alkylene 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 ,Zhi functional group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone, epoxy, ether, thioether, carbonyl, sulfonyl, thionyl, nitro, cyano group, phosphinylidyne functional group, ,Xian functional group of ,Tang functional group of furans functional group.

11. methods according to claim 6, the ring in wherein said ring structure is the saturated cyclic hydrocarbons with 5-6 annular atoms, unsaturated cyclic hydrocarbon, saturated heterocyclic hydrocarbon, unsaturated heterocycle hydrocarbon.

12. method according to claim 11, the heteroatoms that the annular atoms in wherein said ring structure contains one or more O of being selected from, N, S.

13. methods according to claim 11, ring in wherein said ring structure is selected from pentamethylene, hexanaphthene, cyclopentanone, pimelinketone, benzene, cyclopentenes, tetrahydrobenzene, cyclohexadiene, tetrahydrofuran, amylene oxide, piperidines, dioxolane, dioxane, thiacyclopentane, thia hexanaphthene, hexanolactam, caprolactone, oxa-cyclopentanone, oxa-pimelinketone, oxa-tetrahydrobenzene, thia tetrahydrobenzene, furan nucleus, pyrrole ring, thiphene ring, pyridine, pyrimidine, imidazoles, benzo ring hexanone, benzo oxa-pimelinketone, amylene oxide benzo pimelinketone.

14. methods according to claim 13, wherein said ring structure is selected from following one or more functional groups and is replaced: C _1-18chain alkylene, halogen atom, carboxyl, sulfonic group, ester group, nitro, carboxylic acid halides, amido, hydroxyl, acid amides, aldehyde, sulfydryl, ketone, sulfonyl, thionyl.

15. methods according to claim 1 and 2, wherein said connection chain S is selected from and replaces or do not replace and/or by the C at functional group interval _1-20the combination of alkyl, polyoxyethylene glycol, oligomeric/multi-polyamide, oligose, oligomeric/polyphosphate or phosphoric acid salt, oligomeric/poly sulphonamide/sulphonate and said units.

16. methods according to claim 15, 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 ,Zhi functional group, carboxylic acid halides, hydrazides, Urea,amino-, thiosemicarbazide, aldehyde, ketone, epoxy, ether, thioether, carbonyl, sulfonyl, thionyl, nitro, cyano group, phosphinylidyne functional group, ,Xian functional group of ,Tang functional group of furans functional group.

17. methods according to claim 16, the length of wherein said connection chain S is no more than 40nm.

18. methods according to claim 1 and 2, wherein said polymer materials is selected from polyolefine, rubber, urethane, polymeric amide, polycarbonate, polyimide, polyester, fluoro-resin, polyethers, polyvinyl alcohol, polyvinyl acetate (PVA), polyacrylate(s), biopolymer or their blend, matrix material.

19. methods according to claim 18, wherein said polymer materials is selected from: polyethylene, polypropylene, polystyrene, polyvinyl chloride, styrene-butadiene rubber(SBR), paracril, SBS, ethylene-propylene rubber(EPR), chloroprene rubber, silicon rubber, chlorohydrin rubber, polycaprolactam, polyhexamethylene carbonic ether, polyethylene terephthalate, polycaprolactone, tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, polyphenylene oxide, polyoxyethylene glycol; Polyvinyl alcohol, polymethylmethacrylate, chitin, chitosan, polyamino acid, poly(lactic acid) or their blend, matrix material.

20. have the goods of the surface of polymer material forming by the method modification described in claim 1-19 any one.

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